CN114539749A - Biodegradable high-toughness polylactic acid straw - Google Patents
Biodegradable high-toughness polylactic acid straw Download PDFInfo
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- CN114539749A CN114539749A CN202210224363.8A CN202210224363A CN114539749A CN 114539749 A CN114539749 A CN 114539749A CN 202210224363 A CN202210224363 A CN 202210224363A CN 114539749 A CN114539749 A CN 114539749A
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- polylactic acid
- biodegradable
- straw
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- 239000010902 straw Substances 0.000 title claims abstract description 63
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 43
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 42
- 229920001432 poly(L-lactide) Polymers 0.000 claims abstract description 40
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 39
- 239000002667 nucleating agent Substances 0.000 claims abstract description 36
- 239000007822 coupling agent Substances 0.000 claims abstract description 29
- 239000004970 Chain extender Substances 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 25
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 229920001896 polybutyrate Polymers 0.000 claims abstract 3
- 235000012424 soybean oil Nutrition 0.000 claims description 17
- 239000003549 soybean oil Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 8
- 239000000454 talc Substances 0.000 claims description 7
- 229910052623 talc Inorganic materials 0.000 claims description 7
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 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 claims description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 230000035622 drinking Effects 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 26
- 239000002994 raw material Substances 0.000 abstract description 21
- 238000002425 crystallisation Methods 0.000 abstract description 16
- 230000008025 crystallization Effects 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 9
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 25
- 238000005469 granulation Methods 0.000 description 11
- 230000003179 granulation Effects 0.000 description 11
- 239000008187 granular material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000001185 bone marrow Anatomy 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000012745 toughening agent Substances 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to the technical field of polylactic acid materials, and provides a biodegradable high-toughness polylactic acid straw which comprises the following components in parts by weight: 5-95 parts of PLLA, 1-50 parts of PBAT, 3-10 parts of a compatilizer, 0.01-20 parts of a nucleating agent, 0.01-5 parts of a dispersing agent, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-95 parts of a filler. Wherein the compatilizer can promote the compatibility among the raw materials; in the extrusion forming process of PLLA, quasi-orthorhombic crystals and orthorhombic crystals are generated during crystallization; the nucleating agent can promote quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA to be further subjected to stereocomplex to generate a more stable crystal structure and a stereocomplex, the complex forms triangular crystal nuclei at the initial stage of crystallization, and the unique crystallization mode enables the material performance to be more stable, so that the notch impact performance of the straw is further improved.
Description
Technical Field
The invention relates to the technical field of polylactic acid materials, in particular to a biodegradable high-toughness polylactic acid straw.
Background
The straw is a cylindrical hollow plastic product, and is mainly used for drinking beverages in cups and also for sucking bone marrow of long bones of cooked animals.
In the prior art, polylactic acid (PLA) and polybutylene adipate terephthalate (PBAT) are common raw materials for the preparation of drinking straws. Wherein PLA has high rigidity and crystallinity; the PBAT has the characteristics of both poly (adipate-co-terephthalate) and polybutylene terephthalate (PBT), has good ductility and elongation at break, good heat resistance and impact resistance, and good biodegradability of the PLA and the PBAT. However, when using PLA and PBAT to make straws, the tube blank is often very brittle and cannot be cut.
In order to solve the problems, the prior art generally adopts a mode of adding a plasticizer into raw materials to improve the ductility and the flexibility of the materials, so as to solve the problems that a tube blank is very brittle and cannot be cut. However, the notched impact performance of straws obtained with the above-described solution is still relatively low (often lower than 4 KJ/m)2) Thereby causing the straw to be easily chipped off when cut.
Disclosure of Invention
The invention aims to provide a biodegradable high-toughness polylactic acid straw, which has better and excellent notch impact performance, so that the breakage rate of the straw during cutting is reduced.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a biodegradable high-toughness polylactic acid straw which comprises the following components in parts by weight: 5-95 parts of PLLA, 1-50 parts of PBAT, 3-10 parts of a compatilizer, 0.01-20 parts of a nucleating agent, 0.01-5 parts of a dispersant, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-95 parts of a filler;
the nucleating agent is at least one of a D070 nucleating agent, a TMC-300 nucleating agent and a CZ-500 nucleating agent;
the compatilizer is at least one of PBAT-g-GMA, PBAT-g-MHA and PBST-g-GMA;
the preparation method of the biodegradable high-toughness polylactic acid straw comprises the steps of granulating, drying, extruding and molding and annealing in sequence; the extrusion forming device is a single-screw extruder, and the temperature of each part of the single-screw extruder is as follows: 160 ℃ in the first zone, 170 ℃ in the second zone, 180 ℃ in the third zone, 190 ℃ in the fourth zone and 205 ℃ in the machine head.
Preferably, the annealing temperature is 90-120 ℃, and the annealing time is 2-10 min.
Preferably, the weight average molecular weight of the PLLA is 30000-3000000, and the molecular weight distribution is 1.5-5.
Preferably, the weight average molecular weight of the PBAT is 20000-130000, and the molecular weight distribution is 1.5-4.
Preferably, the dispersant comprises at least one of calcium stearate, ethylene bis stearamide, oleamide, erucamide, paraffin wax and polyethylene wax.
Preferably, the plasticizer includes at least one of epoxidized soybean oil, polyethylene glycol, acetyl tributyl citrate, and acetylated monoglyceride.
Preferably, the coupling agent comprises at least one of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, and an aluminum titanate coupling agent.
Preferably, the chain extender includes a polyurethane chain extender and/or an epoxy chain extender.
Preferably, the polyurethane chain extender comprises ADR4375 and/or ADR 4400; the epoxy chain extender comprises CE1105 and/or 3525G.
Preferably, the filler comprises at least one of calcium carbonate, montmorillonite and talc.
The invention provides a biodegradable high-toughness polylactic acid straw, which promotes the compatibility among raw materials by adding a compatilizer into the raw materials, thereby improving the impact property of a notch of the straw; by selecting polylactic acid as a raw material, in the extrusion forming process, PLLA can generate quasi-orthorhombic crystals and orthorhombic crystals during crystallization; by selecting a particularThe substance is used as a nucleating agent, under the action of the nucleating agent, quasi-orthorhombic crystals and orthorhombic crystals formed by the PLLA are further subjected to stereocomplex to generate a more stable crystal structure, namely a stereocomplex, the complex forms triangular crystal nuclei at the initial stage of crystallization, and the unique crystallization mode enables the material performance to be more stable, so that the notch impact performance of the straw is further improved. The experiment result shows that the impact property of the notch of the straw obtained by the technical scheme provided by the invention is not lower than 5.5KJ/m2。
Detailed Description
The invention provides a biodegradable high-toughness polylactic acid straw which comprises the following components in parts by weight: 5-95 parts of PLLA, 1-50 parts of PBAT, 3-10 parts of a compatilizer, 0.01-20 parts of a nucleating agent, 0.01-5 parts of a dispersing agent, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-95 parts of a filler.
The biodegradable high-toughness polylactic acid straw comprises, by weight, PLLA 5-95 parts, preferably 40-80 parts, and more preferably 55-75 parts. In the present invention, the PLLA represents poly-l-lactic acid. In the extrusion forming process, PLLA can generate quasi-orthorhombic crystals and orthorhombic crystals during crystallization; by selecting a specific substance as a nucleating agent, under the action of the nucleating agent, quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA are further subjected to stereocomplex to generate a more stable crystal structure, namely a stereocomplex, the complex forms triangular crystal nuclei at the initial stage of crystallization, and the material performance is more stable due to a unique crystallization mode, so that the notch impact performance of the straw is further improved.
In the invention, the weight average molecular weight of the PLLA is preferably 30000-3000000, more preferably 100000-2000000; the molecular weight distribution is preferably 1.5 to 5, more preferably 2.5 to 3.5. The weight average molecular weight of the PLLA is controlled in the range, so that the problems that the molecular weight is too small, the flowability of the material is changed greatly in the processing process and the toughness of the material is influenced are avoided; the molecular weight is too high, and the melting of the material is difficult; and the PLLA within the molecular weight range is proper in price, so that the cost of the straw is reduced. By controlling the molecular weight distribution in the above range, the PLLA performance is stable.
The source of the PLLA is not specifically defined in the present invention, and conventional commercial products well known to those skilled in the art may be used. In the embodiment of the present invention, the PLLA is a PLLA of an L130 model. In an actual production plant, L in the L130 represents high optical rotation.
The biodegradable high-toughness polylactic acid straw comprises, by weight, 5-95 parts of PLLA, 1-50 parts of PBAT, preferably 5-30 parts of PBAT, and more preferably 10-20 parts of PBAT. In the present invention, the PBAT represents a copolymer of butylene adipate (PBA) and butylene terephthalate (PBT). In the present invention, the PBAT has good ductility and elongation at break, good heat resistance and impact resistance, and excellent biodegradability, and is present as a base material for biodegradable materials.
In the invention, the weight average molecular weight of PBAT is preferably 20000-130000, more preferably 60000-95000; the molecular weight distribution is preferably 1.5 to 4, more preferably 2.5 to 3.5. The weight average molecular weight of the PBAT is controlled in the range, so that the phenomenon that the molecular weight is too small, the flowability of the material is changed greatly in the processing process, and the toughness of the material is influenced is avoided; the molecular weight is too high, and the melting of the material is difficult; meanwhile, the PBAT with the molecular weight is proper in price, and the cost of the straw is reduced. The molecular weight distribution of the PBAT is controlled in the range, and the PBAT has stable performance.
The source of the PBAT is not specified in the present invention, and conventional commercial products well known to those skilled in the art may be used. In the embodiment of the invention, the PBAT is selected from conventional commercial products with the brand number TH 801T.
The biodegradable high-toughness polylactic acid suction pipe provided by the invention comprises 3-10 parts of compatilizer, preferably 5-8 parts of compatilizer, calculated by 5-95 parts of PLLA. In the invention, the compatilizer can promote the compatibility among the raw materials, thereby improving the notch impact performance of the straw.
In the present invention, the compatibilizer is at least one of PBAT-g-GMA, PBAT-g-MHA, and PBST-g-GMA, preferably PBST-g-GMA. . In the present invention, the PBAT-g-GMA represents poly (butylene adipate/terephthalate) grafted glycidyl methacrylate; PBAT-g-MHA represents poly (butylene adipate terephthalate) -grafted maleic anhydride; PBST-g-GMA stands for polybutylene succinate-butylene terephthalate grafted glycidyl methacrylate. In the invention, the PBST-g-GMA graft has the advantages of high grafting efficiency, short polymer synthesis time and the like, and is relatively low in price.
The source of the compatibilizer is not particularly specified in the invention, and the compatibilizer can be prepared by a preparation method well known to a person skilled in the art or a commercially available product can be directly purchased.
The biodegradable high-toughness polylactic acid straw comprises, by weight, 5-95 parts of PLLA, 0.01-20 parts of a nucleating agent, preferably 1-10 parts of the nucleating agent, and more preferably 3-5 parts of the nucleating agent. In the invention, the nucleating agent can promote quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA to be further subjected to stereocomplex, so that a more stable crystal structure and a stereocomplex are generated, triangular crystal nuclei are formed in the complex at the initial stage of crystallization, and the material performance is more stable due to a unique crystallization mode.
In the invention, the nucleating agent is at least one of a D070 nucleating agent, a TMC-300 nucleating agent and a CZ-500 nucleating agent. In the invention, the D070 nucleating agent represents dextrorotatory polylactic acid; TMC-300 represents dibenzoylhydrazide sebacate; CZ-500 represents polyhydrazide imine compounds. In the invention, the nucleating agent can promote the nucleating agent formed by further stereocomplex of quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA, and the obtained straw has better comprehensive performance.
The source of the nucleating agent is not specially specified in the invention, and the nucleating agent is prepared by a preparation method well known to those skilled in the art or a commercially available product is directly purchased.
The biodegradable high-toughness polylactic acid straw comprises, by weight of PLLA 5-95 parts, 0.01-5 parts of a dispersing agent, preferably 0.1-1 part, and more preferably 0.3-0.5 part. In the present invention, the dispersant can uniformly disperse inorganic and organic solid and liquid particles which are difficult to dissolve in liquid, and can prevent the particles from settling and coagulating to form a stable suspension.
In the present invention, the dispersant preferably includes at least one of calcium stearate, ethylene bis stearamide, oleamide, erucamide, paraffin wax and polyethylene wax, preferably ethylene bis stearamide, i.e., EBS. In the invention, the ethylene bis stearamide has low odor and low addition content, has the function of internal and external lubrication, and can be used as the dispersant to obtain the straw with better comprehensive performance.
The source of the dispersant is not particularly specified in the present invention, and the dispersant can be prepared by a preparation method well known to those skilled in the art or a commercially available product can be directly purchased.
The biodegradable high-toughness polylactic acid straw comprises, by weight of PLLA 5-95 parts, 0.01-5 parts of a plasticizer, preferably 0.1-3 parts, and more preferably 0.5-1 part. In the invention, the plasticizer can reduce intermolecular force, so that the viscosity of the polymer is reduced, and the flexibility is enhanced.
In the present invention, the plasticizer preferably includes at least one of epoxidized soybean oil, polyethylene glycol, acetyl tributyl citrate, and acetylated monoglyceride, and more preferably epoxidized soybean oil. In the invention, the epoxy group of the epoxy soybean oil has reactivity with the group resin PLLA, so that the comprehensive performance of the obtained straw material can be further improved.
The source of the plasticizer is not particularly limited in the present invention, and a commercially available product well known to those skilled in the art may be used.
The biodegradable high-toughness polylactic acid straw comprises, by weight, 5-95 parts of a filler, preferably 5-50 parts, and more preferably 10-25 parts of PLLA. In the present invention, the filler may enhance the overall performance of the polymeric material.
In the present invention, the filler preferably includes at least one of calcium carbonate, montmorillonite and talc. In the present invention, the particle diameter D of the filler50Preferably 1.2E3 μm, more preferably 1.5 to 2.5 μm. The invention controls the grain diameter of the filler within the range, can improve the dispersion uniformity of the filler in the raw materials, and further improves the mechanical property of the material; meanwhile, the increase of the production cost caused by the over-small particle size is avoided, so that the raw material cost for producing the straw is reduced.
The source of the filler is not specifically defined in the present invention, and a commercially available product well known to those skilled in the art may be used.
The biodegradable high-toughness polylactic acid suction pipe comprises 0.01-5 parts of coupling agent, preferably 0.1-0.3 part, by weight of 5-95 parts of filler. In the invention, the coupling agent can realize the effect of modifying the filler, thereby improving the dispersibility of the filler in the raw materials.
In the present invention, the coupling agent preferably includes at least one of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, and an aluminum-titanium ester coupling agent, and more preferably an aluminum-titanium ester coupling agent. The aluminum titanate coupling agent is used as the coupling agent of the invention, and is easier to be dispersed uniformly in a raw material system.
The source of the coupling agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
The biodegradable high-toughness polylactic acid straw comprises, by weight of PLLA, 0.01-5 parts of a chain extender, preferably 0.1-1 part, and more preferably 0.3-0.5 part. In the invention, the chain extender can react with the polymer in the raw material, so that the molecular weight of the polymer is improved, and the mechanical property of the material is further improved.
In the present invention, the chain extender preferably includes a polyurethane chain extender and/or an epoxy chain extender, and the polyurethane chain extender preferably includes ADR4375 and/or ADR 4400; the epoxy chain extender preferably includes CE1105 and/or 3525G. The chain extender is selected as the chain extender of the technical scheme of the invention, so that the polymer with proper polymerization degree can be more easily obtained, and the optimal comprehensive performance of the material can be realized due to the proper polymerization degree of the obtained polymer material.
The source of the chain extender is not particularly specified in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the preparation method of the biodegradable high-toughness polylactic acid straw comprises the steps of granulating, drying, extruding and forming and annealing in sequence.
In the present invention, the method for preparing the biodegradable high-toughness polylactic acid straw preferably comprises: and mixing the PLLA, the PBAT, the compatilizer, the coupling agent, the nucleating agent, the chain extender, the dispersant, the filler and the plasticizer, and then sequentially granulating, drying, extruding and molding and annealing to obtain the biodegradable high-toughness polylactic acid straw.
In the present invention, the PLLA, PBAT, compatibilizer, nucleating agent and filler are preferably dried before mixing. The drying method is not particularly limited in the present invention, and the moisture in the raw materials may be removed by a drying method known to those skilled in the art. The invention dries the raw materials in advance, and can avoid the influence of moisture in the raw materials on the granulation process, thereby reducing the performance of the straw.
According to the invention, preferably, the coupling agent and the filler are mixed to obtain the activated filler, and then the activated filler is mixed with PLLA, PBAT, the compatilizer, the nucleating agent, the chain extender, the dispersant and the plasticizer, and then granulation is carried out. The invention is beneficial to improving the dispersibility of the filler in the formula by activating the filler by using the coupling agent in advance.
In the present invention, the apparatus for granulation is preferably a twin-screw extruder. The granulation mode is not specially specified in the invention, and the granules can be obtained by adopting a granulation mode known by a person skilled in the art and utilizing a double-screw extruder for granulation. The invention firstly carries out granulation on the raw materials, is beneficial to improving the dispersity among the raw materials in the later extrusion forming process and further improves the comprehensive performance of the straw.
In the present invention, the temperature of each part of the twin-screw extruder is preferably: 150 ℃ in the first zone, 160 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the fourth zone, 170 ℃ in the fifth zone, 175 ℃ in the sixth zone and 180 ℃ in the machine head; the screw rotating speed of the double-screw extruder is preferably 60-600 rpm, more preferably 100-500 rpm, and most preferably 200-400 rpm; the length-diameter ratio L/D of the screw of the double-screw extruder is preferably (40-72): 1, and more preferably 48: 1. The invention limits all process parameters of the double-screw extruder within the range, and the obtained straw has better comprehensive performance.
The drying method after granulation is not particularly specified in the present invention, and the granules prepared after granulation are dried by a drying method well known to those skilled in the art, and the moisture in the granules during granulation is removed.
In the invention, the extrusion forming device is a single-screw extruder. The extrusion forming operation is not specially specified in the invention, and the straw is prepared by adopting the extrusion forming operation known by the technical personnel in the field and utilizing a single-screw extruder.
In the present invention, the temperature of each part of the single screw extruder is preferably: 160 ℃ in the first area, 170 ℃ in the second area, 180 ℃ in the third area, 190 ℃ in the fourth area and 205 ℃ in a machine head; the screw rotating speed of the single-screw extruder is preferably 100-400 rpm, and more preferably 150-300 rpm; the length-diameter ratio L/D of the screw of the single-screw extruder is preferably 40-60: 1, and more preferably 52: 1; the speed of the single-screw extruder for pulling the pipe blank by the pulling equipment is 0.5-1.5 m/s, and more preferably 1 m/s. The water cooling temperature of the water cooling device of the single-screw extruder is preferably 30-50 ℃, and more preferably 40 ℃. The invention limits the technological parameters of each part of the single screw extruder in the above range, and the obtained straw has good comprehensive performance.
In the invention, the annealing temperature is preferably 90-120 ℃, and more preferably 100-110 ℃; the annealing time is preferably 2 to 10min, and more preferably 4 to 8 min. The invention promotes the crystallization of the material through annealing treatment, thereby improving the heat resistance of the material.
The invention provides a biodegradable high-toughness polylactic acid straw, which promotes the compatibility among raw materials by adding a compatilizer into the raw materials, thereby improving the impact property of a notch of the straw; by selecting polylactic acid as a raw material, in the extrusion forming process, PLLA can generate quasi-orthorhombic crystals and orthorhombic crystals during crystallization; by selecting a specific substance as a nucleating agent, under the action of the nucleating agent, quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA are further subjected to stereocomplex to generate a more stable crystal structure, namely a stereocomplex, the complex forms triangular crystal nuclei at the initial stage of crystallization, and the material performance is more stable due to a unique crystallization mode, so that the notch impact performance of the straw is further improved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the examples, the specific specification or abbreviation of the raw materials is as follows: PLLA (designation L130, weight average molecular weight 207000g/mol, molecular weight distribution 1.8 or designation L175, weight average molecular weight 207000g/mol, molecular weight distribution 1.8), PBAT (designation TH801T, weight average molecular weight 88000, molecular weight distribution 2.2), compatibilizer: PBAT-g-GMA (trade name BP-02), filler: nano calcium carbonate (trade name XF-10, particle diameter D)501.2 μm) or talc (trade name HTP05L, particle size D501.2 μm), coupling agent: aluminum-titanium coupling agent, nucleating agent: d070, plasticizer: epoxidized soybean oil, chain extender: ADR-4400, dispersant: ethylene bis stearamide, EBS for short
Example 1
The components and the dosage are as follows: 58 parts of L130, 12 parts of TH801T, 5 parts of PBST-g-GMA, 3 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated XF-10.
Pretreatment: (1) drying D070, L130, TH801T and PBST-g-GMA in a blast oven at 80 ℃ for 4 h; HTP05L and XF-10 were dried for 4h in a 105 ℃ forced air oven.
(2) 99 parts of nano calcium carbonate and 1 part of aluminum-titanium coupling agent are stirred for 5 minutes at 90 ℃ to obtain activated XF-10.
The preparation method comprises the following specific steps:
(I) mixing the L130, the TH801T, the PBST-g-GMA, the D070 and 0.8 part of epoxy soybean oil in parts by weight for 3min, then sequentially adding 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated XF-10, and mixing for 8min at normal temperature in a high-speed mixer to obtain a mixture;
(II) adding the mixture obtained in the step (I) into a double-screw extruder for extrusion and granulation to obtain granules; the temperature of each zone of the double-screw extruder is as follows: 150 ℃ in the first zone, 160 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the fourth zone, 170 ℃ in the fifth zone, 175 ℃ in the sixth zone and 180 ℃ in the machine head; the rotating speed of the screw is 200rpm, and the length-diameter ratio L/D is 48/1;
(III) drying the granules obtained in the step (II) in a forced air oven at 80 ℃ for 4 hours to obtain dried granules;
(IV) adding the dried granules obtained in the step (III) into a single-screw extruder for extrusion to obtain the biodegradable polylactic acid heat-resistant straw, wherein the temperature of each area of the single-screw extruder is as follows: 160 ℃ in the first area, 170 ℃ in the second area, 180 ℃ in the third area, 190 ℃ in the fourth area, 205 ℃ in the machine head, the rotating speed of the screw is 250rpm, the speed of the traction tube blank of the traction equipment is 1 m/s, and the water cooling temperature of the water cooling device is 40 ℃ to obtain the primary suction tube.
And (V) annealing the primary straw obtained in the step (IV), wherein the annealing temperature is 110 ℃, and the annealing time is 4min, so that the straw is obtained.
Example 2
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 58 parts of L130, 12 parts of TH801T, 5 parts of PBST-g-GMA, 5 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated XF-10.
Example 3
The procedure was the same as in example 1, except that: the filler was changed to talc, and the same procedure was carried out by drying talc in a 105 ℃ forced air oven for 4 hours and stirring the dried talc with 1 part of an aluminum-titanium coupling agent at 90 ℃ for 5 minutes to obtain activated HTP 05L.
The components and the dosage are as follows: 58 parts of L130, 12 parts of TH801T, 5 parts of PBST-g-GMA, 5 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated HTP 05L.
Example 4
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 58 parts of L175, 12 parts of TH801T, 5 parts of PBST-g-GMA, 8 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated HTP 05L.
Example 5
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 58 parts of L175, 12 parts of TH801T, 3 parts of PBST-g-GMA, 5 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated HTP 05L.
Example 6
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 58 parts of LX175, 12 parts of TH801T, 5 parts of PBST-g-GMA, 3 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated XF-10.
Example 7
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 58 parts of L130, 12 parts of TH801T, 5 parts of PBST-g-GMA, 2 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated HTP 05L.
Comparative example 1
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 58 parts of L175, 12 parts of TH801T, 1 part of PBST-g-GMA, 5 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated HTP 05L.
Comparative example 2
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 58 parts of L130, 7 parts of TH801T, 5 parts of PBST-g-GMA, 5 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated HTP 05L.
Comparative example 3
The preparation process is the same as that of example 1, except that the components and the amounts are as follows: 58 parts of L130, 2 parts of TH801T, 5 parts of PBST-g-GMA, 5 parts of D070, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated HTP 05L.
Performance tests were performed on the straws prepared in examples 1 to 7 and comparative examples 1 to 3, and the test results are shown in Table 1.
And (4) testing standard: the notch impact is according to GB/T1843-2008, 1 type; tensile strength GB/T1040.2-2006, type 1A; bending strength GB/T9341-; the Vicat softening temperature is in accordance with GB/T1633-2000.
TABLE 1 Performance test results for straws prepared in examples 1 to 7 and comparative examples 1 to 3
The notch strength results in table 1 show that the compatibilizer in the system can well improve the compatibility of PLLA and PBAT, improve the dispersion condition of the toughening agent and the inorganic powder, and improve the toughness of the material, and the larger the proportion of D-type PLA in the system is, the higher the heat-resistant temperature is; the optical purity of PLLA affects the crystallization of the straw material, and low optical purity PLA is only suitable for preparing cold straw material with low heat resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A biodegradable high-toughness polylactic acid straw comprises the following components in parts by weight: the composite material comprises, by weight, 5-95 parts of PLLA, 1-50 parts of PBAT, 3-10 parts of a compatilizer, 0.01-20 parts of a nucleating agent, 0.01-5 parts of a dispersant, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-95 parts of a filler;
the nucleating agent is at least one of a D070 nucleating agent, a TMC-300 nucleating agent and a CZ-500 nucleating agent;
the compatilizer is at least one of PBAT-g-GMA, PBAT-g-MHA and PBST-g-GMA;
the preparation method of the biodegradable high-toughness polylactic acid straw comprises the steps of granulating, drying, extruding and forming and annealing in sequence; the extrusion forming device is a single-screw extruder, and the temperature of each part of the single-screw extruder is as follows: 160 ℃ in the first zone, 170 ℃ in the second zone, 180 ℃ in the third zone, 190 ℃ in the fourth zone and 205 ℃ in the head.
2. The biodegradable high-toughness polylactic acid straw according to claim 1, wherein the annealing temperature is 90-120 ℃, and the annealing time is 2-10 min.
3. The biodegradable high-toughness polylactic acid straw as claimed in claim 1, wherein the weight average molecular weight of PLLA is 30000-3000000, and the molecular weight distribution is 1.5-5.
4. The biodegradable high-toughness polylactic acid straw according to claim 1, wherein the weight average molecular weight of PBAT is 20000 to 130000, and the molecular weight distribution is 1.5 to 4.
5. The biodegradable, high tenacity polylactic acid straw according to claim 1, wherein said dispersing agent comprises at least one of calcium stearate, ethylene bis stearamide, oleamide, erucamide, paraffin wax and polyethylene wax.
6. The biodegradable, high tenacity polylactic acid straw according to claim 1, wherein said plasticizer comprises at least one of epoxidized soybean oil, polyethylene glycol, acetyl tributyl citrate, and acetylated monoglycerol fatty acid ester.
7. The biodegradable, high tenacity polylactic acid straw according to claim 1, wherein said coupling agent comprises at least one of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, and an aluminum titanium ester coupling agent.
8. The biodegradable, high tenacity polylactic acid straw according to claim 1, wherein said chain extender comprises a polyurethane chain extender and/or an epoxy chain extender.
9. The biodegradable, high tenacity polylactic acid drinking straw according to claim 8, wherein said polyurethane chain extender comprises ADR4375 and/or ADR 4400; the epoxy chain extender comprises CE1105 and/or 3525G.
10. The biodegradable, high tenacity polylactic acid straw according to claim 1, wherein said filler comprises at least one of calcium carbonate, montmorillonite and talc.
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| CN115948036A (en) * | 2022-12-12 | 2023-04-11 | 会通新材料股份有限公司 | Biodegradable material for low-die-opening precipitate suction tube and preparation method thereof |
| CN115960447A (en) * | 2022-12-30 | 2023-04-14 | 中广核高新核材科技（苏州）有限公司 | High-toughness crystalline heat-resistant biodegradable desorption tube material and preparation method thereof |
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| CN113801450A (en) * | 2021-11-10 | 2021-12-17 | 晋江市新迪新材料科技有限公司 | Full-biodegradable modified plastic for high-temperature-resistant extrusion straw product and preparation method thereof |
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| CN111718566A (en) * | 2019-03-22 | 2020-09-29 | 汉达精密电子(昆山)有限公司 | PLA/PBAT biodegradable composite material and product thereof |
| CN113801450A (en) * | 2021-11-10 | 2021-12-17 | 晋江市新迪新材料科技有限公司 | Full-biodegradable modified plastic for high-temperature-resistant extrusion straw product and preparation method thereof |
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| CN115948036A (en) * | 2022-12-12 | 2023-04-11 | 会通新材料股份有限公司 | Biodegradable material for low-die-opening precipitate suction tube and preparation method thereof |
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