CN114045010A - Biodegradable polyester film and preparation method thereof - Google Patents
Biodegradable polyester film and preparation method thereof Download PDFInfo
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- CN114045010A CN114045010A CN202111297977.0A CN202111297977A CN114045010A CN 114045010 A CN114045010 A CN 114045010A CN 202111297977 A CN202111297977 A CN 202111297977A CN 114045010 A CN114045010 A CN 114045010A
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- biodegradable polyester
- polyester film
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- 229920000229 biodegradable polyester Polymers 0.000 title claims abstract description 45
- 239000004622 biodegradable polyester Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920002472 Starch Polymers 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 239000008107 starch Substances 0.000 claims abstract description 29
- 235000019698 starch Nutrition 0.000 claims abstract description 29
- 229920006167 biodegradable resin Polymers 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- 238000010096 film blowing Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000002216 antistatic agent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- -1 polybutylene terephthalate-adipate Polymers 0.000 claims description 15
- 239000004626 polylactic acid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 10
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- MWEZYKWGRQWLKM-UHFFFAOYSA-N n,n-dihydroxyicosan-3-amine Chemical group CCCCCCCCCCCCCCCCCC(CC)N(O)O MWEZYKWGRQWLKM-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 6
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 229920002961 polybutylene succinate Polymers 0.000 claims description 5
- 239000004631 polybutylene succinate Substances 0.000 claims description 5
- 229920002261 Corn starch Polymers 0.000 claims description 4
- 240000003183 Manihot esculenta Species 0.000 claims description 4
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 4
- 239000008120 corn starch Substances 0.000 claims description 4
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 3
- 239000004630 polybutylene succinate adipate Substances 0.000 claims description 3
- 229920001634 Copolyester Polymers 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 229920002463 poly(p-dioxanone) polymer Polymers 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 239000000622 polydioxanone Substances 0.000 claims description 2
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 claims 1
- 229920001707 polybutylene terephthalate Polymers 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 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 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 125000004423 acyloxy group Chemical group 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- CKXDKAOBYWWYEK-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione;hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.O=C1CCC(=O)OCCCCO1 CKXDKAOBYWWYEK-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a biodegradable polyester film and a preparation method thereof, belonging to the technical field of biodegradable materials, wherein the biodegradable polyester film comprises the following raw materials: hard biodegradable resin, soft biodegradable resin, starch, ethyl orthosilicate, ethanol, a compatibilizer, a coupling agent, an opening agent, a dispersing agent, a lubricant, an antioxidant and an antistatic agent; the preparation method of the biodegradable polyester film comprises the following steps: firstly, forming a SiO2@ starch material from tetraethoxysilane, ethanol and starch in a hot water bath, then mixing SiO2@ starch, biodegradable resin, a compatibilizer, a coupling agent, an opening agent, a dispersing agent and a lubricating agent, uniformly stirring to obtain a mixture, then granulating to obtain biodegradable polyester particles, and finally preparing the biodegradable polyester particles into a biodegradable polyester film by adopting a film blowing process; the biodegradable polyester film prepared by the method has good mechanical property and degradation effect, and the SiO2@ starch has excellent dispersibility.
Description
Technical Field
The invention relates to the technical field of biodegradable materials, in particular to a biodegradable polyester film and a preparation method thereof.
Background
White pollution is a pressing issue facing the world at present, plastic film products used at present are made of non-degradable plastics, with the national economic development and social progress, the consumption of people is increasing, more and more waste plastic products are generated, biodegradable resin is completely degraded into carbon dioxide and water in 3-6 months under the environment condition of compostability, and has no pollution to the environment, polylactic acid (PLA), polybutylene terephthalate-adipate (PBAT) and polybutylene succinate (PBS) are most commonly used at present, PLA has high rigidity, PBAT is soft, the PBS performance is between that of PLA and PBS, PBAT + PLA + talcum powder system, PBAT + PLA + calcium carbonate system, PBAT + PLA + starch system, PBAT + PLA + talcum powder system and PBAT + PLA + calcium carbonate system are applied in the field of films at present, and the technical difficulty does not exist in degrading film materials, however, the polyester film material of the PBAT + PLA + starch system is always an industrial technical difficulty, and the problem is that the degradable film prepared by the material has pocked spots and granular spots, which is urgently needed to be solved.
For example, patent CN12111133A discloses a method for preparing polybutylene terephthalate adipate polylactic acid starch ternary blend blown film resin, which comprises grafting starch and maleic anhydride, treating with a coupling agent, blending with biodegradable polyester, granulating, and blowing, but the method can only improve the mechanical properties of polyester film bags, and the surfaces of the manufactured film bags still have grains and pocks, and does not really solve the problem of starch dispersion.
Patent CN 1611531A discloses a starch-based biodegradable film material and a production method thereof, but the matrix resin used in the method is polyethylene which is not degradable, and starch is not dispersed, and the film produced by the method has the disadvantages of low degradation rate, environmental hazard, and granular and pocked grains in the film bag.
Patent CN104479175A discloses a starch-based degradable film and a preparation method thereof, wherein the starch-based degradable film comprises the following components in parts by weight: 100 parts of starch, 15-20 parts of seaweed polyphenol, 15-20 parts of glycerol and 5-10 parts of palygorskite clay. The preparation method does not add matrix resin, and basically cannot be formed into film products by blow molding. .
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a biodegradable polyester film and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the biodegradable polyester film comprises the following raw materials in parts by weight:
3-50 parts of hard biodegradable resin, 35-98 parts of soft biodegradable resin, 4-60 parts of starch, 3-7 parts of ethyl orthosilicate, 40-70 parts of ethanol, 0.1-5 parts of compatibilizer, 0.5-2 parts of coupling agent, 1-6 parts of opening agent, 0.3-2 parts of dispersant, 0.1-2 parts of lubricant, 0.2-1 part of antioxidant and 0.1-2 parts of antistatic agent.
As a further scheme of the invention: the starch is one or more of corn starch, cassava starch, potato starch and wheat starch.
As a further scheme of the invention: the hard biodegradable resin is polylactic acid, the optical purity of the hard biodegradable resin is more than or equal to 95 percent, and the MFR (190 ℃, 2.16kg) is 3-9g/10 min.
As a further scheme of the invention: the soft biodegradable resin is one or a blend of two of polybutylene terephthalate-adipate, polybutylene succinate-adipate, polybutylene succinate-co-butylene terephthalate copolyester, polydioxanone and polypropylene carbonate.
As a further scheme of the invention: the soft biodegradable resin is one or a blend of two of terephthalic acid-butylene adipate, poly (butylene succinate-adipate) and poly (butylene succinate).
As a further scheme of the invention: the coupling agent is isopropyl tri (dioctyl pyrophosphato acyloxy).
As a further scheme of the invention: the opening agent is 7800-mesh talcum powder, the dispersing agent is stearic acid, and the lubricating agent is oxidized polyethylene wax.
As a further scheme of the invention: the antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite, and the antistatic agent is N, N-dihydroxyethyl octadecylamine.
The preparation method of the biodegradable polyester film comprises the following steps:
adding 40-70 parts of ethanol and 3-7 parts of ethyl orthosilicate into a high-speed mixing pot with heating and stirring functions, stirring in a water bath at 80 ℃ for 1h at a high speed, adding 10-40 parts of starch, stirring at a high speed to form gel, aging for 6h, and drying in vacuum at 80 ℃ for 2h to obtain a SiO2@ starch material;
adding 3-50 parts of hard biodegradable resin, 35-98 parts of soft biodegradable resin, 4-40 parts of SiO2@ starch, 0.1-5 parts of compatibilizer, 0.5-2 parts of coupling agent, 1-6 parts of opening agent, 0.3-2 parts of dispersing agent, 0.1-2 parts of lubricating agent, 0.2-1 part of antioxidant and 0.1-2 parts of antistatic agent into a high-speed mixing pot, mixing at low speed for 15min, uniformly mixing, adding into a double-screw extruder, and carrying out mixing, melting, extruding and granulating to prepare biodegradable polyester particles;
and (3) preparing the biodegradable polyester particles by adopting a film blowing process to obtain the biodegradable polyester film.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a biodegradable polyester film and a preparation method thereof, which avoid the problems of complex process, starch retrogradation, uneven plasticization, water absorption and stickiness and easy scorching of starch plasticized by plasticizers (glycerol, sorbitol and the like) in the prior art.
Detailed Description
Example 1
Adding 60kg of ethanol and 4kg of ethyl orthosilicate into a high-speed mixing kettle with heating and stirring functions, stirring in a water bath at 80 ℃ for 1h at a high speed, adding 20kg of corn starch, stirring at a high speed to form gel, aging for 6h, and drying in vacuum at 80 ℃ for 2h to obtain a SiO2@ starch material;
adding 20kg of hard biodegradable resin, 50kg of soft biodegradable resin, 30kg of SiO2@ starch, 1.5kg of isopropyl tris (dioctyl pyrophosphato acyloxy), 4kg of talcum powder, 1kg of stearic acid, 1kg of oxidized polyethylene wax, 0.5kg of tris [ 2.4-di-tert-butylphenyl ] phosphite and 0.5kg of N, N-dihydroxyethyl octadecylamine into a high-speed mixing pot, mixing at a low speed for 15min, adding a double-screw extruder after mixing uniformly, and carrying out mixing, melting, extruding and granulating to prepare biodegradable polyester granules;
and drying the prepared biodegradable polyester particles at 80 ℃ for 4h before film blowing, and then preparing the biodegradable polyester film by adopting a film blowing process.
Example 2
Adding 60kg of ethanol and 4kg of ethyl orthosilicate into a high-speed mixing kettle with heating and stirring functions, stirring in a water bath at 80 ℃ for 1h at a high speed, adding 20kg of cassava starch, stirring at a high speed to form gel, aging for 6h, and drying in vacuum at 80 ℃ for 2h to obtain a SiO2@ starch material;
adding 10kg of hard biodegradable resin, 65kg of soft biodegradable resin, 15kg of SiO2@ starch, 1.5kg of isopropyl tris (dioctyl pyrophosphato acyloxy), 3kg of talcum powder, 1kg of stearic acid, 1kg of oxidized polyethylene wax, 0.5kg of tris [ 2.4-di-tert-butylphenyl ] phosphite and 0.5kg of N, N-dihydroxyethyl octadecylamine into a high-speed mixing pot, mixing at a low speed for 15min, adding a double-screw extruder after mixing uniformly, and carrying out mixing, melting, extruding and granulating to prepare biodegradable polyester granules;
and drying the prepared biodegradable polyester particles at 80 ℃ for 4h before film blowing, and then preparing the biodegradable polyester film by adopting a film blowing process.
Example 3
Adding 65kg of ethanol and 5kg of ethyl orthosilicate into a high-speed mixing kettle with heating and stirring functions, stirring in a water bath at 80 ℃ for 1h at a high speed, adding 30kg of corn starch, stirring at a high speed to form gel, aging for 6h, and drying in vacuum at 80 ℃ for 2h to obtain a SiO2@ starch material;
adding 5kg of hard biodegradable resin, 70kg of soft biodegradable resin, 35kg of SiO2@ starch, 1.5kg of isopropyl tris (dioctyl pyrophosphato acyloxy), 2kg of talcum powder, 0.5kg of stearic acid, 0.5kg of oxidized polyethylene wax, 0.5kg of tris [ 2.4-di-tert-butylphenyl ] phosphite and 0.5kg of N, N-dihydroxyethyl octadecylamine into a high-speed mixing pot, mixing at a low speed for 15min, uniformly mixing, adding into a double-screw extruder, mixing, melting, extruding and granulating to prepare biodegradable polyester granules;
and drying the prepared biodegradable polyester particles at 80 ℃ for 4h before film blowing, and then preparing the biodegradable polyester film by adopting a film blowing process.
Example 4
Adding 65kg of ethanol and 6kg of ethyl orthosilicate into a high-speed mixing kettle with a heating and stirring function, stirring in a water bath at 80 ℃ for 1h at a high speed, adding 30kg of cassava starch, stirring at a high speed to form gel, aging for 6h, and drying in vacuum at 80 ℃ for 2h to obtain a SiO2@ starch material;
adding 8kg of hard biodegradable resin, 60kg of soft biodegradable resin, 20kg of SiO2@ starch, 1kg of isopropyl tris (dioctyl pyrophosphato acyloxy), 2kg of talcum powder, 2kg of stearic acid, 0.5kg of oxidized polyethylene wax, 0.5kg of tris [ 2.4-di-tert-butylphenyl ] phosphite and 0.5kg of N, N-dihydroxyethyl octadecylamine into a high-speed mixing pot, mixing at a low speed for 15min, adding a double-screw extruder after mixing uniformly, and carrying out mixing, melting, extruding and granulating to prepare biodegradable polyester granules;
and drying the prepared biodegradable polyester particles at 80 ℃ for 4h before film blowing, and then preparing the biodegradable polyester film by adopting a film blowing process.
Equipment: friend jia mechanical film blowing machine
Temperature distribution: 150/160/170/175/165/150 deg.C
Winding speed: 3-7m/min
Screw rotation speed: 15-60rpm
And (3) test results:
the mechanical properties of a biodegradable polyester film prepared in examples 1 to 4 were respectively measured, and the results are shown in the following table:
TABLE 1
Note: tensile strength and elongation at break were tested with reference to the standard GB/T1040.3-2006
The biological decomposition rate is tested according to the standard of ASTMD6400/EN13432
In summary, the following steps: the invention provides a biodegradable polyester film and a preparation method thereof, wherein tetraethoxysilane is adopted for hydrolyzing and coating starch, so that the surface of the starch is coated with a SiO2 layer, the starch is favorably dispersed in biodegradable polyester, the problems of grain points, pocking marks, scorching, starch water absorption stickiness and starch regeneration do not exist in finished products of granulation and film blowing, the preparation process is simple, the obtained biodegradable film has high biodegradation rate and excellent mechanical property, and the biodegradable film belongs to an environment-friendly product.
Claims (9)
1. The biodegradable polyester film is characterized by comprising the following raw materials in parts by weight:
3-50 parts of hard biodegradable resin, 35-98 parts of soft biodegradable resin, 4-60 parts of starch, 3-7 parts of ethyl orthosilicate, 40-70 parts of ethanol, 0.1-5 parts of compatibilizer, 0.5-2 parts of coupling agent, 1-6 parts of opening agent, 0.3-2 parts of dispersant, 0.1-2 parts of lubricant, 0.2-1 part of antioxidant and 0.1-2 parts of antistatic agent.
2. The biodegradable polyester film as claimed in claim 1, wherein the starch is one or more of corn starch, tapioca starch, potato starch, wheat starch.
3. The biodegradable polyester film as claimed in claim 1, wherein the hard biodegradable resin is polylactic acid having an optical purity of 95% or more and an MFR (190 ℃, 2.16kg) of 3 to 9g/10 min.
4. The biodegradable polyester film as claimed in claim 1, wherein the soft biodegradable resin is one or a blend of polybutylene terephthalate-adipate, polybutylene succinate-adipate, polybutylene succinate-co-polybutylene terephthalate copolyester, polydioxanone, and polypropylene carbonate.
5. The biodegradable polyester film as claimed in claim 4, wherein the soft biodegradable resin is one or a blend of two of polybutylene terephthalate-adipate, polybutylene succinate-adipate and polybutylene succinate.
6. The biodegradable polyester film as claimed in claim 1, wherein said coupling agent is isopropyltris (dioctylpyrophosphate).
7. The biodegradable polyester film as claimed in claim 1, wherein said opening agent is 7800 mesh talc, said dispersing agent is stearic acid, and said lubricant is oxidized polyethylene wax.
8. The biodegradable polyester film as claimed in claim 1, wherein said antioxidant is tris [ 2.4-di-tert-butylphenyl ] phosphite and said antistatic agent is N, N-dihydroxyethyl octadecylamine.
9. A method for preparing a biodegradable polyester film according to any one of claims 1 to 8, comprising the steps of:
adding 40-70 parts of ethanol and 3-7 parts of ethyl orthosilicate into a high-speed mixing pot with heating and stirring functions, stirring in a water bath at 80 ℃ for 1h at a high speed, adding 10-40 parts of starch, stirring at a high speed to form gel, aging for 6h, and drying in vacuum at 80 ℃ for 2h to obtain a SiO2@ starch material;
adding 3-50 parts of hard biodegradable resin, 35-98 parts of soft biodegradable resin, 4-40 parts of SiO2@ starch, 0.1-5 parts of compatibilizer, 0.5-2 parts of coupling agent, 1-6 parts of opening agent, 0.3-2 parts of dispersing agent, 0.1-2 parts of lubricating agent, 0.2-1 part of antioxidant and 0.1-2 parts of antistatic agent into a high-speed mixing pot, mixing at low speed for 15min, uniformly mixing, adding into a double-screw extruder, and carrying out mixing, melting, extruding and granulating to prepare biodegradable polyester particles;
and (3) preparing the biodegradable polyester particles by adopting a film blowing process to obtain the biodegradable polyester film.
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| CN114957933A (en) * | 2022-06-20 | 2022-08-30 | 万华化学集团股份有限公司 | Starch-based biodegradable PBAT modified material and preparation method thereof |
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