CN115746521A - High-temperature-resistant low-migration controllable-degradation polylactic acid straw and preparation method thereof - Google Patents
High-temperature-resistant low-migration controllable-degradation polylactic acid straw and preparation method thereof Download PDFInfo
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- CN115746521A CN115746521A CN202211397482.XA CN202211397482A CN115746521A CN 115746521 A CN115746521 A CN 115746521A CN 202211397482 A CN202211397482 A CN 202211397482A CN 115746521 A CN115746521 A CN 115746521A
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- polylactic acid
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- hydroxybutyrate
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 109
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 109
- 239000010902 straw Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 21
- 238000013508 migration Methods 0.000 title claims abstract description 18
- -1 butanediol ester Chemical class 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 230000005012 migration Effects 0.000 claims abstract description 12
- 229920005586 poly(adipic acid) Polymers 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000002667 nucleating agent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- FHUDZSGRYLAEKR-UHFFFAOYSA-N 3-hydroxybutanoic acid;4-hydroxybutanoic acid Chemical compound CC(O)CC(O)=O.OCCCC(O)=O FHUDZSGRYLAEKR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 37
- 230000008025 crystallization Effects 0.000 claims description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 16
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 11
- 229940022769 d- lactic acid Drugs 0.000 claims description 11
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical compound OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000005313 fatty acid group Chemical group 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002791 poly-4-hydroxybutyrate Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
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- 125000005456 glyceride group Chemical group 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 229920002961 polybutylene succinate Polymers 0.000 description 7
- 239000004631 polybutylene succinate Substances 0.000 description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
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- 241000335053 Beta vulgaris Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- QDGXHPFKUOZLBV-UHFFFAOYSA-N C(C(=C)C)(=O)OCC1CO1.C(=CC1=CC=CC=C1)C=CC(=O)O Chemical compound C(C(=C)C)(=O)OCC1CO1.C(=CC1=CC=CC=C1)C=CC(=O)O QDGXHPFKUOZLBV-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
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- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 235000021121 fermented vegetables Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000012171 hot beverage Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a high-temperature-resistant low-migration controllable-degradation polylactic acid straw and a preparation method thereof, wherein the straw comprises the following components in percentage by mass: 50-80% of polylactic acid, 7-27% of poly 3-hydroxybutyrate 4-hydroxybutyrate, 10-20% of poly adipic acid/butanediol ester, 0.2-1% of nucleating agent, 0.2-1% of plasticizer, 0.2-1% of dispersant, 0.4-0.8% of anti-hydrolysis agent and 0.4-0.8% of compatilizer; the preparation method comprises the following steps: (1) Mixing polylactic acid, poly 3-hydroxybutyrate 4-hydroxybutyrate and poly adipic acid/butanediol ester, adding a plasticizer, a nucleating agent, a dispersing agent, a hydrolysis resistant agent and a compatilizer, and stirring to obtain a polylactic acid mixture; (2) Adding the polylactic acid mixture into an extrusion device, melting, mixing and extruding to obtain a polylactic acid straw blank, drawing the straw blank, cooling by water, cooling by air, dewatering, cutting, crystallizing, and cooling to obtain the polylactic acid straw. The polylactic acid straw prepared by the invention has the advantages of high temperature resistance, low migration volume, controllable degradation, safety, environmental protection, low cost and high production efficiency.
Description
Technical Field
The invention relates to a straw and a preparation method thereof, in particular to a high-temperature-resistant low-migration controllable-degradation polylactic acid straw and a preparation method thereof.
Background
Polylactic acid (PLA), also known as polylactide, is a thermoplastic aliphatic polyester derived from renewable materials, usually from fermented vegetable starches, such as corn, tapioca, sugar cane or beet pulp. In 2010, polylactic acid became the second most highly consumed biomass plastic in the world. The polylactic acid is applied to preparing the beverage straws, and the defect that the polylactic acid cannot resist high temperature (only can resist 60 ℃) needs to be solved. The PLA straw which is currently marketed is made of 40% of PLA, 10% of talcum powder and 50% of PBS, and can resist high temperature of about 80 ℃. Many hot beverages, however, tend to be at temperatures above 80 c and the PLA straws currently in use are not able to meet their needs. In addition, the polylactic acid material cannot meet the production molding requirements of the existing plastic suction pipe due to the problems of hardness, brittleness, poor toughness and the like, so that the polylactic acid suction pipe cannot comprehensively replace the plastic suction pipe.
The invention patent with publication number CN114133714 discloses a preparation method and a device of a high-temperature-resistant polylactic acid straw, wherein 5-30 parts by weight of talcum powder and 0.1-1 part by weight of organic crystal nucleating agent are added into 100 parts by weight of polylactic acid, the mesh number of the talcum powder is 500-8000 meshes, and modified polylactic acid is obtained after uniform mixing; extruding the modified polylactic acid by using a straw extruder to obtain a polylactic acid straw; the polylactic acid suction pipe is placed in a device for preparing the high-temperature-resistant polylactic acid suction pipe, an infrared heater heats the polylactic acid suction pipe, the heating temperature is controlled to be 60-145 ℃, and the heating time is 15-600s. However, the talc powder has the risk of exceeding the standard of potential fluorine content, the problem of migration of polybutylene succinate (PBS), and the problem of food safety and degradation dispute due to the benzene ring contained in polybutylene adipate/terephthalate (PBAT), so that the problems of food safety and biodegradation are easily caused.
Therefore, it can be known from the above that the existing polylactic acid straw mainly has the following technical problems: the straw has poor heat resistance, is rapidly degraded in a short time to cause the whole straw to be degraded and brittle and can not be used, so that the straw product can lose effectiveness in the shelf life, a large amount of materials are wasted, and the popularization and the use of the environment-friendly polylactic acid material are not facilitated; meanwhile, the talcum powder and the like are added in the production and storage processes of the product, so that potential hazards exist in the safety and the degradation performance of the product.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems in the prior art, the invention aims to provide a polylactic acid straw which is high temperature resistant, low in migration volume, controllable in degradation, safe and environment-friendly, and further provides a preparation method of the polylactic acid straw.
The technical scheme is as follows: the invention relates to a high-temperature-resistant low-migration controllable-degradation polylactic acid straw, which comprises the following components in percentage by mass: 50-80% of polylactic acid, 07-27% of poly 3-hydroxybutyrate 4-hydroxybutyrate (P34 HB), 10-20% of poly adipic acid/butanediol ester (PBA), 0.2-1% of nucleating agent, 0.2-1% of plasticizer, 0.2-1% of dispersant, 0.4-0.8% of anti-hydrolysis agent and 0.4-0.8% of compatilizer.
Further, the optical purity of the polylactic acid is more than or equal to 99 percent, and the melt index is less than or equal to 10g/10min; the poly-3-hydroxybutyrate 4-hydroxybutyrate has an acid value of less than or equal to 30mol/t and a melt index of less than or equal to 10g/10min, is prepared by copolymerizing poly-3-hydroxybutyrate and 4-hydroxybutyrate and is used for improving the resilience of the material; the acid value of the poly adipic acid/butanediol ester is less than or equal to 30mol/t, the melt index is less than or equal to 10g/10min, and the poly adipic acid/butanediol ester is prepared by copolymerizing adipic acid and p-butanediol and is used for improving the low-temperature toughness of the material.
Further, the nucleating agent is multi-arm poly-D-lactic acid, and the preparation method comprises the following steps: the preparation method is characterized in that dextrorotatory lactide and octa-epoxy cage-shaped polyhedral oligomeric silsesquioxane are used as raw materials, stannous octoate is used as a catalyst, and anhydrous xylene is used as a solvent, and the preparation method is prepared by an in-situ ring-opening polymerization method; wherein the purity of the dextro-lactide is more than 99 percent, and the molar fraction of the stannous octoate is 2.0 multiplied by 10 -4 Mol fraction of octa-epoxy cage type polyhedral oligomeric silsesquioxane is 5.0 x 10 -5 Percent, size is 0.3-3nm; the multi-arm poly-D-lactic acid is a three-dimensional network structure, has a regular structure and good compatibility with polylactic acid, is a high-efficiency polylactic acid crystallization nucleating agent and is used for greatly improving the crystallization rate of the polylactic acid.
Furthermore, the plasticizer is citric acid fatty glyceride, the ester content is more than or equal to 99%, the citric acid fatty glyceride belongs to a migration-resistant plasticizer and is used for improving the plasticity of the material, and the 'solvation' effect of the plasticizer can improve the movement speed of a material molecular chain so as to improve the crystallization speed to a certain extent.
Further, the dispersing agent is fatty acid amide, the fatty acid amide is a block copolymer, and an anchoring group of the block copolymer is substituted for a hydrophilic group of the surfactant, so that stable dispersion of each auxiliary agent in the material is realized.
Furthermore, the hydrolysis resistant agent is polycarbodiimide, the polymerization degree is more than or equal to 2000, and terminal carboxyl and water molecules can be captured at normal temperature to form green stable groups, so that the hydrolysis resistance of the material is improved, and the reduction of polylactic acid in the processing and storage processes can be reduced.
Furthermore, the compatilizer is a methyl styrene-methacrylate-glycidyl acrylate polymer, the weight average molecular weight is 5000-6000, the compatilizer can be combined with terminal hydroxyl and terminal carboxyl in the material extrusion processing process, and the polylactic acid, the poly-3-hydroxybutyrate 4-hydroxybutyrate and the poly-adipate/butanediol ester have a large number of terminal hydroxyl and terminal carboxyl, and molecular chains of the polylactic acid, the poly-3-hydroxybutyrate 4-hydroxybutyrate and the poly-adipate/butanediol ester can be connected together by 'hand pulling', so that the molecular chain length is greatly increased, the compatibility of the material is improved, and the terminal carboxyl and the terminal hydroxyl are easy to migrate under the conditions of acetic acid and ethanol due to 'similar compatibility'.
The preparation method of the high-temperature-resistant low-migration and controllable-degradation polylactic acid straw comprises the following steps of:
(1) Mixing polylactic acid, poly 3-hydroxybutyrate 4-hydroxybutyrate and poly adipic acid/butanediol ester, adding a plasticizer, a nucleating agent, a dispersing agent, an anti-hydrolysis agent and a compatilizer in sequence under the stirring condition, and uniformly stirring to form a polylactic acid mixture;
(2) Adding the polylactic acid mixture into extrusion equipment, melting, mixing and extruding to obtain a polylactic acid straw blank, drawing the polylactic acid straw blank by traction equipment, sequentially passing through a water cooling device, an air cooling device, a dewatering device, a cutting device and a crystallizing device, and cooling to obtain the polylactic acid straw.
Further, in the step (1), the stirring temperature is 80-100 ℃, the stirring speed is 100-250r/min, and the stirring time is 5-10min.
Further, in the step (2), the extrusion temperature of the straw blank is 150-200 ℃, the temperature of the extrusion head of the extrusion equipment is generally slightly higher than the extrusion temperature, preferably 160-220 ℃, so that the extrusion is more stable; the drawing speed of the drawing equipment is 0.5-1.5m/s, and the water cooling temperature of the water cooling device is 30-50 ℃; the crystallization device is a tunnel furnace, heating is carried out through a medium-wave infrared lamp tube, the temperature in the tunnel furnace is ensured to be uniform and consistent through air blast circulation, the suction tube can be heated uniformly in the crystallization process, further, crystallization is more sufficient and stable, the crystallization temperature is 90-100 ℃, and the crystallization time is 1.5-2min.
The invention principle is as follows:
(1) According to the polylactic acid suction pipe with high temperature resistance, low migration resistance and controllable degradation, the poly-3-hydroxybutyrate-4-hydroxybutyrate and the poly-adipate/butanediol ester are added into the biodegradable material polylactic acid, the resilience and the heat resistance of the poly-3-hydroxybutyrate-4-hydroxybutyrate are utilized, so that the resilience after the crystallization of the polylactic acid suction pipe is improved, deformation does not occur in the crystallization process, the amorphous super-tough poly-adipate/butanediol ester is used for modifying a crystalline polymer, the crystallization property of the polylactic acid is improved, a high-toughness crystalline copolymer is formed, and the resilience and the toughness of the material are improved; meanwhile, after the polylactic acid is subjected to progressive blending with multi-arm poly-D-lactic acid, the crystallization speed of the polylactic acid is increased, and the crystallization time of the polylactic acid suction pipe in a crystallization tunnel furnace is reduced, so that the production efficiency is improved, and the polylactic acid suction pipe does not contain fluorine and has no fluorine exceeding risk; in addition, compared with the conventional plasticizer, the added citric acid fatty glyceride is more resistant to migration, and the 'solvation' effect of the citric acid fatty glyceride can improve the movement speed of a material molecular chain while improving the plastic property of the polylactic acid material, so that the crystallization speed is further improved to a certain extent; the degradation of the degradable material in an environment containing a large amount of carboxyl and water is greatly accelerated, the poly-carbonized dimethylamine can capture terminal carboxyl and water molecules at normal temperature and form green stable groups, so that the hydrolysis resistance of the material is improved, the degradation of polylactic acid in the processing and storage processes can be reduced, and the controllable degradation is further ensured.
(2) The preparation method of the crystallization process adopts a crystallization tunnel furnace treatment mode, is favorable for ensuring the production efficiency of the polylactic acid crystallization straw, and is not influenced by specifications; meanwhile, the poly-3-hydroxybutyrate 4-hydroxybutyrate and multi-arm poly-D-lactic acid in the formula effectively reduce the deformation phenomenon of polylactic acid in the crystallization production process, the production performance of the straw is ensured, meanwhile, the straw is extruded and molded by adopting a water cooling, air cooling and heating crystallization mode, the quick cooling effect of the straw is ensured, the problem of hydrolysis of the polylactic acid, the poly-3-hydroxybutyrate 4-hydroxybutyrate and the poly adipic acid/butanediol ester caused by long-time contact with water is avoided, the straw is molded by short-time water cooling, and the brittle fracture caused by the concentration of internal stress after quick cooling is avoided.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) The polylactic acid crystallization straw prepared by the invention can effectively improve the thermal stability of the polylactic acid straw and slow down the high-temperature degradation speed of the straw, and meanwhile, the material can effectively capture terminal carboxyl and terminal hydroxyl at normal temperature, so that small molecules are prevented from being generated in the quality guarantee period, and the safety and sanitation of the straw in the quality guarantee period are ensured; in addition, compared with the traditional polylactic acid straw, the mechanical property of the straw is obviously improved;
(2) The preparation method adopted by the invention not only improves the heat-resistant temperature of the polylactic acid straw, but also has lower cost compared with the traditional PBS/PLA (the PBS ratio is larger than the PLA) after the polylactic acid is crystallized, and the heat-resistant requirement and the hardness requirement of the traditional polylactic acid straw can be met by lighter gram weight (about 30 percent lighter).
Detailed Description
The present invention will be further described with reference to specific examples.
Example 1: the polylactic acid straw comprises the following components in percentage by mass:
80 percent of polylactic acid (optical purity is more than or equal to 99 percent),
7 percent of poly 3-hydroxybutyrate 4-hydroxybutyrate (acid value is less than or equal to 30 mol/t),
10 percent of poly adipic acid/butanediol ester (acid value is less than or equal to 30 mol/t),
multi-arm poly-D-lactic acid (EPOSS mole fraction 5.0X 10-5%, size 0.3-3 nm) 0.6%,
0.6 percent of citric acid fatty glyceride,
0.6 percent of fatty acid amide,
0.6 percent of polycarbodiimide,
0.6% of a methylstyrene-methacrylate-glycidyl acrylate polymer.
The preparation method of the polylactic acid straw comprises the following steps:
(1) Sequentially adding citric acid fatty acid glyceride, multi-arm poly-D-lactic acid, fatty acid amide, polycarbodiimide and styrene-acrylate-glycidyl methacrylate polymer into a resin mixture of polylactic acid, poly-3-hydroxybutyrate 4-hydroxybutyrate and poly-adipate/butanediol ester at a stirring speed of 200r/min and a stirring temperature of 80 ℃, and stirring for 5-10min to form a polylactic acid mixture;
(2) Adding the polylactic acid mixture into a double-screw extruder, and carrying out melting, mixing and extrusion to obtain a polylactic acid straw blank, wherein the extrusion temperature of the straw tube blank is 150-200 ℃, the temperature of an extruder head is 160-220 ℃, the polylactic acid straw blank is drawn by a drawing device and sequentially passes through a water cooling device, an air cooling device, a water removal device, a cutting device and a crystallization device, the drawing speed is 0.5-1.5m/s, the water cooling temperature of the water cooling device is controlled to be 30-50 ℃, and the crystallization process is as follows: and (3) adding the straw blank into a crystallization tunnel furnace for annealing crystallization under the conditions that the crystallization temperature is 90 ℃ and the crystallization time is 1.5min, and cooling to obtain the polylactic acid straw.
Example 2: the same procedure as in example 1 was followed except that: the polylactic acid straw comprises the following components in percentage by mass:
50 percent of polylactic acid (optical purity is more than or equal to 99 percent),
27 percent of poly 3-hydroxybutyrate 4-hydroxybutyrate (acid value is less than or equal to 30 mol/t),
20 percent of poly adipic acid/butanediol ester (acid value is less than or equal to 30 mol/t),
multi-arm poly-D-lactic acid (EPOSS mole fraction 5.0X 10-5%, size 0.3-3 nm) 0.6%,
0.6 percent of citric acid fatty glyceride,
0.6 percent of fatty acid amide,
0.6 percent of polycarbodiimide,
0.6% of a methylstyrene-methacrylate-glycidyl acrylate polymer.
Example 3: the same procedure as in example 1 was followed except that: the polylactic acid straw comprises the following components in percentage by mass:
65 percent of polylactic acid (optical purity is more than or equal to 99 percent),
17 percent of poly 3-hydroxybutyrate 4-hydroxybutyrate (acid value is less than or equal to 30 mol/t),
15 percent of poly adipic acid/butanediol ester (acid value is less than or equal to 30 mol/t),
0.6 percent of multi-arm poly-D-lactic acid (EPOSS molar fraction is 5.0 multiplied by 10-5 percent, size is 0.3-3 nm),
0.6 percent of citric acid fatty glyceride,
0.6 percent of fatty acid amide,
0.6 percent of polycarbodiimide,
0.6% of a methylstyrene-methacrylate-glycidyl acrylate polymer.
Example 4: the straw is the same as the polylactic acid straw in the embodiment 1 in the raw material composition ratio, and the differences are as follows: in the step (2) of the preparation method of the polylactic acid straw, the crystallization temperature is 90 ℃ and the crystallization time is 2min.
Example 5: the straw is the same as the polylactic acid straw in the embodiment 1 in the raw material composition ratio, and the differences are as follows: in the step (2) of the preparation method of the polylactic acid straw, the crystallization temperature is 100 ℃, and the crystallization time is 1.5min.
Comparative example 1: a polylactic acid straw was prepared with reference to example 1, except that: the conventional hydrazide nucleating agent is used in the market, and the mark is as follows: TMC-300 is substituted.
Comparative example 2: a polylactic acid straw was prepared with reference to example 1, except that: polycarbodiimide was not used.
Comparative example 3: a conventional PLA heat resistant straw formulation, the differences being: the straw is a conventional PBS/PLA straw formula, and the gram weight is heavier, and the PBS content is higher.
Comparative example 4: a polylactic acid straw was prepared with reference to example 1, except that: the mole fraction of octa-epoxy cage type polyhedral oligomeric silsesquioxane (EPOSS) in the multi-arm poly-D-lactic acid is 1 multiplied by 10 -4 ％。
Comparative example 5: a polylactic acid straw was prepared with reference to example 1, except that: the epoxidized soybean oil plasticizer is used for replacing the citric acid fatty acid glyceride plasticizer.
Examples 1 to 5 and comparative examples 1 to 5 of polylactic acid strawsThe raw material composition, preparation process and product performance are shown in the following tables 1 and 2. As can be seen from tables 1 and 2, the polylactic acid straw prepared by the method can effectively prolong the degradation time and the migration resistance of the straw, and the degradation time and the migration resistance are positively correlated with the content of the polycarbodiimide, so that the degradation time of the product can be adjusted by adjusting the content of the polycarbodiimide, and the product is more resistant to migration by using the citric acid fatty glyceride serving as a plasticizer compared with the traditional plasticizer such as epoxidized soybean oil; meanwhile, the gram weight of the traditional heat-resistant PLA straw product can be effectively reduced, the cost of the biodegradable straw is reduced, and the high and low temperature resistance of the biodegradable straw is improved; in addition, generally speaking, the straw crystallization time is long and the roundness straightness is poor in the crystallization process of products implemented in the industry, and the octaepoxy cage type polyhedral oligomeric silsesquioxane is added to be 5.0 multiplied by 10 in molar fraction -5 % of the multi-arm poly-D-lactic acid can effectively reduce the crystallization time of the polylactic acid straw and improve the straightness and roundness of the polylactic acid straw, and when the molar fraction is too high, indexes such as heat resistance temperature, migration, degradation and the like of the copolymer are poor due to the fact that the relative molecular mass and the decomposition temperature of the copolymer are reduced.
TABLE 1 summary of the composition and preparation of the polylactic acid straw raw materials for examples 1-5 and comparative examples 1-5
TABLE 2 summary of the polylactic acid straw Properties of examples 1-5 and comparative examples 1-5
Claims (10)
1. The utility model provides a high temperature resistant low migration and controllable degradation's polylactic acid straw which characterized in that, the straw includes according to mass percent: 50-80% of polylactic acid, 7-27% of poly-3-hydroxybutyrate 4-hydroxybutyrate, 10-20% of poly-adipate/butanediol ester, 0.2-1% of nucleating agent, 0.2-1% of plasticizer, 0.2-1% of dispersant, 0.4-0.8% of anti-hydrolysis agent and 0.4-0.8% of compatilizer.
2. The pipette as claimed in claim 1, wherein the optical purity of the polylactic acid is not less than 99% and the melt index is not more than 10g/10min.
3. The pipette of claim 1 wherein the poly-3-hydroxybutyrate 4-hydroxybutyrate has an acid number of less than or equal to 30mol/t and a melt index of less than or equal to 10g/10min and is prepared by copolymerizing poly-3-hydroxybutyrate and 4-hydroxybutyrate.
4. The straw according to claim 1, wherein the poly (adipic acid)/butylene glycol ester has an acid value of 30mol/t or less and a melt index of 10g/10min or less and is prepared by copolymerizing adipic acid and butylene glycol.
5. The pipette of claim 1 wherein the nucleating agent is a multi-arm poly-D-lactic acid prepared by the process of: the preparation method is characterized in that dextrorotatory lactide and octa-epoxy cage-shaped polyhedral oligomeric silsesquioxane are used as raw materials, stannous octoate is used as a catalyst, and anhydrous xylene is used as a solvent, and the preparation method is prepared by an in-situ ring-opening polymerization method; wherein the purity of the dextro-lactide is more than 99 percent, and the molar fraction of the stannous octoate is 2.0 multiplied by 10 -4 Mol fraction of octa-epoxy cage type polyhedral oligomeric silsesquioxane is 5.0 x 10 -5 % and the size is 0.3-3nm.
6. The straw according to claim 1, wherein the plasticizer is citric acid fatty acid glyceride, and the ester content is not less than 99%.
7. The straw as claimed in claim 1, wherein the dispersant is fatty acid amide, the anti-hydrolysis agent is polycarbodiimide, and the degree of polymerization is greater than or equal to 2000.
8. The pipette of claim 1 wherein the compatibilizer is a methyl styrene-methacrylate-glycidyl acrylate polymer having a weight average molecular weight of 5000 to 6000.
9. The preparation method of the high temperature resistant low migration and controllable degradation polylactic acid straw according to claim 1, characterized by comprising the following steps:
(1) Mixing polylactic acid, poly 3-hydroxybutyrate 4-hydroxybutyrate and poly adipic acid/butanediol ester, adding a plasticizer, a nucleating agent, a dispersing agent, an anti-hydrolysis agent and a compatilizer in sequence under the stirring condition, and uniformly stirring to form a polylactic acid mixture;
(2) Adding the polylactic acid mixture into extrusion equipment, melting, mixing and extruding to obtain a polylactic acid straw blank, drawing the polylactic acid straw blank by traction equipment, sequentially passing through a water cooling device, an air cooling device, a dewatering device, a cutting device and a crystallizing device, and cooling to obtain the polylactic acid straw.
10. The method according to claim 9, wherein in the step (2), the crystallization device is a tunnel furnace, and the medium wave infrared lamp tube is used for heating, the crystallization temperature is 80-110 ℃, and the crystallization time is 60-120s.
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| CN116606538A (en) * | 2023-06-26 | 2023-08-18 | 苏州优矿塑新材料股份有限公司 | Degradable composite material based on reaction compatibilization, environment-friendly straw and preparation method thereof |
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