CN113549309A - Low-cost biodegradable film and preparation method thereof - Google Patents
Low-cost biodegradable film and preparation method thereof Download PDFInfo
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- CN113549309A CN113549309A CN202110882551.5A CN202110882551A CN113549309A CN 113549309 A CN113549309 A CN 113549309A CN 202110882551 A CN202110882551 A CN 202110882551A CN 113549309 A CN113549309 A CN 113549309A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000881 Modified starch Polymers 0.000 claims description 32
- 239000004368 Modified starch Substances 0.000 claims description 32
- 235000019426 modified starch Nutrition 0.000 claims description 31
- 229920002261 Corn starch Polymers 0.000 claims description 29
- 239000008120 corn starch Substances 0.000 claims description 29
- 229920001896 polybutyrate Polymers 0.000 claims description 23
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 22
- 239000004626 polylactic acid Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- 239000004970 Chain extender Substances 0.000 claims description 13
- 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 description 13
- 238000010096 film blowing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- RQMWTTLUOXUKQW-UHFFFAOYSA-N 2-isocyanatoethoxy(trimethyl)silane Chemical compound C[Si](C)(C)OCCN=C=O RQMWTTLUOXUKQW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000856 Amylose Polymers 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 150000008301 phosphite esters Chemical group 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000008107 starch Substances 0.000 description 12
- 235000019698 starch Nutrition 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound 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 description 3
- 229920000704 biodegradable plastic Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- -1 trimethylsiloxyethyl carbamate Chemical compound 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-UHFFFAOYSA-N alpha-D-glucopyranose Natural products OCC1OC(O)C(O)C(O)C1O WQZGKKKJIJFFOK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-DVKNGEFBSA-N alpha-D-glucose Chemical group OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-DVKNGEFBSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 1
- JYLRDAXYHVFRPW-UHFFFAOYSA-N butane-1,1-diol;terephthalic acid Chemical compound CCCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 JYLRDAXYHVFRPW-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
-
- 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
-
- 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
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- 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)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a low-cost biodegradable film and a preparation method thereof, and relates to the technical field of biodegradable films.
Description
The technical field is as follows:
the invention relates to the technical field of biodegradable films, in particular to a low-cost biodegradable film and a preparation method thereof.
Background art:
PBAT belongs to thermoplastic biodegradable plastics, is a copolymer of butanediol adipate and butanediol terephthalate, and has good ductility and elongation at break as well as good heat resistance and impact performance; in addition, the biodegradable plastic has excellent biodegradability, and is one of the best degradable materials for active and market application in biodegradable plastic research. Under the plastic limit, measures and strength for treating plastic pollution are continuously upgraded all over the country, and a wide market space is met for degradable materials such as PBAT.
But the PBAT capacity is not completely released at the present stage, so that the PBAT price on the market is seriously increased, and the price of the product is finally influenced.
The invention content is as follows:
the invention aims to solve the technical problem of providing a low-cost biodegradable film and a preparation method thereof, wherein the dosage of PBAT is reduced by adding modified starch, and the production cost is reduced while the mechanical property and the degradation property of a film product are not influenced.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the invention aims to provide a low-cost biodegradable film which is prepared from the following raw materials in parts by weight:
40-60 parts of PBAT, 5-20 parts of PLA, 20-40 parts of modified starch, 1-5 parts of talcum powder, 0.3-1 part of chain extender, 0.1-1 part of dispersant, 0.2-1 part of opening agent and 0.1-1 part of antioxidant.
PLA, also called polylactide as english abbreviation of polylactic acid, is a polyester polymer obtained by polymerizing lactic acid as a main raw material, has sufficient and renewable raw material sources, and mainly uses corn, cassava and the like as raw materials; the production process of polylactic acid is pollution-free, and can be biodegraded to realize the circulation in nature, so the polylactic acid is an ideal green high polymer material.
Starch belongs to a natural high molecular material which can be completely biodegraded, the basic constitutional unit is alpha-D-glucopyranose, and covalent polymers formed by connecting glucose together through glycosidic bonds after water molecules are removed from the glucose are starch molecules; the starch has wide source and low price and can be repeatedly regenerated; the starch has hydrogen bonds among molecules, poor solubility, hydrophilicity but difficult water solubility, no melting process during heating, and large polarity difference between the starch and the plastic resin, which leads to poor blending compatibility, so that the mechanical property of the plastic film is reduced due to the increase of the starch content.
The melt index of the PBAT and PLA is 2-10g/10min (190 ℃/2.16 kg).
The modified starch is prepared by taking trimethyl siloxyethyl isocyanate as a modifier.
If A-OH represents a starch molecule, the reaction equation for starch with trimethylsiloxyethyl isocyanate is shown below:
the reaction mechanism is as follows: hydroxyl contained in the molecular structure of the starch reacts with isocyanate groups contained in the molecular structure of trimethylsiloxyethyl isocyanate, and trimethylsiloxyethyl carbamate is grafted to the starch molecules to obtain the modified starch with a novel structure.
The preparation method of the modified starch comprises the following steps: drying corn starch, dissolving the dried corn starch in N, N-dimethylformamide, adding trimethylsiloxyethyl isocyanate and a catalytic amount of dibutyltin dilaurate, heating a reaction system to a reflux state, carrying out heat preservation reaction in the reflux state, continuing reflux reaction for a period of time after the viscosity is not changed, stopping heating, cooling, filtering, adding water into filtrate for washing, carrying out suction filtration, taking filter residues, and drying to obtain modified starch.
The molar ratio of the corn starch to the trimethylsiloxyethyl isocyanate is 2-3:1, and the molar weight of the corn starch is calculated by the contained hydroxyl. Partial hydroxyl in the molecular structure of the starch participates in the reaction, and partial hydroxyl is reserved to ensure the biodegradability of the modified starch.
The mass percentage of amylose in the corn starch is 20-50%.
The talcum powder is nano talcum powder.
The chain extender is an epoxy polymerization type chain extender, and preferably a KL-E chain extender.
The dispersing agent is ethylene bis stearamide or calcium stearate.
The opening agent is erucamide.
The antioxidant is phosphite ester antioxidant.
Another object of the present invention is to provide a method for preparing a low-cost biodegradable film, comprising the following steps:
(1) drying PBAT and PLA;
(2) mixing PBAT, PLA, modified starch, talcum powder, a chain extender, a dispersing agent, an opening agent and an antioxidant according to a weight ratio, adding into a high-speed stirrer, and uniformly mixing;
(3) transferring the uniformly mixed raw materials into a double-screw granulator for melt extrusion, and granulating after cooling to obtain granules;
(4) and (3) placing the obtained granules into a film blowing machine for film blowing to obtain the biodegradable film.
The granulation temperature of the double-screw granulator is 150-160 ℃, and the extrusion speed is 20-30 Hz.
The screw temperature of the film blowing machine is 150-155 ℃, and the extrusion speed is 25-35 Hz.
The invention has the beneficial effects that: the biodegradable film is prepared by adopting the PBAT, the PLA, the modified starch, the talcum powder, the chain extender, the dispersant, the opening agent and the antioxidant as raw materials, wherein the dosage of the PBAT and the PLA is reduced by adding the modified starch, so that the processing cost of the film is reduced, the mechanical property and the degradation property of the film can be ensured, and the problems of high processing cost of the conventional PBAT/PLA biodegradable film and obvious reduction of the mechanical property caused by directly adding the starch are solved.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easily understood, the invention is further described with reference to the specific embodiments.
PBAT is from Shanxi (Shanghai) Chemicals Co., Ltd and has a melt index of 2-4g/10min (190 ℃/2.16 kg).
PLA is from Zhejiang Haizhen biomaterial GmbH, and has a melt index of 2-10g/10min (190 deg.C/2.16 kg).
The nano talcum powder is sourced from talc technology development limited company in Guilin city, and the specification is 1250 meshes.
The corn starch is from Suzhou Qiding chemical industry, Limited liability company, and the content is more than 99%.
Example 1
1. Preparing modified starch:
drying corn starch at 110 ℃, dissolving the corn starch in N, N-dimethylformamide, then adding 0.5mol of trimethyl siloxyethyl isocyanate and a catalytic amount of dibutyltin dilaurate, wherein the molar ratio of the corn starch to the trimethyl siloxyethyl isocyanate is 2:1 (the molar amount of the corn starch is calculated by the contained hydroxyl), the using amount of dibutyltin dilaurate is 0.25 percent of the mass of the corn starch, heating the reaction system to a reflux state, carrying out heat preservation reaction for 6 hours under the reflux state, continuing reflux reaction for 30 minutes after the viscosity is not changed, stopping heating, cooling, filtering, adding water into filtrate for washing, carrying out suction filtration, taking filter residues for drying, and obtaining the modified starch.
2. Preparing a biodegradable film:
(1) PBAT and PLA were dried at 100 ℃.
(2) 55 parts of PBAT, 12 parts of PLA, 24 parts of the modified starch prepared above, 3 parts of nano talcum powder, 0.5 part of KL-E4370 chain extender, 0.5 part of calcium stearate, 0.3 part of erucamide and 0.2 part of antioxidant 168 are mixed according to the weight ratio and added into a high-speed stirrer to be uniformly mixed.
(3) And (3) transferring the uniformly mixed raw materials into a double-screw granulator for melt extrusion, wherein the granulation temperature is 160 ℃, the extrusion speed is 25Hz, and cooling and granulating to obtain granules.
(4) And (3) placing the obtained granules into a film blowing machine for film blowing, wherein the temperature of a screw is 155 ℃, and the extrusion speed is 30Hz, so that the biodegradable film is obtained.
The drying is based on the fact that the mass of the solid is not changed within 30 min.
Example 2
1. Preparing modified starch:
drying corn starch at 110 ℃, dissolving the corn starch in N, N-dimethylformamide, then adding 0.5mol of trimethyl siloxyethyl isocyanate and a catalytic amount of dibutyltin dilaurate, wherein the molar ratio of the corn starch to the trimethyl siloxyethyl isocyanate is 2.5:1 (the molar amount of the corn starch is calculated by the contained hydroxyl group), the using amount of the dibutyltin dilaurate is 0.25 percent of the mass of the corn starch, heating the reaction system to a reflux state, carrying out heat preservation reaction for 6 hours under the reflux state, continuing the reflux reaction for 30 minutes after the viscosity is not changed, stopping heating, cooling, filtering, adding water into filtrate, washing, carrying out suction filtration, taking filter residues, and drying to obtain the modified starch.
2. Preparing a biodegradable film:
(1) PBAT and PLA were dried at 100 ℃.
(2) 50 parts of PBAT, 15 parts of PLA, 22 parts of the prepared modified starch, 4 parts of nano talcum powder, 0.5 part of KL-E4370 chain extender, 0.5 part of ethylene bis stearamide, 0.5 part of erucamide and 0.25 part of antioxidant 168 are mixed according to the weight ratio and added into a high-speed stirrer to be uniformly mixed.
(3) And (3) transferring the uniformly mixed raw materials into a double-screw granulator for melt extrusion, wherein the granulation temperature is 160 ℃, the extrusion speed is 20Hz, and cooling and granulating to obtain granules.
(4) And (3) placing the obtained granules into a film blowing machine for film blowing, wherein the temperature of a screw is 150 ℃, and the extrusion speed is 25Hz, so as to obtain the biodegradable film.
The drying is based on the fact that the mass of the solid is not changed within 30 min.
Example 3
1. Preparing modified starch:
drying corn starch at 110 ℃, dissolving the corn starch in N, N-dimethylformamide, then adding 0.5mol of trimethyl siloxyethyl isocyanate and a catalytic amount of dibutyltin dilaurate, wherein the molar ratio of the corn starch to the trimethyl siloxyethyl isocyanate is 3:1 (the molar amount of the corn starch is calculated by the contained hydroxyl), the using amount of dibutyltin dilaurate is 0.3% of the mass of the corn starch, heating the reaction system to a reflux state, carrying out heat preservation reaction for 8 hours under the reflux state, continuing the reflux reaction for 30min after the viscosity is not changed, stopping heating, cooling, filtering, adding water into filtrate for washing, carrying out suction filtration, taking filter residues for drying, and obtaining the modified starch.
2. Preparing a biodegradable film:
(1) PBAT and PLA were dried at 100 ℃.
(2) 60 parts of PBAT, 16 parts of PLA, 25 parts of the prepared modified starch, 4 parts of nano talcum powder, 0.6 part of KL-E4370 chain extender, 0.5 part of calcium stearate, 0.4 part of erucamide and 0.3 part of antioxidant 168 are mixed according to the weight ratio and added into a high-speed stirrer to be uniformly mixed.
(3) And (3) transferring the uniformly mixed raw materials into a double-screw granulator for melt extrusion, wherein the granulation temperature is 160 ℃, the extrusion speed is 30Hz, and cooling and granulating to obtain granules.
(4) And (3) placing the obtained granules into a film blowing machine for film blowing, wherein the temperature of a screw is 155 ℃, and the extrusion speed is 35Hz, so as to obtain the biodegradable film.
The drying is based on the fact that the mass of the solid is not changed within 30 min.
Comparative example 1
Comparative example 1 was prepared by replacing methylsiloxyethyl isocyanate used in the preparation of the modified starch of example 3 with glycerol and the procedure was otherwise exactly the same as in example 3.
Comparative example 2
Comparative example 2 was prepared by replacing the modified starch used in the preparation of the biodegradable film of example 3 with unmodified corn starch, and the rest of the preparation procedure was exactly the same as in example 3.
Comparative example 3
Comparative example 3 was prepared by removing the modified starch of example 3, i.e., neither modified starch nor unmodified corn starch was added, and adding the modified starch in an amount superimposed on the amount of PLA, and the remaining preparation steps were identical to those of example 3.
The biodegradable films prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to tensile strength tests, testing the tensile strength in the machine direction according to standard GB/T1040.3-2006, with sample dimensions of 200X 15X 0.02mm and a tensile rate of 300 mm/min.
The test results are given in the following table:
| group of | Tensile strength/MPa |
| Example 1 | 26.8 |
| Example 2 | 27.2 |
| Example 3 | 27.9 |
| Comparative example 1 | 22.5 |
| Comparative example 2 | 20.3 |
| Comparative example 3 | 28.4 |
As is clear from the data in the above table, examples 1-3 did not cause a significant decrease in the tensile strength of the film by the preparation and addition of the modified starch, but both the addition of the glycerin-modified starch of comparative example 1 and the addition of the unmodified corn starch of comparative example 2 caused a significant decrease in the tensile strength of the film. And examples 1-3 can reduce the amount of PLA by the addition of the modified starch, thereby reducing the preparation cost of the film.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The low-cost biodegradable film is characterized by being prepared from the following raw materials in parts by weight:
40-60 parts of PBAT, 5-20 parts of PLA, 20-40 parts of modified starch, 1-5 parts of talcum powder, 0.3-1 part of chain extender, 0.1-1 part of dispersant, 0.2-1 part of opening agent and 0.1-1 part of antioxidant.
2. The low cost biodegradable film according to claim 1, characterized in that: the melt index of the PBAT and PLA is 2-10g/10min (190 ℃/2.16 kg).
3. The low cost biodegradable film according to claim 1, characterized in that: the modified starch is prepared by taking trimethyl siloxyethyl isocyanate as a modifier.
4. The low cost biodegradable film according to claim 3, characterized in that: the preparation method of the modified starch comprises the following steps: drying corn starch, dissolving the dried corn starch in N, N-dimethylformamide, adding trimethylsiloxyethyl isocyanate and a catalytic amount of dibutyltin dilaurate, heating a reaction system to a reflux state, carrying out heat preservation reaction in the reflux state, continuing reflux reaction for a period of time after the viscosity is not changed, stopping heating, cooling, filtering, adding water into filtrate, washing, carrying out suction filtration, and drying filter residues to obtain modified starch.
5. The low cost biodegradable film according to claim 4, characterized in that: the molar ratio of the corn starch to the trimethylsiloxyethyl isocyanate is 2-3:1, and the molar weight of the corn starch is calculated by the contained hydroxyl.
6. The low cost biodegradable film according to claim 4, characterized in that: the mass percentage of amylose in the corn starch is 20-50%.
7. The low cost biodegradable film according to claim 1, characterized in that: the talcum powder is nano talcum powder; the chain extender is an epoxy polymerization type chain extender; the dispersing agent is ethylene bis stearamide or calcium stearate; the opening agent is erucamide; the antioxidant is phosphite ester antioxidant.
8. The method for preparing a low-cost biodegradable film according to any one of claims 1 to 7, comprising the steps of:
(1) drying PBAT and PLA;
(2) mixing PBAT, PLA, modified starch, talcum powder, a chain extender, a dispersing agent, an opening agent and an antioxidant according to a weight ratio, adding into a high-speed stirrer, and uniformly mixing;
(3) transferring the uniformly mixed raw materials into a double-screw granulator for melt extrusion, and granulating after cooling to obtain granules;
(4) and (3) placing the obtained granules into a film blowing machine for film blowing to obtain the biodegradable film.
9. The method of claim 8, wherein the step of preparing the biodegradable film comprises: the granulation temperature of the double-screw granulator is 150-160 ℃, and the extrusion speed is 20-30 Hz.
10. The method of claim 8, wherein the step of preparing the biodegradable film comprises: the screw temperature of the film blowing machine is 150-155 ℃, and the extrusion speed is 25-35 Hz.
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| JPH06306103A (en) * | 1993-04-23 | 1994-11-01 | Nichiden Kagaku Kk | Modified starch, manufacture thereof, and resin composition comprising the same |
| CN112111133A (en) * | 2020-08-17 | 2020-12-22 | 江苏碧升生物新材料有限公司 | Preparation method of polybutylene terephthalate adipate/polylactic acid/starch ternary blending film blowing resin |
| CN112430385A (en) * | 2020-12-03 | 2021-03-02 | 辽宁金科塑胶科技有限公司 | Fully-degradable membrane material and preparation and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06306103A (en) * | 1993-04-23 | 1994-11-01 | Nichiden Kagaku Kk | Modified starch, manufacture thereof, and resin composition comprising the same |
| CN112111133A (en) * | 2020-08-17 | 2020-12-22 | 江苏碧升生物新材料有限公司 | Preparation method of polybutylene terephthalate adipate/polylactic acid/starch ternary blending film blowing resin |
| CN112430385A (en) * | 2020-12-03 | 2021-03-02 | 辽宁金科塑胶科技有限公司 | Fully-degradable membrane material and preparation and application thereof |
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