CN111825967B - High-folding-resistance polylactic acid/thermoplastic starch composite material and application thereof - Google Patents
High-folding-resistance polylactic acid/thermoplastic starch composite material and application thereof Download PDFInfo
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- CN111825967B CN111825967B CN202010752158.XA CN202010752158A CN111825967B CN 111825967 B CN111825967 B CN 111825967B CN 202010752158 A CN202010752158 A CN 202010752158A CN 111825967 B CN111825967 B CN 111825967B
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- starch
- thermoplastic starch
- polylactic acid
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- elastomer
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 114
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 114
- 229920008262 Thermoplastic starch Polymers 0.000 title claims abstract description 99
- 239000004628 starch-based polymer Substances 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 229920002472 Starch Polymers 0.000 claims abstract description 45
- 239000008107 starch Substances 0.000 claims abstract description 43
- 235000019698 starch Nutrition 0.000 claims abstract description 43
- 229920001971 elastomer Polymers 0.000 claims abstract description 30
- 239000000806 elastomer Substances 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000004014 plasticizer Substances 0.000 claims abstract description 10
- 238000005469 granulation Methods 0.000 claims abstract description 9
- 230000003179 granulation Effects 0.000 claims abstract description 9
- 239000005003 food packaging material Substances 0.000 claims abstract description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 54
- 238000006065 biodegradation reaction Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- 229920002261 Corn starch Polymers 0.000 claims description 3
- 239000008120 corn starch Substances 0.000 claims description 3
- 235000019265 sodium DL-malate Nutrition 0.000 claims description 3
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 3
- 239000001394 sodium malate Substances 0.000 claims description 3
- 239000001433 sodium tartrate Substances 0.000 claims description 3
- 229960002167 sodium tartrate Drugs 0.000 claims description 3
- 235000011004 sodium tartrates Nutrition 0.000 claims description 3
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 claims description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 229920001244 Poly(D,L-lactide) Polymers 0.000 claims description 2
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 claims description 2
- 229920001434 poly(D-lactide) Polymers 0.000 claims description 2
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 229940074404 sodium succinate Drugs 0.000 claims description 2
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 20
- 238000012545 processing Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 229920000728 polyester Polymers 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 12
- 238000011056 performance test Methods 0.000 description 10
- CTERCLHSWSQHSD-UHFFFAOYSA-N 8-methoxypyrene-1,3,6-trisulfonic acid Chemical compound C1=C2C(OC)=CC(S(O)(=O)=O)=C(C=C3)C2=C2C3=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1 CTERCLHSWSQHSD-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920000229 biodegradable polyester Polymers 0.000 description 2
- 239000004622 biodegradable polyester Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002253 Tannate Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 poly butylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- YPSNMKHPDJVGEX-UHFFFAOYSA-L potassium;sodium;3-carboxy-3-hydroxypentanedioate Chemical compound [Na+].[K+].OC(=O)CC(O)(C([O-])=O)CC([O-])=O YPSNMKHPDJVGEX-UHFFFAOYSA-L 0.000 description 1
- CJWHWKXAABCWLT-UHFFFAOYSA-L potassium;sodium;butanedioate Chemical compound [Na+].[K+].[O-]C(=O)CCC([O-])=O CJWHWKXAABCWLT-UHFFFAOYSA-L 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
- B29B7/826—Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
- B29B7/92—Wood chips or wood fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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
- C08L2201/06—Biodegradable
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention belongs to the technical field of biodegradable materials, and discloses a fully biodegradable polylactic acid/thermoplastic starch composite material with high folding resistance and low cost and an application thereof. The composite material is obtained by melt extrusion and granulation of polylactic acid and modified thermoplastic starch elastomer; the modified thermoplastic starch elastomer is prepared by mixing starch, a plasticizer and an organic polybasic acid metal salt, and then extruding and granulating. The invention adopts proper organic polybasic acid metal salt and processing technique to obtain the thermoplastic starch elastomer with low modulus and high extensibility, and then the thermoplastic starch elastomer is compounded with polylactic acid to obtain the polylactic acid/thermoplastic starch composite material with high performance and reduced cost, the folding endurance times of the composite material exceed 1000 times, the addition amount of the modified thermoplastic starch elastomer can exceed 20 wt%, the defects of reduced mechanical property of polyester blend caused by the addition of traditional thermoplastic starch, large polyester degradation amplitude caused by higher carboxyl content and the like are overcome, and the composite material can be applied to the fields of food packaging materials and the like.
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, and particularly relates to a fully biodegradable polylactic acid/thermoplastic starch composite material with high folding resistance and low cost and an application thereof.
Background
The development of fully biodegradable polymers to replace traditional petroleum-based polymers is an important way to achieve sustainable development. Polylactic acid is biodegradable polyester of a bio-based source, has excellent comprehensive performance and is one of the most potential green macromolecules. However, the polylactic acid has relatively high production cost and high brittleness, and cannot be used in the field of flexible wearing, thereby greatly limiting the wide application of the polylactic acid. The cheap green natural high molecular starch or thermoplastic starch (TPS) and the TPS are adopted for melt blending, so that the cost is reduced, but the TPS is brittle and has poor compatibility with polylactic acid, and the mechanical property of the blend is reduced sharply with the increase of the addition amount of the TPS, so that the practical application of the polylactic acid/thermoplastic starch composite material is seriously hindered.
In order to solve the above problems, a chemically synthesized compatibilizer is generally used to improve the interfacial compatibility between the polylactic acid and the TPS. Different from the direction, natural organic acids such as citric acid, malic acid, tartaric acid and the like have a multi-carboxyl/hydroxyl structure, on one hand, the acid hydrolysis of starch can be realized, the rigid long-chain structure of the starch is damaged, so that the flexibility of the molecular chain segment of the starch is improved, a hydrogen bond crosslinking network can be formed between the acid carboxyl/hydroxyl and the starch hydroxyl to form a full biomass elastomer, and the multi-functional organic acids can also improve the interface compatibility of a polyester/starch blending system through a coupling effect. However, in the processing process, the existence of acidic micromolecules has catalytic degradation effect on full-biodegradable polyesters such as polylactic acid, poly butylene succinate and the like. Furthermore, the resulting product may accelerate the degradation of the polyester during storage, thereby reducing its useful life.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a polylactic acid/thermoplastic starch composite material which has high folding resistance, low cost and full biodegradation.
The invention also aims to provide the application of the polylactic acid/thermoplastic starch composite material with high folding resistance, low cost and full biodegradation in the field of food packaging materials.
The purpose of the invention is realized by the following scheme:
a polylactic acid/thermoplastic starch composite material with high folding resistance, low cost and full biodegradation is prepared from polylactic acid and modified thermoplastic starch elastomer through melt extrusion and granulating.
Wherein the mass ratio of the polylactic acid to the modified thermoplastic starch elastomer is preferably 9:1-6.5: 3.5.
Wherein the temperature of the melt extrusion is preferably 145-175 ℃.
Wherein the polylactic acid can be at least one of PLLA, PDLA, PDLLA and the like. The polylactic acid is dried for 4-12h at 80-100 ℃ for standby before use.
Furthermore, the modified thermoplastic starch elastomer is obtained by mixing starch, a plasticizer and an organic polybasic acid metal salt, and then extruding and granulating.
Wherein the organic polybasic acid metal salt can be at least one of sodium malate, sodium tartrate, potassium citrate, sodium succinate, potassium tannate, etc. The organic polybasic acid metal salt of the invention can form a gel crosslinking structure with the thermoplastic starch through ionic bonds and multiple hydrogen bonds, thereby obtaining the thermoplastic starch elastomer.
Wherein the mass ratio of the used organic polybasic acid metal salt to the sum of the starch and the plasticizer is 0.25:100-5: 100.
The plasticizer may be at least one of glycerol, ethylene glycol, pentaerythritol, urea, and the like, and preferably glycerol.
Wherein the mass ratio of the starch to the plasticizer is preferably 85:15-60:40, and more preferably 7: 3.
Wherein the temperature of the extrusion granulation is preferably 90-140 ℃.
Wherein the starch can be wheat starch, corn starch, potato starch, pea starch, cassava starch, yam starch, etc. The starch preferably has a water content of 2 to 13 wt.%.
The invention adopts starch as a matrix, and the starch and the organic polybasic acid metal salt form a gel crosslinking structure based on metal ions and multiple hydrogen bonds through gelatinization, thereby having the characteristics of a thermoplastic elastomer. Wherein, after extrusion granulation, the viscosity-average molecular weight of the system is reduced by 10-30%, and the carboxyl content is 0.1-0.8%.
The modified thermoplastic starch elastomer and the polylactic acid are compounded to prepare the polylactic acid/thermoplastic starch composite material with high folding endurance, low cost and full biodegradation, wherein when the modified thermoplastic starch elastomer is extruded in the preparation process, the organic polybasic acid metal salt has the functions of electrostatic adsorption, physical crosslinking and plasticization, the thermoplastic elastomer is shown, the organic hydrophobic part of the organic polybasic acid metal salt can realize that the thermoplastic starch elastomer and the polylactic acid have good interface compatibility, the folding endurance of the composite material can be obviously improved after the modified thermoplastic starch elastomer and the polylactic acid are compounded, and the application value in the field of flexible materials is shown. The preparation process has the advantages of high efficiency, environmental protection and the like, the adding proportion of each component is low, and all the used reagents are edible green materials.
According to the invention, an appropriate organic polybasic acid metal salt and a processing technology are adopted, an ionic group and multiple hydrogen bond acting forces are introduced into TPS at the same time, the thermoplastic starch elastomer with low modulus and high extensibility is obtained by regulating the molecular weight of starch in TPS, the classical acting force and the hydrogen bond strength, and then the thermoplastic starch elastomer is compounded with polylactic acid to obtain the polylactic acid/thermoplastic starch composite material with high performance and reduced cost, so that the influence of organic acid on the degradation performance of polyester is reduced, and the service life of the blend is prolonged.
The polylactic acid/thermoplastic starch composite material with high folding resistance, low cost and full biodegradation provided by the invention has good mechanical property and outstanding high folding resistance, the folding resistance times of the composite material exceed 1000 times, which are far higher than 16 times of pure PLA, the tensile strength is 28.8MPa, and higher Young modulus and unnotched impact strength are maintained, which are 1029MPa and 38.4KJ/m respectively2。
The invention overcomes the defects of reduced mechanical property of polyester blend caused by the addition of traditional thermoplastic starch, large polyester degradation amplitude caused by higher carboxyl content and the like, simultaneously, the processing technology is green and environment-friendly, and the obtained polylactic acid/thermoplastic starch composite material has excellent comprehensive performance, outstanding folding resistance and easy processing, and can be applied to the fields of food packaging materials, disposable tableware and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the processing is convenient and fast, and no pollution is caused: the organic polybasic acid metal salt in the composite material is ionized with the thermoplastic starch in the extrusion process, and multiple hydrogen bonds are constructed, and the introduced electrostatic acting force and multiple hydrogen bonds are beneficial to realizing the construction of physical cross-linking points, so that the rigid long-chain structure of the starch is damaged, the melt strength of the thermoplastic starch is reduced, the melt fluidity of the thermoplastic starch is improved, and the advantages of convenient plasticizing processing and elastic recovery and the like are achieved.
2. The polylactic acid/thermoplastic starch composite material has excellent folding resistance: under the catalytic action of the organic polybasic acid metal salt, the modified thermoplastic starch has good melt fluidity, can obtain good shear dispersion in a polylactic acid matrix, and has the elastomer-like characteristics of low modulus and high elongation; the hydrophobic part of the metal salt of the organic polyacid also has a coupling effect, which can improve the interfacial interaction between TPS and PLA. Thus, the modified thermoplastic starch-based elastomer can induce shear yielding of the polylactic acid matrix during folding, thereby enabling it to exhibit high folding resistance. The folding times are more than 1000 times, which is far higher than 16 times of pure PLA.
3. Green and environment-friendly: the raw materials of the invention are starch, green plasticizer, organic polybasic acid metal salt and polylactic acid, the processing process is convenient, no toxic and harmful substances are generated, the addition amount of the cheap modified thermoplastic starch elastomer is more than 20 wt%, and the blend has the effects of reducing cost and improving biodegradability.
Drawings
FIG. 1 is a graph showing the mechanical properties of TPS and MTPS-1 obtained in example 1.
FIG. 2 is a graph showing the folding endurance of PLA, PLA/TPS, and PLA/MTPS-1 of example 8 and PLA/MTPS-3 of example 9.
FIG. 3 is a graph showing the mechanical properties of PLA, PLA/TPS, and PLA/MTPS-1 of example 8 and PLA/MTPS-3 of example 9.
FIG. 4 is a microstructure of the frozen brittle fracture surface of PLA/TPS and PLA/MTPS-1 of example 8 and PLA/MTPS-3 of example 9.
FIG. 5 is a fractured surface micro-topography of PLA, PLA/TPS and PLA/MTPS-3 of example 9.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available without specific reference. The method is a conventional method unless otherwise specified. The preparation method adopts thermoplastic processing equipment comprising common plastic machinery such as an extruder, banburying and the like. The polylactic acid/thermoplastic starch composite material can be efficiently formed by injection molding, extrusion, mould pressing and other thermoplastic processing methods, and the forming temperature is between 170 and 210 DEG C
The following examples 1-7 are for the preparation of modified thermoplastic starch elastomers, wherein the starch is corn starch; the twin-screw extruder was model SHJ-26. The working parameters of the double-screw extruder are as follows: zone 1 is 90 deg.C, zone 2 is 120 deg.C, zone 3 is 130 deg.C, zone 4 is 140 deg.C, zone 5 is 145 deg.C, zone 6 is 145 deg.C, zone 7 is 140 deg.C, head temperature is 135 deg.C, and screw rotation speed is 80 rpm.
Example 1: preparation of modified thermoplastic starch elastomer
Premixing starch and glycerol according to a mass ratio of 7:3, adding 1 wt% of tartaric acid according to the total mass of the starch and the glycerol, and then extruding and granulating the mixture through a double-screw reaction to obtain modified thermoplastic starch (MTPS-1).
Example 2: preparation of modified thermoplastic starch elastomer
Premixing starch and glycerol according to a mass ratio of 7:3, adding 2 wt% of sodium tartrate according to the total mass of the starch and the glycerol, and then extruding and granulating the mixture through double-screw reaction to obtain modified thermoplastic starch (MTPS-2).
Example 3: preparation of modified thermoplastic starch elastomer
Premixing starch and glycerol according to a mass ratio of 7:3, adding 3 wt% of potassium sodium tartrate according to the total mass of the starch and the glycerol, mixing, and performing double-screw reaction extrusion and granulation on the mixture to obtain the modified thermoplastic starch (MTPS-3).
Example 4: preparation of modified thermoplastic starch elastomer
Premixing starch and glycerol according to a mass ratio of 7:3, adding 4 wt% of sodium potassium succinate according to the total mass of the starch and the glycerol, mixing, and performing double-screw reaction extrusion and granulation on the mixture to obtain the modified thermoplastic starch (MTPS-4).
Example 5: preparation of modified thermoplastic starch elastomer
Starch and glycerol are premixed according to the mass ratio of 7:3, then succinic acid with the weight percentage of 3 percent is added according to the total mass of the starch and the glycerol for mixing, and then the mixture is extruded and granulated through twin-screw reaction to obtain the modified thermoplastic starch (MTPS-5).
Example 6: preparation of modified thermoplastic starch elastomer
Premixing starch and glycerol according to a mass ratio of 7:3, adding 3 wt% of potassium sodium malate according to the total mass of the starch and the glycerol, mixing, and performing double-screw reaction extrusion and granulation on the mixture to obtain modified thermoplastic starch (MTPS-6).
Example 7: preparation of modified thermoplastic starch elastomer
Premixing starch and glycerol according to a mass ratio of 7:3, adding 2 wt% of sodium potassium citrate according to the total mass of the starch and the glycerol, mixing, and performing double-screw reaction extrusion and granulation on the mixture to obtain modified thermoplastic starch (MTPS-7).
Comparative example 1:
the thermoplastic starch (TPS) is prepared by premixing starch and glycerol according to the mass ratio of 7:3, and then extruding and granulating through double-screw reaction.
FIG. 1 is a graph showing the mechanical properties of TPS of comparative example 1 and MTPS-1 obtained in example 1. The tensile test was carried out according to GB/T1040-2006 at a speed of 5 mm/min. As can be seen from fig. 1: compared with TPS, MTPS-1 prepared by the invention shows low modulus and high elongation rate elastomer characteristics, which are mainly attributed to plasticizing and physical crosslinking effects of metal salts of organic polybasic acid.
Examples 8-18 below are for the preparation of the PLA/MTPS composite of the present invention, PLA being model 4032D from Nature Works, USA.
Comparative example 2:
the PLA/TPS is obtained by melt-extruding the thermoplastic starch (TPS) and the PLA in the mass ratio of 3:7 (the temperature is 145-175 ℃, the screw rotation speed is 80 r/min) and granulating in the prior art.
Example 8:
the MTPS-1 obtained in the example 1 and the PLA are premixed according to the mass ratio of 3:7, and then are extruded by a double screw reaction (the temperature is 145-.
Example 9:
the MTPS-1 obtained in the example 1 and the PLA are premixed according to the mass ratio of 1:9, and then are extruded by a twin-screw reaction (the temperature is 145-175 ℃, the screw rotating speed is 80 r/min) and cut into granules to obtain the PLA/MTPS-3 blend.
The composite material prepared as above was subjected to a performance test, and the results are shown in fig. 2 to 5.
FIG. 2 is a graph showing the folding endurance of PLA, PLA/TPS, and PLA/MTPS-1 of example 8 and PLA/MTPS-3 of example 9.
The folding endurance test mainly comprises the following steps: test specimens (40X 12X 2 mm) produced by injection molding were initially introduced3) One end of the specimen was fixed in a pneumatic jig and pre-folded once, then repeatedly folded at 180 ° (plus or minus 90 °) until the specimen broke, and the number of folds was recorded (plus or minus 90 ° was recorded as 1 time). The folding frequency was about 30 times/min, room temperature environment. Each sample was tested in triplicate and the results averaged. As can be seen from fig. 2: after the polylactic acid and the thermoplastic starch are blended, the mechanical property is sharply reduced, and the polylactic acid and the thermoplastic starch are broken after being folded; the PLA/MTPS composite material of the invention has excellent folding resistance, wherein the folding resistance times of the PLA/MTPS-1 are more than 1000 times and are far higher than 16 times of pure PLA.
FIG. 3 is a graph showing the mechanical properties of PLA, PLA/TPS, and PLA/MTPS-1 of example 8 and PLA/MTPS-3 of example 9.
The tensile test is carried out according to GB/T1040-2006, and the speed is 5 mm/min; unnotched impact tests were carried out according to GB/T1843-2008. As can be seen from fig. 3: the mechanical property of the polylactic acid and the thermoplastic starch after blending is reduced sharply, the PLA/MTPS composite material of the invention has good comprehensive mechanical property, the tensile strength, namely Young modulus and the like, is obviously improved compared with the PLA/TPS, and the unnotched impact strength is obviously higher than that of pure PLA.
FIG. 4 is a microstructure of the frozen brittle fracture surface of PLA/TPS and PLA/MTPS-1 of example 8 and PLA/MTPS-3 of example 9. As can be seen from fig. 4: compared with PLA/TPS, the PLA/MTPS composite material has improved interface compatibility, and the TPS has smaller and more uniform dispersion size.
FIG. 5 is a fractured surface micro-topography of PLA, PLA/TPS and PLA/MTPS-3 of example 9. As can be seen from fig. 5: compared with PLA and PLA/TPS, the fold section of the PLA/MTPS blend has a remarkable layered fibrillating structure, so that energy is dissipated in time by continuously increasing the surface area of the material in the folding process, the integral fracture of the material is avoided, and the PLA/MTPS blend has excellent folding resistance.
Example 10:
MTPS-1 obtained in example 1 and PLA are premixed according to the mass ratio of 2.5:7.5, and then are extruded by twin-screw reaction (the temperature is 145-175 ℃, the screw rotating speed is 80 r/min), and the mixture of PLA/MTPS-2 is obtained by cutting into granules. The performance test results are similar to those in embodiments 8 and 9, and are not repeated here.
Example 11:
the MTPS-2 obtained in the example 2 and the PLA are premixed according to the mass ratio of 1:9, and then are extruded by a double screw reaction (the temperature is 145-. The performance test results are similar to those in embodiments 8 and 9, and are not repeated here.
Example 12:
the MTPS-2 obtained in the example 2 and the PLA are premixed according to the mass ratio of 2:8, and then are extruded by a double screw reaction (the temperature is 145-. The performance test results are similar to those in embodiments 8 and 9, and are not repeated here.
Example 13:
MTPS-2 obtained in example 2 and PLA are premixed according to the mass ratio of 1.5:8.5, and then are extruded by twin-screw reaction (the temperature is 145-175 ℃, the screw rotation speed is 80 r/min), and the mixture of PLA/MTPS-6 is obtained by cutting into granules. The performance test results are similar to those in embodiments 8 and 9, and are not repeated here.
Example 14:
the MTPS-3 obtained in the example 3 and the PLA are premixed according to the mass ratio of 2:8, and then are extruded by a double screw reaction (the temperature is 145-. The performance test results are similar to those in embodiments 8 and 9, and are not repeated here.
Example 15:
the MTPS-3 obtained in the example 3 and the PLA are premixed according to the mass ratio of 3:7, and then are extruded by a double screw reaction (the temperature is 145-. The performance test results are similar to those in embodiments 8 and 9, and are not repeated here.
Example 16:
MTPS-4 obtained in example 4 and PLA are premixed according to the mass ratio of 3:7, and then a PLA/MTPS-9 blend is obtained by twin-screw reaction extrusion (temperature 145-. The performance test results are similar to those in embodiments 8 and 9, and are not repeated here.
Example 17:
MTPS-5 obtained in example 5 and PLA are premixed according to the mass ratio of 2:8, and then a PLA/MTPS-10 blend is obtained by twin-screw reaction extrusion (temperature 145-. The performance test results are similar to those in embodiments 8 and 9, and are not repeated here.
Example 18:
MTPS-6 obtained in example 6 and PLA are premixed according to the mass ratio of 2:8, and then a PLA/MTPS-11 blend is obtained by twin-screw reaction extrusion (temperature 145-. The performance test results are similar to those in embodiments 8 and 9, and are not repeated here.
In conclusion, the PLA/MTPS full-biodegradable composite material prepared by the invention has excellent folding resistance and good mechanical property. The optimal folding times of the composite material exceed 1000 times and are far greater than 16 times of PLA; the tensile strength is 27.2-28.8MPa, the Young modulus is 916-1029MPa, and the unnotched impact strength is 14.7KJ/m of pure PLA2The pressure is increased to 33.2-38.4KJ/m2. The method of the invention obviously improves the folding resistance of the PLA/TPS composite material, overcomes the defect of the reduction of the mechanical property of the polyester matrix caused by the addition of the traditional TPS, has the TPS content of 10-35 wt%, has the advantages of cost reduction and biodegradability improvement, and is convenient and pollution-free to process.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A polylactic acid/thermoplastic starch composite material with high folding resistance, low cost and full biodegradation is characterized in that the polylactic acid/thermoplastic starch composite material is obtained by melt extrusion and granulation of polylactic acid and modified thermoplastic starch elastomer; the modified thermoplastic starch elastomer is obtained by mixing starch, a plasticizer and an organic polybasic acid metal salt, and then extruding and granulating;
the organic polybasic acid metal salt comprises at least one of sodium malate, sodium tartrate, potassium citrate and sodium succinate;
the mass ratio of the polylactic acid to the modified thermoplastic starch elastomer is 9:1-6.5: 3.5;
the mass ratio of the organic polybasic acid metal salt to the sum of the starch and the plasticizer is 0.25:100-5: 100;
the plasticizer is glycerol.
2. The highly fold-resistant, low-cost, fully biodegradable polylactic acid/thermoplastic starch composite according to claim 1, characterized in that: the mass ratio of the starch to the plasticizer is 85:15-60: 40.
3. The highly fold-resistant, low-cost, fully biodegradable polylactic acid/thermoplastic starch composite according to claim 1, characterized in that: the melt extrusion temperature was 145-175 ℃.
4. The highly fold-resistant, low-cost, fully biodegradable polylactic acid/thermoplastic starch composite according to claim 1, characterized in that: the temperature of the extrusion granulation is 90-140 ℃.
5. The highly fold-resistant, low-cost, fully biodegradable polylactic acid/thermoplastic starch composite according to claim 1, characterized in that: the polylactic acid comprises at least one of PLLA, PDLA and PDLLA; the starch comprises at least one of wheat starch, corn starch, potato starch, pea starch, cassava starch and yam starch.
6. Use of the high folding endurance, low cost, fully biodegradable polylactic acid/thermoplastic starch composite material according to any one of claims 1 to 5 in the field of food packaging materials.
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| CN1354196A (en) * | 2001-12-17 | 2002-06-19 | 武汉华丽环保科技有限公司 | Starch-based biodegradable material and its preparation method |
| WO2008117682A1 (en) * | 2007-03-27 | 2008-10-02 | Sankyo Co., Ltd. | Non-animal derived soft capsule shell and soft capsule having the same |
| CN102408690A (en) * | 2011-09-28 | 2012-04-11 | 成都市新津事丰医疗器械有限公司 | Thermoplastic starch modified polylactic acid material |
| CN108929527A (en) * | 2018-07-10 | 2018-12-04 | 华南理工大学 | A kind of PBAT/ modified starch full-biodegradable film and its preparation method and application having both high ductibility and high obstructing performance |
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| CN1354196A (en) * | 2001-12-17 | 2002-06-19 | 武汉华丽环保科技有限公司 | Starch-based biodegradable material and its preparation method |
| WO2008117682A1 (en) * | 2007-03-27 | 2008-10-02 | Sankyo Co., Ltd. | Non-animal derived soft capsule shell and soft capsule having the same |
| CN102408690A (en) * | 2011-09-28 | 2012-04-11 | 成都市新津事丰医疗器械有限公司 | Thermoplastic starch modified polylactic acid material |
| CN108929527A (en) * | 2018-07-10 | 2018-12-04 | 华南理工大学 | A kind of PBAT/ modified starch full-biodegradable film and its preparation method and application having both high ductibility and high obstructing performance |
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