CN113583255A - Polyglycolic acid emulsion and preparation method thereof - Google Patents
Polyglycolic acid emulsion and preparation method thereof Download PDFInfo
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 76
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 76
- 239000000839 emulsion Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000004945 emulsification Methods 0.000 title claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 70
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 34
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 34
- 229920002258 tannic acid Polymers 0.000 claims abstract description 34
- 229940033123 tannic acid Drugs 0.000 claims abstract description 34
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 34
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010439 graphite Substances 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 18
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- 230000004888 barrier function Effects 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 14
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- -1 tannic acid modified graphite Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000004970 Chain extender Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 230000001804 emulsifying effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 description 38
- 239000002904 solvent Substances 0.000 description 17
- 239000000725 suspension Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920006238 degradable plastic Polymers 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229920001634 Copolyester Polymers 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- HIWLPPCYBVXAFL-UHFFFAOYSA-N hexanoic acid;2-hydroxybutanoic acid Chemical compound CCC(O)C(O)=O.CCCCCC(O)=O HIWLPPCYBVXAFL-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical compound OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000071 poly(4-hydroxybutyrate) Polymers 0.000 description 2
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000013547 stew Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 238000002604 ultrasonography Methods 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
- 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
- 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
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
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- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
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Abstract
The invention provides a polyglycolic acid emulsion, which comprises the following components: 40-100 parts of polyglycolic acid, 20-50 parts of polyhydroxyalkanoate, 1-5 parts of tannic acid, 1-3 parts of graphite flake, 1-10 parts of silane coupling agent and 1-10 parts of nano silicon dioxide. The application also provides a preparation method of the polyglycolic acid emulsion and a high-barrier material. The film formed by the polyglycolic acid emulsion obtained by selecting specific components and limiting the content of the components has high barrier property and can be degraded.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to polyglycolic acid emulsion and a preparation method thereof.
Background
In recent years, with the popularization of plastic forbidden requirements at home and abroad, more and more degradable plastics are applied to the lives of people. In the foreseeable future, the comprehensive application of the degradable plastics to the living aspects of people is a necessary situation, and the functional high-barrier package can also meet the arrival of the degradable plastics. However, the oxygen transmission capacity and the water vapor transmission capacity of the existing degradable plastic are both one order of magnitude larger than those of the existing conventional high-barrier K film, so that the degradable plastic film cannot be used for high-barrier packaging.
Most of the existing solutions are to use non-degradable high-barrier materials to modify degradable plastics, but the modified plastics are degradable plastics, but plastic particles generated after degradation of the modified plastics after the non-degradable materials are used are more harmful to the environment and the ocean.
Polyglycolic acid (PGA) is an ideal completely biodegradable material, can be completely degraded within 1-3 months, is non-toxic and harmless, and the final degradation products are carbon dioxide and water, which are certified by safe biodegradable plastic materials in the United states, European Union and Japan, and have better application prospects in the fields of medical sutures, degradable plastics and the like. The barrier property of polyglycolic acid (PGA) to oxygen and water vapor is 100 times that of PET and 1000 times that of PLA, the barrier property to gas is not affected by the environmental temperature basically, and the polyglycolic acid (PGA) becomes an ideal packaging material for various foods, daily necessities and medicines. Although polyglycolic acid has excellent properties, the processing property is poor, the high crystallization causes the high processing temperature, the high processing temperature also causes the excessive degradation of the material, thereby affecting the properties of the material, and the processing mode using the conventional plastic has extremely high requirements on equipment for the use.
PVDC used for coating the existing high-barrier material cannot be recycled and cut, and carcinogens such as dioxin can be generated after combustion, so that the PVDC is prohibited from being used by legislation in many countries; although PVOH used for coating high barrier materials can achieve high barrier performance, its barrier performance is greatly reduced with the increase of ambient humidity, which makes it unusable in high moisture product packaging. Therefore, the provision of the polyglycolic acid material which has high barrier property, is degradable and has a simple preparation process is of great significance.
Disclosure of Invention
The invention aims to provide a high-barrier degradable polyglycolic acid emulsion.
In view of the above, the present application provides a polyglycolic acid emulsion comprising the following components:
40-100 parts by weight of polyglycolic acid;
20-50 parts by weight of polyhydroxyalkanoate;
1-5 parts by weight of tannic acid;
1-3 parts by weight of graphite flakes;
1-10 parts by weight of a silane coupling agent;
1-10 parts by weight of nano silicon dioxide;
0.5-1 part by weight of a chain extender;
100-300 parts by weight of chloroform;
10-100 parts by weight of ethanol;
10-50 parts by weight of dimethylformamide;
200-400 parts of deionized water.
Preferably, the number average molecular weight of the polyglycolic acid is 1000 to 10000; the silane coupling agent is selected from one of KH550 and KH 570; the chain extender is selected from one or more of BASF Joncry ADR-4368C/CS and ADR-4370S, ADR-4300.
Preferably, the polyglycolic acid is contained in an amount of 50 to 80 parts by weight.
Preferably, the content of the polyhydroxyalkanoate is 20 to 40 parts by weight.
Preferably, the content of the tannic acid is 1 to 3 parts by weight.
Preferably, the content of the nano silicon dioxide is 1-6 parts by weight.
Preferably, the content of the ethanol is 10 to 60 parts by weight.
The application also provides a preparation method of the polyglycolic acid emulsion, which comprises the following steps:
A) heating polyglycolic acid and polyhydroxyalkanoate, adding a chain extender, and reacting; mixing the obtained polymer with chloroform to obtain a polymer solution;
mixing nano silicon dioxide, ethanol and a silane coupling agent, and reacting to obtain modified nano silicon dioxide;
B) pre-emulsifying the modified nano silicon dioxide and the polymer solution, adding deionized water, and emulsifying at a high speed to obtain an original emulsion;
C) heating, reacting and modifying tannic acid, dimethyl formamide and graphite flakes, and drying to obtain tannic acid modified graphite flakes;
D) and mixing the tannic acid modified graphite flakes with the original emulsion to obtain the polyglycolic acid emulsion.
Preferably, the stirring speed of the pre-emulsification is 10000-15000 rpm, and the stirring speed of the emulsification is 20000-3000 rpm.
The application also provides a high-barrier material which consists of a substrate and a film coated on the surface of the substrate, wherein the film is formed by the polyglycolic acid emulsion or the polyglycolic acid emulsion prepared by the preparation method.
The application provides a polyglycolic acid emulsion, which comprises raw materials such as polyglycolic acid, polyhydroxyalkanoate, tannic acid, graphite flake, a silane coupling agent, nano-silica and the like with specific content, and the long-chain Polyhydroxyalkanoate (PHA) is added into polyglycolic acid (PGA) for chain extension copolymerization, so that the molecular weight of a polymer is increased, the complete degradation time of the polyglycolic acid is prolonged, and the service life of the polyglycolic acid is prolonged; the tannin modified graphite flake is intercalated and blended in the emulsion, so that the barrier property of the polymer emulsion after film forming can be greatly improved. Furthermore, the polymer solution is emulsified and liquefied by high-speed stirring, and then is processed by emulsion coating, so that the high-temperature environment required by conventional plastic processing is avoided, the requirements of the production process on equipment are reduced, and the degradation of materials in the high-temperature processing process is also reduced.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the problem that the coating barrier property of a high-barrier material is poor or difficult to degrade in the prior art, the application provides a polyglycolic acid emulsion which has better degradability and barrier property as a coating liquid, and specifically, the embodiment of the invention discloses a polyglycolic acid emulsion which comprises the following components;
40-100 parts by weight of polyglycolic acid;
20-50 parts by weight of polyhydroxyalkanoate;
1-5 parts by weight of tannic acid;
1-3 parts by weight of graphite flakes;
1-10 parts by weight of a silane coupling agent;
1-10 parts by weight of nano silicon dioxide;
0.5-1 part by weight of a chain extender;
100-300 parts by weight of chloroform;
10-100 parts by weight of ethanol;
10-50 parts by weight of dimethylformamide;
200-400 parts of deionized water.
In the polyglycolic acid emulsion provided by the present application, the polyglycolic acid is a main molecular chain of the polyglycolic acid emulsion as a main component, provides a basis for high barrier property of the polyglycolic acid emulsion, has a number average molecular weight of 1000 to 10000, and is contained in an amount of 40 to 100 parts by weight, more specifically, 45 to 80 parts by weight, and more specifically, 50 to 65 parts by weight.
The polyhydroxy fatty acid ester is used as a main chain component for producing a macromolecular chain through reaction and adjusting the degradation performance of the emulsion after film forming, and is one or more copolyesters in polyhydroxy fatty acid ester containing C3-C9 linear alkyl, wherein the content of the polyhydroxy fatty acid ester is 20-50 parts by weight, more specifically, the content of the polyhydroxy fatty acid ester is 20-40 parts by weight.
The content of the tannic acid serving as a modifier of the graphite flake is 1-5 parts by weight, and more specifically, the content of the tannic acid is 1-3 parts by weight.
The graphite flake is modified by tannic acid and then added into emulsion, and after the emulsion forms a film, the barrier property of the film can be improved, wherein the content of the graphite flake is 1-3 parts by weight. The impact on barrier properties goes from low to high to low as the graphite flake content goes from low to high.
The silane coupling agent is a modifier of polyglycolic acid and polyhydroxyalkanoate, and is contained in an amount of 1 to 10 parts by weight, more specifically, 1 to 5 parts by weight, and more specifically, 2 to 4.5 parts by weight.
The modified nano silicon dioxide is added into the emulsion, so that the barrier property of the film can be improved, the content of the nano silicon dioxide is 1-10 parts by weight, more specifically 1-6 parts by weight, and more specifically 2-5.5 parts by weight.
The chain extender is selected from one or more of BASF Joncry ADR-4368C/CS, ADR-4370S and ADR-4300; the chain extender is used as a catalyst for polyglycolic acid and polyhydroxyalkanoate, and is contained in an amount of 0.5 to 1 part by weight, more specifically, 0.7 to 0.9 part by weight.
The chloroform and the ethanol are respectively used as a main solvent and an auxiliary solvent, and the content of the chloroform and the ethanol is 100-300 parts by weight and 10-100 parts by weight respectively, more specifically, the content of the chloroform is 130-250 parts by weight, and the content of the ethanol is 20-50 parts by weight.
The content of the dimethylformamide as a graphite modification solvent is 10-50 parts by weight, and more specifically, the content of the dimethylformamide is 20-45 parts by weight.
The present application also provides a method of preparing a polyglycolic acid emulsion, comprising the steps of:
A) heating polyglycolic acid and polyhydroxyalkanoate, adding a chain extender, and reacting; mixing the obtained polymer with chloroform to obtain a polymer solution;
mixing nano silicon dioxide, ethanol and a silane coupling agent, and reacting to obtain modified nano silicon dioxide;
B) pre-emulsifying the modified nano silicon dioxide and the polymer solution, adding deionized water, and emulsifying at a high speed to obtain an original emulsion;
C) heating, reacting and modifying tannic acid, dimethyl formamide and graphite flakes, and drying to obtain tannic acid modified graphite flakes;
D) and mixing the tannic acid modified graphite flakes with the original emulsion to obtain the polyglycolic acid emulsion.
In the application, polyglycolic acid and polyhydroxyalkanoate are heated, then a chain extender is added for reaction, the obtained polymer is mixed with chloroform to obtain a polymer solution, and in the process, the polyglycolic acid and the polyhydroxyalkanoate undergo chain extension copolymerization to prolong the degradation time of the polyglycolic acid and prolong the service life. The heating temperature is 230-250 ℃, and the reaction time is 1-2 h.
Meanwhile, the modified nano silicon dioxide is prepared by modifying silicon dioxide, so that the barrier property of the emulsion is improved. Mixing silicon dioxide with ethanol and a silane coupling agent, carrying out ultrasonic dispersion and then reacting to obtain a suspension, and separating the suspension at 10000-15000 rpm to obtain the modified nano silicon dioxide.
According to the invention, the modified nano silicon dioxide and the polymer solution are pre-emulsified, and then deionized water is added for emulsification to obtain original emulsion; the stirring speed of pre-emulsification is 10000-15000 rpm, and the stirring speed of emulsification is 20000-3000 rpm.
The application has carried out the modification of graphite flake simultaneously, and it is specifically that add tannic acid and prepare into solution in the dimethylformamide solvent, place the graphite flake in solution, heat to rise to 40 ~ 50 ℃, 30 ~ 60min after the ultrasonic oscillation stews, uses centrifuge 600rpm centrifugation 20 ~ 60s, puts the centrifugation result in 105 ℃ oven stoving 12 hours, obtains tannic acid modified graphite flake. And finally, mixing the prepared tannic acid modified graphite flake with the original emulsion to obtain the polyglycolic acid emulsion. The process comprises the following steps: mixing the tannic acid modified graphite flake with the original emulsion at the stirring speed of 200-400 rpm, and performing rotary evaporation to obtain the polyglycolic acid emulsion.
The application also provides a high-barrier material which consists of a substrate and a film coated on the surface of the substrate, wherein the film is formed by the polyglycolic acid emulsion in the scheme. The matrix is well known to those skilled in the art and no particular limitation is imposed on this application.
For further understanding of the present invention, the following examples are provided to illustrate the polyvinyl alcohol emulsion of the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
S1, adding 55 parts of polyglycolic acid and 25 parts of hydroxybutyrate hexanoic acid copolyester into a reaction kettle, heating to 235 ℃, stirring and dissolving uniformly, adding 0.9 part of chain extender, and stirring and reacting for 2 hours;
s2, cooling the reacted polymer to normal temperature, washing with water, drying, and dissolving in 150 parts of solvent chloroform to obtain a polymer solution;
s3, adding 5.2 parts of nano silicon dioxide into 20 parts of ethanol, stirring at a high speed of 300rpm, and performing ultrasonic dispersion for 30 minutes to obtain a suspension; adding 4.3 parts of silane coupling agent into the suspension, and ultrasonically mixing for 10 minutes; after being uniformly mixed, the mixture is heated to 73 ℃ for reaction for 6 hours, and then the suspension is centrifugally separated at 12000rpm, cleaned and dried to obtain modified nano silicon dioxide;
s4, adding the modified nano silicon dioxide into the polymer solution obtained in S2, stirring at a high speed of 11000rpm for pre-emulsification, adding the pre-emulsified solution into 325 parts of deionized water, and stirring at a super high speed of 23000rpm for emulsification to obtain an original emulsion;
s5, adding 2.5 parts of tannic acid into 40 parts of DMF solvent to prepare a solution, placing 2 parts of graphite flakes into the solution, heating to 48 ℃, ultrasonically shaking for 60min, standing, centrifuging for 60s at 600rpm by using a centrifuge, and placing the centrifuged product into a 105 ℃ oven to dry for 12 hours to obtain tannic acid modified graphite flakes;
s6, adding the tannic acid modified graphite flake into the original emulsion of S4, stirring and dispersing uniformly at a stirring speed of 350rpm, performing rotary evaporation on the emulsion after uniform dispersion, and removing redundant solvent to obtain the high-barrier degradable polyglycolic acid (PGA) emulsion.
Example 2
S1, adding 40 parts of polyglycolic acid and 35 parts of hydroxybutyrate hexanoic acid copolyester into a reaction kettle, heating to 240 ℃, stirring and dissolving uniformly, adding 0.7 part of chain extender, and stirring and reacting for 1.5 hours;
s2, cooling the reacted polymer to normal temperature, washing with water, drying, and dissolving in 180 parts of solvent chloroform to obtain a polymer solution;
s3, adding 5 parts of nano silicon dioxide into 50 parts of ethanol, stirring at a high speed of 500rpm, and performing ultrasonic dispersion for 30 minutes to obtain a suspension; adding 3.8 parts of silane coupling agent into the suspension, ultrasonically mixing for 10 minutes, uniformly mixing, heating to 75 ℃ for reacting for 8 hours, and then centrifugally separating, cleaning and drying the suspension at 12000rpm to obtain modified nano-silicon dioxide;
s4, adding the modified nano silicon dioxide into the polymer solution obtained in S2, stirring and pre-emulsifying at a high speed of 12000rpm, adding the pre-emulsified solution into 260 parts of deionized water, and stirring and emulsifying at a super high speed of 23000rpm to obtain an original emulsion;
s5, adding 2 parts of tannic acid into 30 parts of DMF solvent to prepare a solution, placing 1.5 parts of graphite flakes into the solution, heating to 48 ℃, ultrasonically oscillating for 60min, standing, centrifuging for 50s at 600rpm by using a centrifuge, and placing the centrifuged product into a 105 ℃ oven to dry for 12 hours to obtain tannic acid modified graphite flakes;
s6, adding the tannic acid modified graphite flake into the original emulsion of S4, stirring and dispersing uniformly at the stirring speed of 400 rpm. After the emulsion is uniformly dispersed, the emulsion is subjected to rotary evaporation to remove the redundant solvent, and the high-barrier degradable polyglycolic acid (PGA) emulsion of the invention can be obtained.
Example 3
S1, adding 47 parts of polyglycolic acid and 40 parts of poly 3-hydroxybutyrate/4-hydroxybutyrate copolymer into a reaction kettle, heating to 245 ℃, stirring and dissolving uniformly, adding 0.5 part of chain extender, and stirring and reacting for 1.5 hours;
s2, cooling the reacted polymer to normal temperature, washing with water, drying, and dissolving in 200 parts of chloroform solvent to obtain a polymer solution;
s3, adding 4.2 parts of nano silicon dioxide into 30 parts of ethanol, stirring at a high speed of 300rpm, and performing ultrasonic dispersion for 30 minutes to obtain a suspension; 2 parts of silane coupling agent were added to the suspension and mixed by ultrasound for 15 minutes. After being uniformly mixed, the mixture is heated to 75 ℃ to react for 8 hours, and then the suspension is centrifugally separated at 12000rpm, cleaned and dried to obtain modified nano silicon dioxide;
s4, adding the modified nano silicon dioxide into the polymer solution obtained in the step S2, stirring at a high speed of 15000rpm for pre-emulsification, adding the pre-emulsified solution into 360 parts of deionized water, and stirring at a super high speed of 25000rpm for emulsification to obtain an original emulsion;
s5, adding 1.5 parts of tannic acid into 30 parts of DMF solvent to prepare a solution, placing 1.5 parts of graphite flakes in the solution, heating to 48 ℃, ultrasonically shaking for 50min, standing, centrifuging for 60s at 600rpm by using a centrifuge, and placing the centrifuged product in a 105 ℃ oven to dry for 12 hours to prepare tannic acid modified graphite flakes;
s6, adding the tannic acid modified graphite flake into the original emulsion of S4, stirring and dispersing uniformly at the stirring speed of 300rpm, performing rotary evaporation on the emulsion after uniform dispersion, and removing redundant solvent to obtain the high-barrier degradable polyglycolic acid (PGA) emulsion.
Example 4
S1, adding 55 parts of polyglycolic acid and 30 parts of poly 3-hydroxybutyrate/4-hydroxybutyrate copolymer into a reaction kettle, heating to 230 ℃, stirring and dissolving uniformly, adding 0.8 part of chain extender, and stirring for reacting for 2 hours;
s2, cooling the reacted polymer to normal temperature, washing with water, drying, and dissolving in 210 parts of solvent chloroform to obtain a polymer solution;
s3, adding 4.5 parts of nano silicon dioxide into 25 parts of ethanol, stirring at a high speed of 300rpm, and performing ultrasonic dispersion for 45 minutes to obtain a suspension; adding 3.5 parts of silane coupling agent into the suspension, ultrasonically mixing for 10 minutes, uniformly mixing, heating to 75 ℃ for reaction for 10 hours, and then centrifugally separating, cleaning and drying the suspension at 12000rpm to obtain modified nano-silicon dioxide;
s4, adding the modified nano silicon dioxide into the polymer solution obtained in S2, stirring at a high speed of 11000rpm for pre-emulsification, adding the pre-emulsified solution into 325 parts of deionized water, and stirring at a super high speed of 23000rpm for emulsification to obtain an original emulsion;
s5, adding 1.5 parts of tannic acid into 35 parts of DMF solvent to prepare a solution, placing 2 parts of graphite flakes into the solution, heating to 45 ℃, ultrasonically shaking for 40min, standing, centrifuging for 40s at 600rpm by using a centrifuge, placing the centrifuged product into a 105 ℃ oven, and drying for 12 hours to obtain tannic acid modified graphite flakes;
s6, adding the tannic acid modified graphite flake into the original emulsion of S4, stirring and dispersing uniformly at a stirring speed of 350rpm, performing rotary evaporation on the emulsion after uniform dispersion, and removing redundant solvent to obtain the high-barrier degradable polyglycolic acid (PGA) emulsion.
Comparative example
S1, adding 55 parts of polyglycolic acid and 25 parts of hydroxybutyrate hexanoic acid copolyester into a reaction kettle, heating to 235 ℃, stirring and dissolving uniformly, adding 0.9 part of chain extender, and stirring and reacting for 2 hours;
s2, cooling the reacted polymer to normal temperature, washing with water, drying, and dissolving in 150 parts of solvent chloroform to obtain a polymer solution;
s3, adding 5.2 parts of nano silicon dioxide into 20 parts of ethanol, stirring at a high speed of 300rpm, and performing ultrasonic dispersion for 30 minutes to obtain a suspension; adding 4.3 parts of silane coupling agent into the suspension, and ultrasonically mixing for 10 minutes; after being uniformly mixed, the mixture is heated to 73 ℃ for reaction for 6 hours, and then the suspension is centrifugally separated at 12000rpm, cleaned and dried to obtain modified nano silicon dioxide;
s4, adding the modified nano silicon dioxide into the polymer solution obtained in the step S2, stirring and pre-emulsifying at a high speed of 11000rpm, adding the pre-emulsified solution into 325 parts of deionized water, and stirring and emulsifying at a super high speed of 23000rpm to obtain a comparative emulsion.
The performance of the examples and the comparative examples was measured, and the results are shown in table 1;
TABLE 1 comparative data table of the properties of the examples and comparative examples
Oxygen transmission test results the emulsions of the invention were tested coated on a BOPLA substrate of 20 μm thickness, with a coating thickness of 2 μm. The test standard is GB/T19789.
Degradation time test standard GB/T32163.2-2015.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
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. A polyglycolic acid emulsion comprising the following components:
2. the polyglycolic acid emulsion according to claim 1, wherein the polyglycolic acid has a number average molecular weight of 1000 to 10000; the silane coupling agent is selected from one of KH550 and KH 570; the chain extender is selected from one or more of BASF Joncry ADR-4368C/CS and ADR-4370S, ADR-4300.
3. The polyglycolic acid emulsion according to claim 1, which contains 50 to 80 parts by weight of polyglycolic acid.
4. The polyglycolic acid emulsion according to claim 1, wherein the content of the polyhydroxyalkanoate is 20 to 40 parts by weight.
5. The polyglycolic acid emulsion according to claim 1, wherein the content of tannic acid is 1 to 3 parts by weight.
6. The polyglycolic acid emulsion according to claim 1, wherein the content of the nano-silica is 1 to 6 parts by weight.
7. The polyglycolic acid emulsion according to claim 1, wherein the content of ethanol is 10 to 60 parts by weight.
8. The method for preparing a polyglycolic acid emulsion according to claim 1, comprising the steps of:
A) heating polyglycolic acid and polyhydroxyalkanoate, adding a chain extender, and reacting; mixing the obtained polymer with chloroform to obtain a polymer solution;
mixing nano silicon dioxide, ethanol and a silane coupling agent, and reacting to obtain modified nano silicon dioxide;
B) pre-emulsifying the modified nano silicon dioxide and the polymer solution, adding deionized water, and emulsifying at a high speed to obtain an original emulsion;
C) heating, reacting and modifying tannic acid, dimethyl formamide and graphite flakes, and drying to obtain tannic acid modified graphite flakes;
D) and mixing the tannic acid modified graphite flakes with the original emulsion to obtain the polyglycolic acid emulsion.
9. The method according to claim 8, wherein the pre-emulsification is stirred at 10000 to 15000rpm, and the emulsification is stirred at 20000 to 3000 rpm.
10. A high barrier material comprising a substrate and a film coated on the surface of the substrate, wherein the film is formed from the polyglycolic acid emulsion according to any one of claims 1 to 7 or the polyglycolic acid emulsion prepared by the preparation method according to any one of claims 8 to 9.
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