CN113956505A - Polylactic acid emulsion, preparation method and application thereof - Google Patents
Polylactic acid emulsion, preparation method and application thereof Download PDFInfo
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- CN113956505A CN113956505A CN202111293991.3A CN202111293991A CN113956505A CN 113956505 A CN113956505 A CN 113956505A CN 202111293991 A CN202111293991 A CN 202111293991A CN 113956505 A CN113956505 A CN 113956505A
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- polylactic acid
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- acid emulsion
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- 239000000839 emulsion Substances 0.000 title claims abstract description 107
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 91
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 35
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000004888 barrier function Effects 0.000 claims abstract description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 16
- 239000004417 polycarbonate Substances 0.000 claims abstract description 16
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 13
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 13
- -1 polytrimethylene carbonate Polymers 0.000 claims abstract description 13
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 13
- 229920001661 Chitosan Polymers 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 96
- 238000003756 stirring Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 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 claims description 5
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- BNKAOFCGRFIIHY-UHFFFAOYSA-N 1,3-dioxacyclotridecan-2-one Chemical compound O=C1OCCCCCCCCCCO1 BNKAOFCGRFIIHY-UHFFFAOYSA-N 0.000 claims description 3
- LGCNDZIFJKHQHB-UHFFFAOYSA-N 1,3-dioxacycloundecan-2-one Chemical compound O=C1OCCCCCCCCO1 LGCNDZIFJKHQHB-UHFFFAOYSA-N 0.000 claims description 3
- VKSWWACDZPRJAP-UHFFFAOYSA-N 1,3-dioxepan-2-one Chemical compound O=C1OCCCCO1 VKSWWACDZPRJAP-UHFFFAOYSA-N 0.000 claims description 3
- PPMCFKAXXHZLMX-UHFFFAOYSA-N 1,3-dioxocan-2-one Chemical compound O=C1OCCCCCO1 PPMCFKAXXHZLMX-UHFFFAOYSA-N 0.000 claims description 3
- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000012661 block copolymerization Methods 0.000 abstract description 2
- 150000002009 diols Chemical class 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 239000012785 packaging film Substances 0.000 abstract description 2
- 229920006280 packaging film Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000004945 emulsification Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 2
- 239000008108 microcrystalline cellulose Substances 0.000 description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006381 polylactic acid film Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- 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
- C08K3/34—Silicon-containing compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention relates to the technical field of polymer packaging films, in particular to polylactic acid emulsion, and a preparation method and application thereof. The polylactic acid emulsion comprises the following preparation raw materials in parts by weight: 40-60 parts of polylactic acid; 20-40 parts of carboxyl-terminated polytrimethylene carbonate; 120-180 parts of chloroform; 40-60 parts of N, N-dimethylformamide; 50-80 parts of aliphatic polycarbonate polyol; 120-200 parts of ethyl acetate; 10-20 parts of an emulsifier; 2-10 parts of water-soluble chitosan; 2-6 parts of talcum powder; 1-5 parts of a chain extender; 500-1000 parts of water. The invention carries out block copolymerization modification on polylactic acid and carboxyl-terminated polytrimethylene carbonate in a solvent, then carries out esterification reaction with aliphatic polycarbonate diol, dissolves in the solvent for emulsification, and then reduces the pressure to obtain polylactic acid emulsion. The polylactic acid emulsion can obtain better barrier property and can be degraded when being used as a barrier coating.
Description
Technical Field
The invention relates to the technical field of polymer packaging films, in particular to polylactic acid emulsion, and a preparation method and application thereof.
Background
PLA polylactic acid resin is a well-known environment-friendly plastic, is not only a 100% plant-based source, but also a 100% fully-degradable plastic, integrates safety, non-toxicity and environment friendliness, and is the first choice of an environment-friendly plastic product. The modified BOPLA film after biaxial stretching and heat setting has physical and mechanical properties meeting the requirements of common product packaging.
Compared to conventional BOPP films, BOPLA films have a relatively high water vapour permeability, which is a considerable disadvantage for their use as a packaging material, resulting in limited use and failure to apply to most product packaging.
Aiming at the problem of barrier property, the barrier property of BOPLA is improved by multilayer coextrusion, coating high barrier layer, modified grafting and other methods in the conventional system. However, the above-described improved scheme still has the following problems:
1. the non-degradable material is used while high barrier is provided, so that the product cannot be completely degraded, the purpose of complete degradation cannot be achieved, and the significance of using the degradable material is reduced;
2. the modified material is used for production, the production cost is high, and the whole membrane needs to be modified;
3. the multilayer co-extrusion is carried out, only the surface layer is modified, and the performance difference among the multiple layers can cause the production process of the bidirectional BOPLA to be complex and difficult to solve.
Chinese patent CN111253603B provides a microcrystalline cellulose reinforced biaxially oriented polylactic acid film and a preparation method thereof, wherein microcrystalline cellulose is used to modify polylactic acid during the production process, resulting in that the maximum extrusion temperature during the processing process can reach 230 ℃, but at a temperature higher than 200 ℃, the polylactic acid component will begin to decompose to different degrees, resulting in the performance reduction of the film.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polylactic acid emulsion, a preparation method and an application thereof, and the polylactic acid emulsion provided by the present invention can obtain a better barrier property and can be degraded simultaneously when used as a barrier coating.
The invention provides a polylactic acid emulsion which is prepared from the following raw materials in parts by weight:
preferably, the polylactic acid is levorotatory polylactic acid;
the polymerization degree of the polylactic acid is 1000-3000.
Preferably, the aliphatic polycarbonate polyol includes at least one of 1, 4-butylene carbonate, 1, 5-pentylene carbonate, 1, 6-hexylene carbonate, 1, 8-octylene carbonate, and 1, 10-decylene carbonate.
Preferably, the emulsifier comprises tween 80, Brij30 or tween 61;
the chain extender comprises diphenylmethane diisocyanate and/or dicyclohexylmethane diisocyanate.
The invention also provides a preparation method of the polylactic acid emulsion, which comprises the following steps:
A) mixing the solution a and the solution b to obtain a mixed solution; the solution a comprises polylactic acid and chloroform; the solution b comprises carboxyl terminated polytrimethylene carbonate and N, N-dimethylformamide;
B) reacting the mixed solution with a chain extender at 80-100 ℃ under the condition of protective gas to obtain a first product solution;
C) reacting the first product solution with the solution c at 70-90 ℃ under the condition of protective gas to obtain a second product solution; the solution c comprises aliphatic polycarbonate polyol and ethyl acetate;
D) mixing deionized water, an emulsifier and water-soluble chitosan to obtain a solution d;
dropwise adding the second product solution into the stirred solution d to obtain emulsion e;
E) stirring and mixing the emulsion e and the talcum powder to obtain emulsion f;
F) reducing the stirring speed of the emulsion f, reducing the pressure to be below 10kPa, and removing the solvent in the emulsion f to reduce the content of VOC to be below 30 g/L;
G) and (3) cooling to normal temperature, and adjusting the pH value to 8-11 to obtain the polylactic acid emulsion.
Preferably, in the step B), the reaction time is 4-10 h;
the reaction time is 5-10 h.
Preferably, in the step D), the dripping time is 2-3 h;
in the dropping process, the temperature of the solution d is controlled to be less than or equal to 40 ℃;
the stirring speed of the solution d is 100-300 rpm.
Preferably, in the step E), the rotation speed of stirring and mixing is 80-160 rpm;
the stirring and mixing time is 3-6 h;
and reducing the stirring speed of the emulsion f to 60-100 rpm.
The invention also provides an application of the polylactic acid emulsion as a barrier coating, or an application of the polylactic acid emulsion prepared by the preparation method as the barrier coating.
The present invention also provides a film comprising a barrier coating, comprising:
a film;
and a barrier coating layer compounded on the film;
the barrier coating is prepared from the polylactic acid emulsion or prepared from the polylactic acid emulsion prepared by the preparation method.
The invention provides a polylactic acid emulsion which is prepared from the following raw materials in parts by weight: 40-60 parts of polylactic acid; 20-40 parts of carboxyl-terminated polytrimethylene carbonate; 120-180 parts of chloroform; 40-60 parts of N, N-dimethylformamide; 50-80 parts of aliphatic polycarbonate polyol; 120-200 parts of ethyl acetate; 10-20 parts of an emulsifier; 2-10 parts of water-soluble chitosan; 2-6 parts of talcum powder; 1-5 parts of a chain extender; 500-1000 parts of water. The invention carries out block copolymerization modification on polylactic acid and carboxyl-terminated polytrimethylene carbonate in a solvent, then carries out esterification reaction with aliphatic polycarbonate diol to form esterified cross-linking, then dissolves the esterified cross-linking in the solvent, emulsifies the solution in water, and reduces the pressure to form emulsion, thereby obtaining the polylactic acid emulsion. The polylactic acid emulsion provided by the invention can be used as a barrier coating of a film, and the polylactic acid emulsion can be prepared into the film containing the barrier coating, so that the film has excellent oxygen resistance, is biodegradable and is environment-friendly.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a polylactic acid emulsion which is prepared from the following raw materials in parts by weight:
the raw materials for preparing the polylactic acid emulsion comprise polylactic acid. In certain embodiments of the present invention, the polylactic acid is 40 to 60 parts by weight.
In certain embodiments of the invention, the polylactic acid is levorotatory polylactic acid. In the present invention, the polymerization degree of the polylactic acid is preferably 1000 to 3000. In some embodiments, the polylactic acid has a degree of polymerization of 1500 to 1800, 2000 to 2300, or 2500 to 3000.
The preparation raw material of the polylactic acid emulsion also comprises carboxyl-terminated polytrimethylene carbonate. In certain embodiments of the present invention, the carboxyl-terminated polytrimethylene carbonate is present in an amount of 20 to 40 parts by weight. The carboxyl-terminated polytrimethylene carbonate of the present invention is not particularly limited in its source, and can be generally commercially available.
The polylactic acid emulsion provided by the invention also comprises chloroform as a raw material for preparation. In certain embodiments of the present invention, the chloroform is present in an amount of 120 to 180 parts by weight.
The raw materials for preparing the polylactic acid emulsion also comprise N, N-dimethylformamide. In certain embodiments of the present invention, the N, N-dimethylformamide is present in an amount of 40 to 60 parts by weight.
The raw materials for preparing the polylactic acid emulsion also comprise aliphatic polycarbonate polyol. In certain embodiments of the present invention, the aliphatic polycarbonate polyol is 50 to 80 parts by weight.
In certain embodiments of the present invention, the aliphatic polycarbonate polyol comprises at least one of 1, 4-butylene carbonate, 1, 5-pentylene carbonate, 1, 6-hexylene carbonate, 1, 8-octylene carbonate, and 1, 10-decylene carbonate.
The raw materials for preparing the polylactic acid emulsion also comprise ethyl acetate. In certain embodiments of the present invention, the ethyl acetate is 120 to 200 parts by weight.
The raw materials for preparing the polylactic acid emulsion also comprise an emulsifier. In certain embodiments of the present invention, the emulsifier is 10 to 20 parts by weight.
In certain embodiments of the invention, the emulsifier comprises tween 80, Brij30, or tween 61.
The raw materials for preparing the polylactic acid emulsion also comprise water-soluble chitosan. In some embodiments of the present invention, the water-soluble chitosan is 2 to 10 parts by weight. The source of the water-soluble chitosan is not particularly limited in the present invention, and may be generally commercially available.
The polylactic acid emulsion provided by the invention also comprises talcum powder as a raw material for preparation. In some embodiments of the present invention, the talc powder is 2 to 6 parts by weight.
The preparation raw material of the polylactic acid emulsion also comprises a chain extender. In certain embodiments of the present invention, the weight part of the chain extender is 1 to 5 parts.
In certain embodiments of the present invention, the chain extender comprises diphenylmethane diisocyanate and/or dicyclohexylmethane diisocyanate.
The preparation raw material of the polylactic acid emulsion also comprises water. In certain embodiments of the present invention, the water is 500 to 1000 parts by weight. In certain embodiments, the water is deionized water.
The invention also provides a preparation method of the polylactic acid emulsion, which comprises the following steps:
A) mixing the solution a and the solution b to obtain a mixed solution; the solution a comprises polylactic acid and chloroform; the solution b comprises carboxyl terminated polytrimethylene carbonate and N, N-dimethylformamide;
B) reacting the mixed solution with a chain extender at 80-100 ℃ under the condition of protective gas to obtain a first product solution;
C) reacting the first product solution with the solution c at 70-90 ℃ under the condition of protective gas to obtain a second product solution; the solution c comprises aliphatic polycarbonate polyol and ethyl acetate;
D) mixing deionized water, an emulsifier and water-soluble chitosan to obtain a solution d;
dropwise adding the second product solution into the stirred solution d to obtain emulsion e;
E) stirring and mixing the emulsion e and the talcum powder to obtain emulsion f;
F) reducing the stirring speed of the emulsion f, reducing the pressure to be below 10kPa, and removing the solvent in the emulsion f to reduce the content of VOC to be below 30 g/L;
G) and (3) cooling to normal temperature, and adjusting the pH value to 8-11 to obtain the polylactic acid emulsion.
In the preparation method of the polylactic acid emulsion provided by the invention, the adopted raw material components and the proportion are the same as above, and are not described again.
In step A):
the method for preparing the solution a and the solution b is not particularly limited, and the method for preparing the solution known to those skilled in the art can be used.
In step B):
in certain embodiments of the invention, step B) comprises:
and placing the mixed solution in a reaction device, vacuumizing until the vacuum degree is not more than 1kPa, filling protective gas, adding a chain extender, and reacting at 80-100 ℃ to obtain a first product solution.
In certain embodiments of the invention, a vacuum is applied to a vacuum of 5kPa or 6 kPa.
In certain embodiments of the invention, the shielding gas is nitrogen.
In some embodiments of the present invention, the reaction time is 4 to 10 hours.
In step C):
in certain embodiments of the invention, the shielding gas is nitrogen.
The method for preparing the solution c is not particularly limited in the present invention, and a method for preparing a solution well known to those skilled in the art may be used.
In certain embodiments of the invention, step C) comprises:
mixing the first product solution with a solution c, and reacting the first product solution with the solution c at 70-90 ℃ under the condition of protective gas to obtain a second product solution; the solution c comprises an aliphatic polycarbonate polyol and ethyl acetate.
In some embodiments of the present invention, after the mixing, further comprising: stirring for 2-5 h.
In some embodiments of the present invention, the reaction time is 5 to 10 hours.
In step D):
in some embodiments of the present invention, the stirring speed of the solution d is 100 to 300 rpm.
In some embodiments of the invention, the dropping time is 2-3 h.
In certain embodiments of the present invention, the temperature of the solution d is controlled to be less than or equal to 40 ℃ during the dropwise addition. In some embodiments, the temperature of the solution d is controlled to be 32-38 ℃ or 33 ℃ during the dropping process.
In step E):
in some embodiments of the present invention, the rotation speed of the stirring and mixing is 80 to 160 rpm.
In some embodiments of the invention, the stirring and mixing time is 3-6 h.
In step F):
in some embodiments of the present invention, the stirring speed of the emulsion f is reduced to 60 to 100 rpm.
In certain embodiments of the invention, the reduced pressure is at ambient temperature.
In certain embodiments of the present invention, the step of removing the solvent from the emulsion f comprises:
and (3) vacuumizing to boil and evaporate the solvent in the emulsion, and simultaneously introducing a small amount of air to sweep, so as to take away the evaporated solvent and remove the solvent in the emulsion f.
After the solvent in the emulsion f is removed, the VOC content of the emulsion f is reduced to be below 30 g/L. In certain embodiments, the VOC content of the emulsion f is reduced to 30g/L, 25g/L, or 20 g/L.
Step G):
in certain embodiments of the invention, the agent used to adjust the pH is ammonia.
In certain embodiments of the invention, the pH is adjusted to 10, 9 or 11.
The invention also provides an application of the polylactic acid emulsion as a barrier coating, or an application of the polylactic acid emulsion prepared by the preparation method as the barrier coating. In particular, the polylactic acid emulsion can be used as a barrier coating of a film.
The present invention also provides a film comprising a barrier coating, comprising:
a film;
and a barrier coating layer compounded on the film;
the barrier coating is prepared from the polylactic acid emulsion or prepared from the polylactic acid emulsion prepared by the preparation method.
In certain embodiments of the present invention, the film may be a BOPLA film, but is not limited to only BOPLA films.
In certain embodiments of the present invention, the barrier coating has a thickness of 0.5 to 5 μm. In certain embodiments, the barrier coating has a thickness of 1.5 μm.
In certain embodiments of the invention, a film comprising a barrier coating is prepared according to the following method:
a) under the tension of 40-100N, unwinding and flatly unfolding a BOPLA film, carrying out corona treatment on the surface of the BOPLA film to be coated, wherein the surface tension value of the treated film is not less than 40 dyne value;
b) uniformly coating polylactic acid emulsion on the corona surface of the BOPLA film; the polylactic acid emulsion is the polylactic acid emulsion or the polylactic acid emulsion prepared by the preparation method;
c) and after coating, drying, rolling and pressing a roller to obtain the film containing the barrier coating.
In step a):
in certain embodiments of the present invention, the tension is 70N.
In certain embodiments of the present invention, the treated film has a surface tension value of 40 dynes.
In step b):
in some embodiments of the present invention, the coating speed is 100-300 m/min, and the coating thickness is 1-6 g/m2. In certain embodiments, the production speed of the coating is 180m/min and the thickness of the coating is 2g/m2。
In step c):
in some embodiments of the present invention, the drying temperature is 70-110 ℃. In certain embodiments, the temperature of the oven drying is 90 ℃.
In some embodiments of the invention, the tension of the rolling is 50-70N. In certain embodiments, the take-up tension is 70N.
In certain embodiments of the invention, the pressure of the press roll is not less than 0.5 kg. In certain embodiments, the pressure of the nip roll is 2.5 kg.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to describe the polylactic acid emulsion, its preparation method and application in detail, but should not be construed as limiting the scope of the present invention.
Example 1
Preparation of polylactic acid emulsion:
1. heating 55 parts by weight of polylactic acid with the polymerization degree of 1500-1800 to dissolve the polylactic acid in 120 parts by weight of chloroform solvent to obtain a solution a; 24 parts by weight of carboxyl-terminated polytrimethylene carbonate was dissolved in 46 parts by weight of N, N-dimethylformamide to obtain a solution b. And (3) mixing the solution a and the solution b, adding the mixture into a reaction device, vacuumizing to 5kpa, introducing nitrogen for protection, adding 2.5 parts by weight of chain extender diphenylmethane diisocyanate, and reacting for 5 hours at 83 ℃ to obtain a first product solution.
2. 55 parts by weight of 1, 4-butanediol polycarbonate was dissolved in 150 parts by weight of ethyl acetate to obtain a solution c. And mixing the first product solution with the solution c, stirring for 2.5h, heating to 77 ℃, and reacting for 6.5h under the protection of nitrogen to obtain a second product solution.
3. Adding 12 parts by weight of emulsifier Tween 80 and 5 parts by weight of water-soluble chitosan into 550 parts by weight of deionized water to obtain a solution d; dropwise adding the second product solution into a stirred (200rpm) solution d to obtain an emulsion e; the dripping time is controlled to be 2 hours; during the dropwise addition, the temperature of the solution d was controlled to 33 ℃.
4. Stirring (150rpm) and mixing the emulsion e with 4 parts by weight of talcum powder for 3 hours to obtain emulsion f;
5. and (3) reducing the stirring speed of the emulsion f to 80rpm, reducing the pressure to be below 10kPa at normal temperature, vacuumizing to boil and evaporate the solvent in the emulsion, introducing a small amount of air to blow, taking away the evaporated solvent, and removing the solvent in the emulsion f to reduce the content of VOC to 30 g/L.
6. And cooling to normal temperature, adding ammonia water to adjust the pH value to 10, and discharging to obtain the polylactic acid emulsion.
Example 2
Preparation of polylactic acid emulsion:
1. heating and dissolving 48 parts by weight of polylactic acid with the polymerization degree of 2000-2300 in 135 parts by weight of chloroform solvent to obtain a solution a; 30 parts by weight of carboxyl-terminated polytrimethylene carbonate was dissolved in 44 parts by weight of N, N-dimethylformamide to obtain a solution b. And (3) mixing the solution a and the solution b, adding the mixture into a reaction device, vacuumizing until the weight is 5kpa, introducing nitrogen for protection, adding 2.5 parts by weight of chain extender dicyclohexylmethane diisocyanate, and reacting for 5 hours at 85 ℃ to obtain a first product solution.
2. 58 parts by weight of 1, 6-hexanediol polycarbonate was dissolved in 145 parts by weight of ethyl acetate to obtain a solution c. And mixing the first product solution with the solution c, stirring for 3h, heating to 77 ℃, and reacting for 7h under the protection of nitrogen to obtain a second product solution.
3. Adding 14 parts by weight of emulsifier Brij30 and 6 parts by weight of water-soluble chitosan into 600 parts by weight of deionized water to obtain solution d; dropwise adding the second product solution into a stirred (200rpm) solution d to obtain an emulsion e; the dripping time is controlled to be 2 hours; during the dropwise addition, the temperature of the solution d was controlled to 33 ℃.
4. Stirring (150rpm) and mixing the emulsion e with 5 parts by weight of talcum powder for 3 hours to obtain emulsion f;
5. and (3) reducing the stirring speed of the emulsion f to 80rpm, reducing the pressure to be below 10kPa at normal temperature, vacuumizing to boil and evaporate the solvent in the emulsion, introducing a small amount of air to blow, taking away the evaporated solvent, and removing the solvent in the emulsion f to reduce the content of VOC to 25 g/L.
6. And cooling to normal temperature, adding ammonia water to adjust the pH value to 9, and discharging to obtain the polylactic acid emulsion.
Example 3
Preparation of polylactic acid emulsion:
1. heating and dissolving 60 parts by weight of polylactic acid with the polymerization degree of 2500-3000 in 140 parts by weight of chloroform solvent to obtain a solution a; 35 parts by weight of carboxyl-terminated polytrimethylene carbonate was dissolved in 50 parts by weight of N, N-dimethylformamide to obtain a solution b. And (3) mixing the solution a and the solution b, adding the mixture into a reaction device, vacuumizing until the weight is 6kpa, introducing nitrogen for protection, adding 2.5 parts by weight of chain extender diphenylmethane diisocyanate, and reacting at 85 ℃ for 5 hours to obtain a first product solution.
2. 60 parts by weight of 1, 10-decanediol polycarbonate was dissolved in 148 parts by weight of ethyl acetate to obtain a solution c. And mixing the first product solution with the solution c, stirring for 3h, heating to 77 ℃, and reacting for 6.5h under the protection of nitrogen to obtain a second product solution.
3. Adding 14 parts by weight of emulsifier Tween 61 and 6 parts by weight of water-soluble chitosan into 600 parts by weight of deionized water to obtain a solution d; dropwise adding the second product solution into a stirred (200rpm) solution d to obtain an emulsion e; the dripping time is controlled to be 2 hours; during the dropwise addition, the temperature of the solution d was controlled to 33 ℃.
4. Stirring (150rpm) and mixing the emulsion e with 4 parts by weight of talcum powder for 3 hours to obtain emulsion f;
5. and (3) reducing the stirring speed of the emulsion f to 100rpm, reducing the pressure to be below 10kPa at normal temperature, vacuumizing to boil and evaporate the solvent in the emulsion, introducing a small amount of air to blow and sweep, taking away the evaporated solvent, and removing the solvent in the emulsion f to reduce the content of VOC to 20 g/L.
6. And cooling to normal temperature, adding ammonia water to adjust the pH value to 11, and discharging to obtain the polylactic acid emulsion.
Example 4
Films containing coatings were prepared from the polylactic acid emulsions of examples 1 to 3, respectively:
1. and under the tension of 70N, unreeling the BOPLA film, flatly unfolding the BOPLA film, feeding the BOPLA film into corona treatment equipment, and carrying out corona treatment on the surface of the BOPLA film to be coated, wherein the tension of the treated film reaches a 40 dyne value.
2. The polylactic acid emulsion prepared in example 1 was uniformly coated on the corona side of the BOPLA film by a top-coating apparatus at a production speed of 180m/min and a coating thickness of 2.0g/m2。
3. And drying the coated film after coating in an oven at the temperature of 90 ℃.
4. And (3) rolling the dried coating film by a rolling device with rolling tension of 70N and compression roller pressure of 2.5kg to obtain a film M-1 with a coating, wherein the thickness of the coating is 1.5 mu M.
The polylactic acid emulsions of example 2 and example 3 were subjected to the above-mentioned steps, respectively, to prepare films M-2 and M-3 having a coating layer.
The properties of the films M-1, M-2, M-3 and BOPLA films were examined and the results are shown in Table 1. Specifically, the oxygen permeation quantity of the film is detected according to the GB/T19789-2005 standard, and the biodegradation performance of the film is detected according to the GB/T19277.1-2011 standard.
TABLE 1 results of testing the properties of films M-1, M-2, M-3 and BOPLA films
The experimental result shows that the oxygen permeation quantity of the film containing the barrier coating prepared by the invention is less than 16cc/m224h 0.1Mpa, the oxygen barrier performance is better.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The polylactic acid emulsion is prepared from the following raw materials in parts by weight:
2. the polylactic acid emulsion according to claim 1, wherein the polylactic acid is a levorotatory polylactic acid;
the polymerization degree of the polylactic acid is 1000-3000.
3. The polylactic acid emulsion according to claim 1, wherein the aliphatic polycarbonate polyol comprises at least one of 1, 4-butylene carbonate, 1, 5-pentylene carbonate, 1, 6-hexylene carbonate, 1, 8-octylene carbonate, and 1, 10-decylene carbonate.
4. The polylactic acid emulsion according to claim 1, wherein the emulsifier comprises tween 80, Brij30, or tween 61;
the chain extender comprises diphenylmethane diisocyanate and/or dicyclohexylmethane diisocyanate.
5. A preparation method of polylactic acid emulsion comprises the following steps:
A) mixing the solution a and the solution b to obtain a mixed solution; the solution a comprises polylactic acid and chloroform; the solution b comprises carboxyl terminated polytrimethylene carbonate and N, N-dimethylformamide;
B) reacting the mixed solution with a chain extender at 80-100 ℃ under the condition of protective gas to obtain a first product solution;
C) reacting the first product solution with the solution c at 70-90 ℃ under the condition of protective gas to obtain a second product solution; the solution c comprises aliphatic polycarbonate polyol and ethyl acetate;
D) mixing deionized water, an emulsifier and water-soluble chitosan to obtain a solution d;
dropwise adding the second product solution into the stirred solution d to obtain emulsion e;
E) stirring and mixing the emulsion e and the talcum powder to obtain emulsion f;
F) reducing the stirring speed of the emulsion f, reducing the pressure to be below 10kPa, and removing the solvent in the emulsion f to reduce the content of VOC to be below 30 g/L;
G) and (3) cooling to normal temperature, and adjusting the pH value to 8-11 to obtain the polylactic acid emulsion.
6. The preparation method according to claim 5, wherein in the step B), the reaction time is 4-10 h;
the reaction time is 5-10 h.
7. The preparation method according to claim 5, wherein in the step D), the dropwise adding time is 2-3 h;
in the dropping process, the temperature of the solution d is controlled to be less than or equal to 40 ℃;
the stirring speed of the solution d is 100-300 rpm.
8. The preparation method according to claim 5, wherein in the step E), the rotation speed of stirring and mixing is 80-160 rpm;
the stirring and mixing time is 3-6 h;
and reducing the stirring speed of the emulsion f to 60-100 rpm.
9. The use of the polylactic acid emulsion according to any one of claims 1 to 4 as a barrier coating, or the use of the polylactic acid emulsion prepared by the preparation method according to any one of claims 5 to 8 as a barrier coating.
10. A film comprising a barrier coating, comprising:
a film;
and a barrier coating layer compounded on the film;
the barrier coating is prepared from the polylactic acid emulsion as defined in any one of claims 1 to 4, or prepared from the polylactic acid emulsion prepared by the preparation method as defined in any one of claims 5 to 8.
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