CN114806112B - Heat-resistant polylactic acid straw and preparation method thereof - Google Patents
Heat-resistant polylactic acid straw and preparation method thereof Download PDFInfo
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- CN114806112B CN114806112B CN202210302069.4A CN202210302069A CN114806112B CN 114806112 B CN114806112 B CN 114806112B CN 202210302069 A CN202210302069 A CN 202210302069A CN 114806112 B CN114806112 B CN 114806112B
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 118
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 118
- 239000010902 straw Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- -1 diglycolic acid butanediol ester Chemical class 0.000 claims abstract description 44
- 239000004970 Chain extender Substances 0.000 claims abstract description 21
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 19
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 18
- 239000003549 soybean oil Substances 0.000 claims abstract description 16
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 239000002667 nucleating agent Substances 0.000 claims abstract description 12
- 229920000414 polyfuran Polymers 0.000 claims abstract description 11
- 229920005692 JONCRYL® Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 10
- YLWQQYRYYZPZLJ-UHFFFAOYSA-N 12-hydroxy-n-[2-(12-hydroxyoctadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC(O)CCCCCC YLWQQYRYYZPZLJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 229920001634 Copolyester Polymers 0.000 claims description 3
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- OXDXXMDEEFOVHR-CLFAGFIQSA-N (z)-n-[2-[[(z)-octadec-9-enoyl]amino]ethyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCNC(=O)CCCCCCC\C=C/CCCCCCCC OXDXXMDEEFOVHR-CLFAGFIQSA-N 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- HETBCUMLBCUVKC-UHFFFAOYSA-N n-[2-(dodecanoylamino)ethyl]dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC HETBCUMLBCUVKC-UHFFFAOYSA-N 0.000 claims 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 13
- 238000005520 cutting process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005452 bending Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 230000035622 drinking Effects 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- AOJJSUZBOXZQNB-VTZDEGQISA-N 4'-epidoxorubicin Chemical group O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-VTZDEGQISA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- QEVGZEDELICMKH-UHFFFAOYSA-L 2-(carboxylatomethoxy)acetate Chemical compound [O-]C(=O)COCC([O-])=O QEVGZEDELICMKH-UHFFFAOYSA-L 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GFQOFGWPGYRLAO-UHFFFAOYSA-N dodecanamide;ethene Chemical compound C=C.CCCCCCCCCCCC(N)=O.CCCCCCCCCCCC(N)=O GFQOFGWPGYRLAO-UHFFFAOYSA-N 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- SWSBIGKFUOXRNJ-CVBJKYQLSA-N ethene;(z)-octadec-9-enamide Chemical compound C=C.CCCCCCCC\C=C/CCCCCCCC(N)=O.CCCCCCCC\C=C/CCCCCCCC(N)=O SWSBIGKFUOXRNJ-CVBJKYQLSA-N 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 235000012171 hot beverage Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D23/00—Producing tubular articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
- B29C2071/022—Annealing
-
- 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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a heat-resistant polylactic acid straw, which comprises the following raw materials in parts by weight based on 100 parts by weight of the total amount: 50-89 parts of polylactic acid; 5-15 parts of polyfurandicarboxylic acid/diglycolic acid butanediol ester; 5-30 parts of talcum powder; 0.3-1 part of nucleating agent; 0.2-1 part of chain extender; 0.3-2 parts of epoxidized soybean oil; 0.2-1 part of lubricant; the invention uses biodegradable poly furan dicarboxylic acid/diglycolic acid butanediol ester as the toughening component of the polylactic acid straw, and simultaneously uses the epoxidized soybean oil and the chain extender as the compatilizer, thereby solving the problem that the polylactic acid straw is easy to cut and crack in the production process; and the polylactic acid straw is gradually and fully crystallized by adopting a sectional annealing treatment process in the preparation process of the polylactic acid straw, so that the heat resistance of the polylactic acid straw can be obviously improved. The heat-resistant polylactic acid straw provided by the invention has the heat-resistant temperature of more than 90 ℃, and the straw notch is not cracked in the cutting process of straw preparation, and the straw is not deformed in the annealing process.
Description
Technical Field
The invention belongs to the technical field of degradable polylactic acid materials, and particularly relates to a heat-resistant polylactic acid straw and a preparation method thereof.
Background
Along with the improvement of the living standard of people, beverage such as milk tea, coffee and the like become an important component of leisure and recreation in daily life of people, so that the continuous increase of the demands of disposable beverage straws is also driven. However, conventional disposable drinking straws mainly use polypropylene as a raw material, and the drinking straws are difficult to recover and can not be rapidly degraded, so that serious white pollution is caused when the drinking straws are used in a large amount. In the prior art, researchers have attempted to use polylactic acid straws having biodegradable properties instead of conventional polypropylene straws.
However, polylactic acid materials are hard and brittle, and the phenomenon of incision cracking easily occurs in the process of producing the polylactic acid straw by adopting the existing straw molding process. In addition, polylactic acid has a very slow crystallization rate and a low glass transition temperature, so that the thermal deformation temperature of the polylactic acid is only about 58 ℃, and the polylactic acid straw is softened and deformed after being contacted with hot drinks, so that the basic function of the straw is lost, and the use requirement of consumers cannot be met. The polylactic acid straw is subjected to secondary crystallization by adopting a common annealing process, and the heat-resistant temperature of the polylactic acid straw can be improved to a certain extent, but the polylactic acid straw is easy to bend and deform in the annealing process, so that the attractiveness and the use are affected.
The Chinese patent document with publication number of CN112521735A discloses a PLA heat-resistant straw and a preparation method thereof, wherein the PLA heat-resistant straw is extruded and prepared by adopting a three-layer coextrusion technology and comprises an outer layer, a middle layer and an inner layer which are sequentially connected, and the outer layer and the inner layer comprise the following components in parts by weight: 36 to 73 parts of copolymerized polylactic acid, 10 to 20 parts of aromatic polyester, 10 to 20 parts of aliphatic polyester, 5 to 20 parts of inorganic filler, 1 to 2 parts of polylactic acid nucleating agent and 1 to 2 parts of lubricant; the middle layer adopts aliphatic polyester. The heat resistance of the straw is better and reaches the level of more than 120 ℃, but the equipment requirement is high, the cost is high, and the introduction of the copolymerized polylactic acid can influence the biodegradability of the straw.
The Chinese patent document with publication number of CN110804287A discloses a heat-resistant modified polylactic acid composite material, which comprises the following raw material components: polylactic acid, polybutylene succinate, polybutylene adipate/terephthalate, erucamide, acetyl tributyl citrate, glycidyl methacrylate grafted ethyl methacrylate copolymer, antioxidant 10760 and talcum powder. The invention improves the heat resistance of the polylactic acid composite material by introducing a fully biodegradable polybutylene succinate component with excellent heat resistance, toughening treatment by adopting the polybutylene adipate/terephthalate and the superfine talcum powder to promote the crystallization behavior of a composite system, but the superfine talcum powder is easy to agglomerate and raw materials are not easy to obtain during blending.
Disclosure of Invention
Aiming at the problems of poor toughness, low heat-resistant temperature, easiness in generating incision cracking in the production process and the like of the polylactic acid straw in the prior art, the invention provides the heat-resistant polylactic acid straw which is excellent in heat resistance, the heat-resistant temperature can reach more than 90 ℃, and the incision of the straw is not cracked in the cutting process and the straw is not deformed in the annealing process.
The technical scheme adopted is as follows:
the heat-resistant polylactic acid straw comprises the following raw materials in 100 parts by weight:
the polybutylene furan dicarboxylate is biodegradable random copolyester, comprises a first repeating unit with a structure shown in a formula (I) and a second repeating unit with a structure shown in a formula (II),
the invention prepares the heat-resistant polylactic acid straw by taking polylactic acid, polyfurandicarboxylic acid/diglycolic acid butanediol ester, talcum powder, nucleating agent, chain extender, epoxidized soybean oil and lubricant as raw materials. Wherein the poly (furandicarboxylic acid)/diglycolic acid butanediol ester is a bio-based copolyester, has excellent ductility, good gas barrier property and good biodegradability, can obviously improve the toughness of the polylactic acid straw, the nucleating agent can gradually improve the crystallinity of the polylactic acid straw during the sectional annealing treatment, obviously improve the heat resistance of the polylactic acid straw without bending deformation, and the components cooperatively play roles and finally improve the toughness and the heat resistance of the polylactic acid straw by combining a forming process.
Preferably, the weight average molecular weight of the polylactic acid is 150000 ～ 250000g/mol, and the optical purity is more than or equal to 96%.
Preferably, when the molar ratio of the first repeating unit of the structure shown in the formula (I) to the second repeating unit of the structure shown in the formula (II) is 1:1, the poly furan dicarboxylic acid/diglycolic butanediol ester has good degradation performance and excellent mechanical performance, and is suitable for preparing the heat-resistant polylactic acid straw.
The synthesis method of the poly (furandicarboxylic acid)/diglycolic acid butanediol ester comprises the following steps: under protective atmosphere, dimethyl furan-2, 5-dicarboxylate, diglycolic acid and butanediol were mixed according to a ratio of 1:1: 2.4-3, adding a dibutyl tin oxide catalyst, prepolymerizing for 3-4 hours at 170-190 ℃, adding antimony trioxide, and reacting for 2-3 hours at 210-230 ℃ and 30-50 Pa to obtain the poly (furandicarboxylic acid)/diglycolic butanediol ester. The poly (furandicarboxylic acid)/diglycolic acid butanediol ester obtained by the method can obviously improve the toughness of the product polylactic acid straw, and solves the problem of notch cracking of the polylactic acid straw in the production process.
The weight average molecular weight of the poly (furandicarboxylic acid) and the diglycolic butanediol ester is 50000-80000 g/mol.
Preferably, the particle size of the talcum powder is 1000-3000 meshes; the talcum powder with smaller size can play a role of heterogeneous nucleation, can be used as an inorganic nucleating agent, and improves the heat resistance of the polylactic acid straw to a certain extent; further preferably, the particle size of the talc is 1500 to 3000 mesh.
The nucleating agent is at least one of ethylene bis-stearic acid amide, ethylene bis-12-hydroxystearic acid amide, ethylene bis-lauric acid amide and ethylene bis-oleic acid amide; the addition of the organic nucleating agent is beneficial to further improving the crystallization rate of the polylactic acid, and the crystallization degree of the polylactic acid straw is obviously increased in the sectional annealing treatment process, so that the heat-resistant temperature of the polylactic acid straw is effectively improved.
The chain extender is a Pasteur chain extender Joncryl ADR-4400 or a Pasteur chain extender Joncryl ADR-4468; joncryl ADR-4400 and Joncryl ADR-4468 are oligomers containing multiple epoxy functional groups, and the epoxy functional groups can simultaneously react with hydroxyl or carboxyl ends on molecular chains of polylactic acid and polyfurandicarboxylic acid/diglycolic acid butanediol ester to generate a graft copolymer to play a role of a compatilizer, so that the toughness of the polylactic acid straw is improved.
In addition, the addition of the epoxidized soybean oil in the formula system is beneficial to the uniform dispersion of the nucleating agent and the chain extender in the premixing process and improves the mechanical property of the polylactic acid suction pipe; on the other hand, the epoxidized soybean oil is also a compound with a polyepoxy group, which can play roles in compatibilization and plasticization, and further improve the toughness of the polylactic acid straw.
The invention also provides a preparation method of the heat-resistant polylactic acid straw, which comprises the following steps:
(1) Premixing 50-89 parts by mass of polylactic acid, 5-15 parts by mass of polyfurandicarboxylic acid/diglycolic acid butanediol ester, 5-30 parts by mass of talcum powder, 0.3-1 part by mass of nucleating agent, 0.2-1 part by mass of chain extender, 0.3-2 parts by mass of epoxidized soybean oil and 0.2-1 part by mass of lubricant to obtain a premix;
(2) Melt blending the premix, extruding and granulating to obtain polylactic acid modified material;
(3) And extruding the polylactic acid modified material, and carrying out sectional annealing treatment to obtain the heat-resistant polylactic acid straw.
The method adopts the raw materials with the specific composition, combines the means of adding the nucleating agent to improve the crystallization rate of the polylactic acid and gradually improving the crystallization degree of the polylactic acid by adopting a sectional annealing process to improve the heat resistance of the polylactic acid suction pipe; the segmented annealing treatment can lead the polylactic acid straw obtained after tube extrusion to be primarily crystallized at a lower temperature, then be further crystallized at a higher temperature, finally realize the purpose of full crystallization and avoid the polylactic acid straw from bending or deforming due to excessively fast crystallization shrinkage.
Preferably, in the step (1), the premix is obtained by drying and dehumidifying polylactic acid and polyfurandicarboxylic acid/diglycolic butanediol ester and premixing the polylactic acid and the polyfurandicarboxylic acid/diglycolic butanediol ester with other components according to a formula.
In the step (2), the conditions of melt blending are as follows: the premix is put into a double screw extruder and is melt blended at 165-185 ℃.
In the step (3), the pipe extruding step specifically includes: and adding the polylactic acid modified material into a straw extruder, and melting, extruding, water-cooling, air-cooling, traction, water removal, cutting and obtaining the polylactic acid straw.
Preferably, the polylactic acid suction pipe obtained after pipe extrusion is placed in a sectional tunnel oven to complete sectional annealing treatment, the sectional tunnel oven is provided with independent and separated temperature control units, a certain interval is arranged between every two temperature control units, the temperature control precision is good, no interference exists between every two temperature control units, and the preparation of the heat-resistant polylactic acid suction pipe is facilitated.
In the step (3), the sectional annealing treatment is divided into four stages, and the treatment parameters of the first stage are as follows: 90-95 ℃ for 0.25-1 min; the treatment parameters of the second stage are 100-105 ℃ and 0.25-1 min; the treatment parameters of the third stage are 110-115 ℃ and 0.25-1 min; the treatment parameters of the fourth stage are 120-125 ℃ and 0.25-1 min. The segmented annealing treatment can be used for preparing the polylactic acid suction pipe with excellent heat resistance, and can effectively prevent the polylactic acid suction pipe from bending or deforming due to excessively rapid crystallization shrinkage.
Compared with the prior art, the invention has the beneficial effects that:
(1) The polylactic acid straw provided by the invention is biodegradable, has excellent heat resistance, can reach a heat resistance temperature of more than 90 ℃, and is free from cracking in a straw notch in a cutting process and deformation in an annealing process of straw preparation.
(2) The invention uses biodegradable poly furan dicarboxylic acid/diglycolic acid butanediol ester as the toughening component of the polylactic acid straw, and uses the epoxidized soybean oil and the chain extender as the compatilizer, thereby solving the problem that the polylactic acid straw is easy to cut and crack in the production process.
(3) The invention adopts the sectional annealing treatment process to make the polylactic acid straw gradually and fully crystallize, which can obviously improve the heat resistance of the polylactic acid straw and prevent the polylactic acid straw from bending or deforming due to excessively rapid crystallization and shrinkage.
Drawings
FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of the polybutylene furan dicarboxylate/diglycolate obtained in the examples, wherein a, b, c 1 ～c 4 、d 1 ～d 4 Respectively represent hydrogen protons with different chemical shifts in the polyfurandicarboxylic acid/diglycolic butanediol ester.
Detailed Description
The invention is further elucidated below in connection with the drawings and the examples. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
Examples 1 to 4 and comparative examples 1 to 4:
the weight average molecular weight of the polylactic acid used was 210000g/mol, and the optical purity was 98%.
The particle size of the talcum powder is 3000 meshes.
The poly (furandicarboxylic acid)/diglycolic acid butanediol ester is prepared by the following method: dimethyl furan-2, 5-dicarboxylate, diglycolic acid and butanediol in the ratio of 1:1:3, adding the mixture into a reaction kettle filled with nitrogen in a molar ratio, mixing by mechanical stirring, then adding dibutyl tin oxide as a catalyst, and pre-polymerizing for 3-4 hours at the reaction temperature of 180 ℃; then adding antimony trioxide into a reaction kettle, raising the reaction temperature to 220 ℃, vacuumizing to 30-50 Pa, and after the reaction is continued for 2 hours, ending the reaction to obtain the poly (furan dicarboxylic acid)/diglycolic acid butanediol ester with the weight average molecular weight of 70000 g/mol.
In the polyfurandicarboxylic acid/diglycolic acid butanediol ester, the mol ratio of the first repeating unit of the structure shown in the formula (I) to the second repeating unit of the structure shown in the formula (II) is 1:1,
the nuclear magnetic resonance hydrogen spectrum of the polybutylene furan dicarboxylate/diglycolic acid butanediol ester is shown in figure 1, wherein a, b and c 1 ～c 4 、d 1 ～d 4 Respectively represent hydrogen protons with different chemical shifts in the polyfurandicarboxylic acid/diglycolic butanediol ester. Successful preparation of the polybutylene furan dicarboxylate/diglycolate was demonstrated.
Example 1
(1) Drying polylactic acid and polyfurandicarboxylic acid/diglycolic acid butanediol ester in a baking oven at 60 ℃ for 12 hours; the raw materials with the following weight portions are weighed according to the formula: 76.4 parts of dried polylactic acid, 5 parts of dried poly furan dicarboxylic acid/diglycolic acid butanediol ester, 15 parts of talcum powder, 1 part of ethylene bis-12-hydroxystearamide, 0.6 part of Joncryl ADR-4468 chain extender, 1.5 parts of epoxidized soybean oil and 0.5 part of TPW665 lubricant; weighing the raw materials according to a formula, and adding the raw materials into a high-speed mixer for premixing to obtain a premix;
(2) The premix is melt blended at the processing temperature of 165-180 ℃ by a double screw extruder, and the polylactic acid modified material is obtained after extrusion granulation; adding the obtained polylactic acid modified material into a straw extruder, setting the equipment temperature to 170-185 ℃, extruding the polylactic acid modified material out of a straw blank after melting and mixing, and then obtaining the polylactic acid straw after water cooling, air cooling, traction, water removal and cutting, wherein the water cooling temperature is 30 ℃, and the speed of drawing the straw blank is 1 m/s.
(3) And placing the polylactic acid suction pipe on a transmission chain mesh belt of a sectional tunnel oven, enabling the polylactic acid suction pipe to pass through each temperature control unit at a speed of 3m/min, wherein the temperature of each temperature control unit is 90 ℃, 100 ℃, 110 ℃ and 120 ℃, each independent temperature control unit is constant temperature, and the time for passing through each temperature control unit is 0.33min, so that the heat-resistant polylactic acid suction pipe is finally obtained.
Example 2
A heat-resistant polylactic acid drinking straw was obtained with reference to the preparation process of example 1, with the difference that: in the step (1), the raw material formula is as follows: 70.8 parts of dried polylactic acid, 5 parts of dried poly furan dicarboxylic acid/diglycolic acid butanediol ester, 20 parts of talcum powder, 1 part of ethylene bis-12-hydroxystearamide, 0.6 part of Joncryl ADR-4468 chain extender, 2 parts of epoxidized soybean oil and 0.6 part of TPW665 lubricant.
Example 3
A heat-resistant polylactic acid drinking straw was obtained with reference to the preparation process of example 1, with the difference that:
in the step (1), the raw material formula is as follows: 67.6 parts of dried polylactic acid, 8 parts of dried poly furan dicarboxylic acid/diglycolic acid butanediol ester, 20 parts of talcum powder, 1 part of ethylene bis-12-hydroxystearamide, 0.8 part of Joncryl ADR-4468 chain extender, 2 parts of epoxidized soybean oil and 0.6 part of TPW665 lubricant;
in the step (3), the temperature of each temperature control unit of the sectional tunnel oven is 95 ℃, 105 ℃, 115 ℃, 125 ℃ respectively, the moving speed of the transmission chain mesh belt is 2m/min, and the time for passing through each temperature control unit is 0.5min.
Example 4
A heat-resistant polylactic acid drinking straw was obtained with reference to the preparation process of example 1, with the difference that:
in the step (1), the raw material formula is as follows: 60.4 parts of dried polylactic acid, 10 parts of dried poly furan dicarboxylic acid/diglycolic acid butanediol ester, 25 parts of talcum powder, 0.8 part of ethylene bis-12-hydroxystearamide, 1 part of Joncryl ADR-4468 chain extender, 2 parts of epoxidized soybean oil and 0.8 part of TPW665 lubricant.
In the step (3), the temperature of each temperature control unit of the sectional tunnel oven is 95 ℃, 105 ℃, 115 ℃, 125 ℃ respectively, the moving speed of the transmission chain mesh belt is 2m/min, and the time for passing through each temperature control unit is 0.5min.
Comparative example 1
The polylactic acid drinking straw was obtained by referring to the preparation process of example 1, with the difference that:
in the step (1), the raw material formula is as follows: 75.8 parts of dried polylactic acid, 20 parts of talcum powder, 1 part of ethylene bis-12-hydroxystearamide, 0.6 part of Joncryl ADR-4468 chain extender, 2 parts of epoxidized soybean oil and 0.6 part of TPW665 lubricant.
Comparative example 2
The polylactic acid drinking straw was obtained by referring to the preparation process of example 1, with the difference that:
in the step (1), the raw material formula is as follows: 67.6 parts of dried polylactic acid, 8 parts of dried poly furan dicarboxylic acid/diglycolic acid butanediol ester, 20 parts of talcum powder, 1 part of ethylene bis-12-hydroxystearamide, 0.8 part of Joncryl ADR-4468 chain extender, 2 parts of epoxidized soybean oil and 0.6 part of TPW665 lubricant;
in the step (3), the polylactic acid suction pipe obtained after pipe extrusion is placed in a common tunnel oven, the temperature of the oven is set to be 95-100 ℃, the moving speed of a transmission chain mesh belt is 2m/min, and the time for passing through the tunnel oven is 0.5min.
Comparative example 3
The polylactic acid drinking straw was obtained by referring to the preparation process of example 1, with the difference that:
in the step (1), the raw material formula is as follows: 67.6 parts of dried polylactic acid, 8 parts of dried poly furan dicarboxylic acid/diglycolic acid butanediol ester, 20 parts of talcum powder, 1 part of ethylene bis-12-hydroxystearamide, 0.8 part of Joncryl ADR-4468 chain extender, 2 parts of epoxidized soybean oil and 0.6 part of TPW665 lubricant;
in the step (3), the polylactic acid suction pipe obtained after pipe extrusion is placed in a common tunnel oven, the temperature of the oven is set to be 110-115 ℃, the moving speed of a transmission chain mesh belt is 2m/min, and the time for passing through the tunnel oven is 0.5min.
Comparative example 4
The polylactic acid drinking straw was obtained by referring to the preparation process of example 1, with the difference that:
in the step (1), the raw material formula is as follows: 67.6 parts of dried polylactic acid, 8 parts of dried poly furan dicarboxylic acid/diglycolic acid butanediol ester, 20 parts of talcum powder, 1 part of ethylene bis-12-hydroxystearamide, 0.8 part of Joncryl ADR-4468 chain extender, 2 parts of epoxidized soybean oil and 0.6 part of TPW665 lubricant.
In the step (3), the polylactic acid suction pipe obtained after pipe extrusion is placed in a common tunnel oven, the temperature of the oven is set to be 120-125 ℃, the moving speed of a transmission chain mesh belt is 2m/min, and the time for passing through the tunnel oven is 0.5min.
Sample analysis
The performance of the polylactic acid straws produced in examples 1 to 4 and comparative examples 1 to 4 is shown in Table 1.
TABLE 1 Performance of polylactic acid straws in examples and comparative examples
| Name of the name | Incision state | Heat resistant temperature (DEG C) | Shaping quality |
| Example 1 | Does not crack | 96 | No bending deformation |
| Example 2 | Does not crack | 95 | No bending deformation |
| Example 3 | Does not crack | 92 | No bending deformation |
| Example 4 | Does not crack | 90 | No bending deformation |
| Comparative example 1 | Cracking of | / | No bending deformation |
| Comparative example 2 | Does not crack | 70 | No bending deformation |
| Comparative example 3 | Does not crack | 75 | Slightly bending deformation |
| Comparative example 4 | Does not crack | 92 | Severe bending deformation |
Note that: and placing the polylactic acid straw into the edible oil with slow temperature rise, wherein the temperature when the straw is stirred and deformed is the heat-resistant temperature.
As can be seen from the data in Table 1, the heat-resistant polylactic acid straw provided by the invention has good toughness and heat resistance, and is beneficial to the selection of raw material components and the step of sectional annealing treatment in the preparation process.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The heat-resistant polylactic acid straw is characterized by comprising the following raw materials in parts by weight based on 100 parts by weight of the total:
the polybutylene furan dicarboxylate is biodegradable random copolyester, comprises a first repeating unit with a structure shown in a formula (I) and a second repeating unit with a structure shown in a formula (II),
in the polyfurandicarboxylic acid/diglycolic butanediol ester, the molar ratio of the first repeating unit of the structure shown in the formula (I) to the second repeating unit of the structure shown in the formula (II) is 1:1; the weight average molecular weight of the polyfurandicarboxylic acid/diglycolic acid butanediol ester is 50000-80000 g/mol;
the preparation method of the heat-resistant polylactic acid straw comprises the following steps:
(1) Premixing 50-89 parts by mass of polylactic acid, 5-15 parts by mass of polyfurandicarboxylic acid/diglycolic acid butanediol ester, 5-30 parts by mass of talcum powder, 0.3-1 part by mass of nucleating agent, 0.2-1 part by mass of chain extender, 0.3-2 parts by mass of epoxidized soybean oil and 0.2-1 part by mass of lubricant to obtain a premix;
(2) Melt blending the premix, extruding and granulating to obtain polylactic acid modified material;
(3) The polylactic acid modified material is subjected to tube extrusion and sectional annealing treatment to obtain the heat-resistant polylactic acid straw;
in the step (3), the sectional annealing treatment is divided into four stages, and the treatment parameters of the first stage are as follows: 90-95 ℃ for 0.25-1 min; the treatment parameters of the second stage are 100-105 ℃ and 0.25-1 min; the treatment parameters of the third stage are 110-115 ℃ and 0.25-1 min; the treatment parameters of the fourth stage are 120-125 ℃ and 0.25-1 min.
2. The heat-resistant polylactic acid straw according to claim 1, wherein the polylactic acid has a weight average molecular weight of 150000 ～ 250000g/mol and an optical purity of 96% or more.
3. The heat-resistant polylactic acid suction pipe according to claim 1, wherein,
the synthesis method of the poly (furandicarboxylic acid)/diglycolic acid butanediol ester comprises the following steps: under protective atmosphere, dimethyl furan-2, 5-dicarboxylate, diglycolic acid and butanediol were mixed according to a ratio of 1:1: 2.4-3, adding a dibutyl tin oxide catalyst, prepolymerizing for 3-4 hours at 170-190 ℃, adding antimony trioxide, and reacting for 2-3 hours at 210-230 ℃ and 30-50 Pa to obtain the poly furan dicarboxylic acid/diglycolic butanediol ester.
4. The heat-resistant polylactic acid suction pipe according to claim 1, wherein the particle size of the talcum powder is 1000-3000 mesh.
5. The heat resistant polylactic acid straw of claim 1, wherein the nucleating agent is at least one of ethylene bis-stearamide, ethylene bis-12-hydroxystearamide, ethylene bis-lauramide and ethylene bis-oleamide.
6. The heat-resistant polylactic acid suction pipe according to claim 1, wherein the chain extender is basf chain extender Joncryl ADR-4400 or basf chain extender Joncryl ADR-4468.
7. The heat resistant polylactic acid straw according to claim 1, wherein in step (2), the melt blending conditions are: the premix is put into a double screw extruder and is melt blended at 165-185 ℃.
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| CN113698746A (en) * | 2021-08-27 | 2021-11-26 | 昌亚新材料科技有限公司 | Degradable heat-resistant polylactic acid pipe and preparation method and application thereof |
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| CN113698746A (en) * | 2021-08-27 | 2021-11-26 | 昌亚新材料科技有限公司 | Degradable heat-resistant polylactic acid pipe and preparation method and application thereof |
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