WO2023246221A1 - 一种耐温pla刀叉勺及其制备方法 - Google Patents
一种耐温pla刀叉勺及其制备方法 Download PDFInfo
- Publication number
- WO2023246221A1 WO2023246221A1 PCT/CN2023/085163 CN2023085163W WO2023246221A1 WO 2023246221 A1 WO2023246221 A1 WO 2023246221A1 CN 2023085163 W CN2023085163 W CN 2023085163W WO 2023246221 A1 WO2023246221 A1 WO 2023246221A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- spoon
- pla
- cutlery
- fork
- knife
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 47
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000001746 injection moulding Methods 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 210000001161 mammalian embryo Anatomy 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- 210000002257 embryonic structure Anatomy 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000002667 nucleating agent Substances 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- -1 compatibilizer Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000000546 pharmaceutical excipient Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims description 2
- 239000004970 Chain extender Substances 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000004595 color masterbatch Substances 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000012745 toughening agent Substances 0.000 claims description 2
- 229920001896 polybutyrate Polymers 0.000 claims 2
- 238000005452 bending Methods 0.000 abstract description 47
- 229920000747 poly(lactic acid) Polymers 0.000 description 110
- 239000004626 polylactic acid Substances 0.000 description 110
- 238000012360 testing method Methods 0.000 description 21
- 229920003023 plastic Polymers 0.000 description 16
- 239000004033 plastic Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 13
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 8
- 239000004631 polybutylene succinate Substances 0.000 description 8
- 229920002961 polybutylene succinate Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 235000020965 cold beverage Nutrition 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000011324 bead Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 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 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 235000021268 hot food Nutrition 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000002699 waste material Substances 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 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
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
-
- 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
- B29C71/0063—After-treatment of articles without altering their shape; Apparatus therefor for changing crystallisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/28—Tools, e.g. cutlery
- B29L2031/286—Cutlery
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
Definitions
- the invention belongs to the technical field of tableware and relates to a temperature-resistant PLA knife, fork and spoon and a preparation method thereof.
- PLA cutlery and spoons are injection molded products with extremely short production cycles; in addition, PLA has a high glass transition temperature (50-60°C) and slow crystallization; regardless of the formula, even if a nucleating agent is added, PLA Injection molded products usually do not crystallize completely. Not only is the strength not high, but it also deforms when exposed to heat. It requires subsequent heat treatment to ensure stable product quality.
- general heat treatment methods drying tunnel, oven, hot blowing, infrared heating
- PLA cutlery and spoons after heat treatment are generally not resistant to bending and are prone to bending brittle fracture. It can be seen that making PLA into cutlery, forks and spoons with excellent performance is still a major challenge for the tableware manufacturing industry.
- the PLA cutlery and spoon raw materials in step (1) include the following components in terms of mass:
- the main material is PLA
- the filler is selected from any one or a combination of talc, calcium carbonate, silica, bentonite, coffee grounds powder and bamboo powder;
- the modifier is selected from any nucleating agent, antioxidant, antistatic agent, antibacterial agent, color masterbatch, compatibilizer, toughening agent, lubricant, release agent, chain extender or cross-linking agent.
- nucleating agent antioxidant, antistatic agent, antibacterial agent, color masterbatch, compatibilizer, toughening agent, lubricant, release agent, chain extender or cross-linking agent.
- the amount and type of fillers and modifiers added are such that they do not affect the effect of carbon dioxide, the performance of cutlery, forks and spoons, and the concept of environmental protection; according to actual needs, the modifiers may not be added.
- the PLA is selected from a single brand or a blend of multiple brands.
- the PLA cutlery and spoon raw materials in step (1) use pellets prepared through an extrusion blending granulation process.
- the carbon dioxide soaking method described in step (2) is: the PLA knife, fork and spoon sample embryo is placed in a temperature-adjustable sealed container that is resistant to high temperature and high pressure, and the Inject carbon dioxide into a sealed container, soak at constant temperature and pressure, quickly release the pressure after soaking, open the container, take out the sample, and cool it at room temperature to obtain the product; the high temperature and high pressure resistant container is any sealed container with adjustable temperature and pressure resistance.
- the holding temperature is 45-110°C
- the holding pressure is 4-12MPa
- the holding time is 6-60min
- the pressure release speed is 5-45MPa/s.
- the carbon dioxide is supercritical carbon dioxide fluid or subcritical carbon dioxide fluid.
- the products provided by the invention are:
- the holding pressure is ⁇ 7 MPa and ⁇ 12 MPa, and the pressure is released Speed ⁇ 24 MPa/s; preferably, the holding pressure is ⁇ 9 MPa and ⁇ 10.5 MPa, and the pressure release speed is ⁇ 31 MPa/s; the density of the obtained knife, fork and spoon product is 0-30% lower than the density of the knife, fork and spoon embryo ( Excluding 0).
- the invention also provides a temperature-resistant PLA knife, fork and spoon.
- the knife, fork and spoon is a micro-foamed product, and the density of the knife, fork and spoon is reduced by 5-30% compared to the knife, fork and spoon embryo. It has temperature resistance above 65°C.
- the present invention has the following beneficial effects:
- the present invention provides a new method for preparing PLA cutlery and spoons. Under certain temperature and pressure conditions, carbon dioxide fluid can quickly dissolve and penetrate into PLA cutlery and spoons, which can eliminate the inherent problems caused by the molecular orientation of injection molding. Stress assists the movement of PLA macromolecular chains, adjusts the spatial structure arrangement of PLA macromolecular chains, induces PLA to complete crystallization without causing bending deformation of the cutlery, and changes the strength and temperature resistance of PLA cutlery; when carbon dioxide Fluid Better results can be obtained when using supercritical fluid carbon dioxide.
- the present invention has better brittle tear resistance.
- General heat treatment (oven, hot drying tunnel) usually produces large spherulites of PLA; however, CO2 treatment can obtain small PLA grains, so it can improve the brittle fracture performance of PLA.
- the present invention allows carbon dioxide to rapidly vaporize and expand through rapid pressure relief, which can produce micro-nano pore structures inside PLA cutlery, reducing product density, increasing toughness, and resistance to bending and brittle cracking.
- the process parameters of the present invention can be accurately controlled, and the product quality has high stability; because the cutlery, fork, and spoon embryos are soaked in carbon dioxide, and the process parameters can be accurately controlled, the products can be processed with each other and within the product. To achieve uniformity, the product design shape remains unchanged.
- the temperature resistance of the present invention is adjustable and is suitable for the use requirements of various hot and cold meals; the PLA cutlery and spoons of the present invention can generally withstand temperatures >65°C and can be used in Western food and cold drinks; the PLA cutlery and spoons can also be used in Western food and cold drinks. It can withstand temperatures above 100°C, meeting the requirements for hot food and hot vegetable food with oil.
- the present invention can reduce costs. Since the carbon dioxide immersion treatment of cutlery can induce complete crystallization of PLA, so less or no nucleating agent can be used, and crystallized PLA cutlery can also be made. This alone can reduce raw material costs by 10%. In addition, cutlery, forks and spoons can also be made into micro-nano cell structures, thereby reducing the amount of raw materials used and lowering the production cost of the product. In addition, the present invention can use general brands of PLA, which is also beneficial to reducing the production cost of the product.
- the present invention uses PLA as the main material, and the cutlery and spoon products produced thereby are biodegradable, and the waste after use will not cause environmental pollution.
- This invention helps to promote PLA cutlery and spoons to replace existing PP or PS cutlery and spoons.
- This invention narrows the price difference between traditional plastic tableware and biodegradable plastic tableware, and at the same time has a better appearance and is white. , or silvery white.
- the present invention also provides a new cutlery and spoon.
- the cutlery and spoons currently on the market are all non-foaming cutlery and spoons, but the cutlery and spoons of the present invention are in the form of micro-foaming.
- the cutlery and spoons of the present invention are in the form of micro-foaming.
- PLA cutlery and spoons acquired new properties after micro-foaming. In addition to temperature resistance, it also has the function of resisting bending and brittle fracture, making it Knives, forks and spoons can prevent accidental breakage during chewing, making people feel more comfortable and safe.
- the method for measuring the density of cutlery, forks and spoons in the examples is:
- the density of the knife, fork and spoon embryo is d 0
- the knife, fork and spoon product density is d f .
- the micro-nano cell structure is generated inside the knife, fork and spoon, and the density decrease percentage X is:
- Chatillon CS225 dynamometer equipped with a manual mechanical clamp for the sample, connect a curved indenter with an arc diameter of 10mm and a length of 50mm, and use a plastic spoon (the total length of the spoon head plus handle is 140mm, and the handle is 90mm)
- the test method is as follows: fix the weakest point of the spoon handle (100mm from the spoon head) to the clamp, with the concave surface of the spoon facing upward, and press the curved indenter (almost in contact) on the spoon handle 70mm from the spoon head (i.e.
- the edge of the clamp 30mm away from the indenter
- Table 1-3 The composition of PLA in the raw material formula of cutlery, forks and spoons
- one or two blends of PLA are used as the main material, and PBAT or PBS or a blend of PBAT and PBS is used as the auxiliary material (no auxiliary material can be added as well) ), using talcum powder as filler, TBC (plasticizer) and calcium stearate (lubricant) as modifiers, a total of ten formulas of PLA knife, fork and spoon embryos were prepared from 01 to 10.
- the preparation process is: through the extruder blending and granulation process, raw material particles of various formulas are prepared. These raw material particles are then used through the injection molding process of the injection molding machine to prepare PLA cutlery, forks and spoon prototypes with predetermined shapes, sizes and weights. These PLA cutlery and spoon-like embryos are not temperature-resistant (the maximum temperature resistance is ⁇ 60°C).
- the density of the sample increased slightly ( ⁇ 1%), and the sample shape was significantly deformed; the temperature resistance of knives, forks and spoons in 01 and 04 was ⁇ 65°C, while the temperature resistance of knives, forks and spoons in 02 and 03 was ⁇ 80°C and ⁇ 75°C; the 02 sample broke in the bending resistance test, and the other samples did not break in the bending resistance test.
- the temperature resistance of 06 and 08 cutlery and spoons is ⁇ 80°C, and the temperature resistance of 05, 07 and 010 cutlery and spoons is ⁇ 90°C. °C, the temperature resistance of 09 cutlery and spoons is ⁇ 95 °C; all samples of 05-010 did not break in the bending resistance test.
- the density of 05-07, 09 and 010 decreased by 12.4%, 15.1%, 11.3%, 8.9% and 10.7% respectively; the temperature resistance of 05 and 010's cutlery and spoons is ⁇ 70°C, 06
- the temperature resistance of knives, forks and spoons of 07 and 07 is ⁇ 65°C, and the temperature resistance of knives, forks and spoons of 09 is ⁇ 75°C; the sample did not break in the bending resistance test.
- the density of PLA cutlery can be reduced by 8-29%, and its temperature resistance can vary between 65-95°C depending on the formula composition or the treatment process conditions. ;
- the samples of the present invention basically have improved resistance to bending brittle fracture or bending brittleness.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Emergency Medicine (AREA)
- Table Equipment (AREA)
Abstract
本发明属于餐饮具的技术领域,涉及一种耐温PLA刀叉勺的制备方法,所述方法包括以下步骤:(1)PLA刀叉勺原料经注塑机注塑成型,制备得到刀叉勺样胚,刀叉勺样胚中含有未能完成结晶的PLA;(2)刀叉勺样胚经过恒温恒压的二氧化碳浸泡处理,使刀叉勺样胚中未结晶的PLA完成结晶,制备得到耐温性≥65℃的PLA刀叉勺产品。本发明还提供了一种耐温PLA刀叉勺,所述刀叉勺为微发泡产品,所述刀叉勺的密度相对于刀叉勺样胚降低5-30%,所述刀叉勺具有65℃以上的耐温性。本发明提供的耐温PLA刀叉勺及其制备方法,所制备的PLA刀叉勺具有耐温、耐弯曲脆裂的优点,还可生物降解,是新一代的环保刀叉勺产品。
Description
本发明属于餐饮具的技术领域,涉及一种耐温PLA刀叉勺及其制备方法。
刀叉勺是餐饮具中最常见的用品。塑料餐具以其价廉物美、无毒无味、清洁卫生、用餐前后无须清洗、用完即扔、使用方便,生产便捷,产能无限,已成为了现代社会文明生活发展的一种标志性产物。无论是交通出行或野外工作就餐,还是参加各种大型活动后成千上万人的快速就餐,一次性塑料刀叉勺都成为了不可或缺的必备用品,给就餐活动带来了极大便利。
随着现代人生活和工作节奏加快,快餐和外卖行业兴起和不断发展,一次性塑料刀叉勺的用量仍在快速增长。然而由于塑料刀叉勺大都采用传统塑料[PS(聚苯乙烯),PP(聚丙烯),等]生产制备,每年都要消耗成千上万吨塑料资源,且废弃物又污染环境,现已成为国家“禁塑令”首先要禁止生产和销售的一次性塑料产品之一。
现在市场上的一次性塑料刀叉勺大多都是由PS或PP两种原料生产制备的。PS刀叉勺材质坚硬,外观透明。而PP刀叉勺材质坚韧,抗弯曲,不脆裂,耐温性好。尽管它们物美价廉,使用方便,已满足各种餐饮食品的要求,但是它们都是传统塑料,不降解,也不易回收(成本太高)。
可生物降解塑料PLA(聚乳酸)刀叉勺是餐饮具开发的新品。由于PLA与传统塑料PP性能相当,因此它被选作为替代PP原料生产餐具。但是发现,未结晶PLA餐具太软,不能满足强度的要求,也不耐热,遇热变形;完全结晶的PLA餐具可耐热,但脆性较大,很容易弯曲脆裂;现已发现,添加剂如滑石粉,既可以成核促进PLA结晶,改善材质强度和硬度,又可以降低原材料成本;加入柔性的可生物降解高聚物如PBAT(己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物)或PBS(聚丁二酸-丁二醇酯),可以增韧,改善PLA弯曲脆裂。由此可见,通过对PLA进行适当(增强、增韧、抗脆裂,降成本)改性,PLA刀叉勺是可以满足一次性塑料餐具性能要求,有望发展成为传统塑料餐具的替代产品。
现有的PLA刀叉勺大多都是注塑产品,生产周期极短;再加上PLA玻璃化转变温度(50-60℃)较高,结晶缓慢;无论配方如何,即使添加了成核剂, PLA注塑制品通常也不能结晶完全。不仅强度不高,而且遇热还要变形,必须后续热处理,产品方能质量稳定。然而由于一般热处理(烘道、烘箱、热吹风、红外加热)方法都不容易做到精确调控和均匀一致,产品容易变形,质量波动,次品和废品率较高。即使这样,热处理后的PLA刀叉勺一般都不抗弯折,容易发生弯曲脆性断裂。可见,要把PLA做成性能优异的刀叉勺产品,仍然是餐饮具制造业的一大挑战。
有关耐温PLA刀叉勺研究报道很少,CN112778726A提出了一种PLA耐热刀叉勺及生产方法。使用外消旋聚乳酸作为PLA材料,以提高其玻璃化转变温度(Tg)和熔融温度(Tm);加入成核剂,以促进材料结晶;注塑成型后再进入热烘道结晶,得到PLA耐热刀叉勺产品。但由于外消旋聚乳酸是将左旋聚乳酸和右旋聚乳酸形成特殊立构结构的产品,产能有限,目前价格较高,不容易做大市场规模。目前市场上PLA耐热刀叉勺大多都采用高熔点、快结晶的PLA为原料,辅以成核剂和加工助剂,通过热烘道再结晶方法,来制备生产耐热PLA产品。由于热烘道不容易做到均匀加热,产品容易变形,为此,最近有人采用注塑产品快速浸泡热水方式,让PLA结晶,但这很难保证产品不吸水,而微量水的介入可能成为产品后续老化变质的隐患。
本发明针对现有技术的不同,提供了一种耐温PLA刀叉勺及其制备方法,所制备的PLA刀叉勺具有耐温、耐弯曲脆裂的优点,还可生物降解,是新一代的环保刀叉勺产品。
为解决上述技术问题,本发明的目的通过下述技术方案得以实现:
一种耐温PLA刀叉勺的制备方法,所述方法包括以下步骤:
(1)PLA刀叉勺原料经注塑机注塑成型,制备得到刀叉勺样胚,刀叉勺样胚中含有未能完成结晶的PLA;
(2)刀叉勺样胚经过恒温恒压的二氧化碳浸泡处理,使刀叉勺样胚中未结晶的PLA完成结晶,制备得到耐温性≥65℃(是指最高耐热温度≥65℃)的PLA刀叉勺产品。
在上述的一种耐温PLA刀叉勺的制备方法中,步骤(1)中所述PLA刀叉勺原料以质量计包括以下组分:
主料50-80%
辅料0-20%
填料10-30%
改性剂0-5%;
所述主料为PLA;
所述辅料为PBAT、PBS或PBAT与PBS的共混物;根据实际需要,所述辅料也可以不添加;
所述填料选自滑石粉、碳酸钙、二氧化硅、膨润土、咖啡渣粉和竹粉中的任一种或多种组合;
所述改性剂选自成核剂、抗氧剂、抗静电剂、抗菌剂、色母、相容剂、增韧剂、润滑剂、脱模剂、扩链剂或交联剂中的任一种或多种组合;添加的填料和改性剂用量和种类以不影响二氧化碳作用效果、刀叉勺性能和环保理念为度;根据实际需要,所述改性剂也可以不添加。
在上述的一种耐温PLA刀叉勺的制备方法中,所述PLA选自单一牌号或者多个牌号的共混物。
在上述的一种耐温PLA刀叉勺的制备方法中,步骤(1)中所述PLA刀叉勺原料使用经过挤出共混造粒工艺制备而成的粒料。
在上述的一种耐温PLA刀叉勺的制备方法中,步骤(2)中所述二氧化碳浸泡的方式是:PLA刀叉勺样胚放置在耐高温高压的可调温密闭容器中,所述密闭容器中注入二氧化碳,恒温保压浸泡,浸泡完成后快速泄压,打开容器,取出样品,室温冷却,得到产品;所述耐高温高压的容器是可调控温度的、耐压的任何密闭容器。
在上述的一种耐温PLA刀叉勺的制备方法中,步骤(2)中保压温度为45-110℃,保压压力为4-12MPa,保压时间为6-60min,泄压速度为5-45MPa/s。
在上述的一种耐温PLA刀叉勺的制备方法中,所述二氧化碳为超临界二氧化碳流体或者亚临界二氧化碳流体。
在上述的一种耐温PLA刀叉勺的制备方法中,通过调整配方和浸泡参数,可以获得不同耐温性的刀叉勺产品,一般而言,在相同的配方下,保压温度越高,得到的刀叉勺产品的耐温性越高。
本发明所提供的产品分别为:
耐温刀叉勺产品,耐温性≥65℃且<100℃中的任一温度;这种产品适合西餐和冷饮食品使用;
高耐温刀叉勺产品,耐温性>100℃;这种产品适合热饮食品和带油热菜食品使用。
在上述的一种耐温PLA刀叉勺的制备方法中,通过调整浸泡参数,可以获得低密度的刀叉勺产品;可选的,所述保压压力≥7 MPa且<12 MPa,泄压速度≥24 MPa/s;优选的,保压压力≥9 MPa且<10.5 MPa,泄压速度≥31 MPa/s;所获得刀叉勺产品密度比刀叉勺样胚密度降低0-30%(不含0)。
本发明还提供了一种耐温PLA刀叉勺,所述刀叉勺为微发泡产品,所述刀叉勺的密度相对于刀叉勺样胚降低5-30%,所述刀叉勺具有65℃以上的耐温性。
本发明和现有技术相比,具有如下有益效果:
1、本发明提供了一种新的PLA刀叉勺的制备方法,在一定的温度和压力条件下,二氧化碳流体可快速溶解渗透到PLA刀叉勺中,可消除注塑分子取向所带来的内应力,协助PLA大分子链运动,可调整PLA大分子链的空间结构排列,在不造成刀叉勺弯曲变形情况下,诱导PLA完成结晶,改变PLA刀叉勺的强度和耐温性;当二氧化碳流体使用超临界流体二氧化碳时可以获得更好的效果。
2、本发明具有更好的抗脆性撕裂性能,一般热处理(烘箱、热烘道)通常产生PLA大球晶;而CO2处理却能够得到PLA小微晶粒,因此可改善PLA脆性断裂性能。
3、本发明通过快速卸压,让二氧化碳急剧气化膨胀,可以在PLA刀叉勺内部产生微纳米泡孔结构,使得产品密度降低、韧性增加、可耐弯曲脆裂。
4、本发明的工艺参数可以精准调控,产品质量稳定性高;由于刀叉勺样胚是浸泡在二氧化碳中处理,又加上可以精确调控工艺参数,所以产品彼此之间和产品内部都可以做到均匀一致,产品设计形状不变。
5、本发明的耐温性可调,适合各种冷热餐食的使用要求;本发明PLA刀叉勺一般都可以耐温>65℃,可在西餐和冷饮食品使用;PLA刀叉勺也可做到耐温>100℃以上,满足热饮食品和带油热菜食品使用要求。
6、本发明生产效率高,采用二氧化碳处理技术后,由于不再受注塑样胚是否结晶所限,PLA刀叉勺配方组成可简化,注塑成型生产周期可缩短,样胚完全结晶是在二氧化碳浸泡容器中批量生产完成的,最终PLA刀叉勺产品的生产效率可提升10%以上。
7、本发明可降低成本,由于二氧化碳浸泡处理刀叉勺,可诱导PLA结晶完全,所以可少用或者不用成核剂,同样可做成结晶的PLA刀叉勺。仅此一项就可降低原材料成本10%。此外,刀叉勺也可以做成微纳米泡孔结构,从而减少原材料用量,降低产品的生产成本。另外,本发明可使用一般牌号的PLA,也有利于降低产品的生产成本。
8、本发明采用PLA作为主料,由此生产的刀叉勺产品可生物降解,使用后的废弃物不会造成环境污染。
9、本发明有助于促进PLA刀叉勺替代现有的PP或PS刀叉勺,本发明缩小了传统塑料餐具与可生物降解塑料餐具在价格上差异,同时具有更好的外观,呈白色、或银白色。
10、本发明还提供了一种新的刀叉勺,现有市场上的刀叉勺均为非发泡刀叉勺,但本发明的刀叉勺采用微发泡的形式。在对二氧化碳流体处理PLA刀叉勺进行深入研究的过程中,研发人员发现,PLA刀叉勺经过微发泡之后获得了新特性,在耐温之外,还有抗弯曲脆断的作用,使得刀叉勺在使用的时候可以防止咀嚼意外脆断,使人感觉更加舒适和安全。
下面通过具体实施方式的描述对本发明作进一步说明,但这并非是对本发明的限制,本领域技术人员根据本发明的基本思想,可以做出各种修改或者改进,但是只要不脱离本发明的基本思想,均在本发明的范围之内。
本实施例中各试验数据的测定方法如下:
1、实施例中刀叉勺密度测定方法是:
根据阿基米德浮力原理,采用排水法,分别称取刀叉勺样品在空气中重量(W
1)和在水中重量(W
2),两者的重量差即为样品所受的浮力(F),它等于样品体积(V
s)乘上水的密度(d
w)。从而可计算出样品的密度(d
s)。
F = W
1-W
2= d
w* V
s
d
s=W
1/V
s =d
w*W
1/(W
1-W
2)
2、实施例中刀叉勺密度下降百分数的计算方法是:
刀叉勺样胚密度d
0, 刀叉勺产品密度d
f,经过二氧化碳处理后,刀叉勺内部产生微纳米泡孔结构,其密度下降百分数X为:
X (%) = (d
0 – d
f)/d
0*100
3、实施例中刀叉勺耐温性的测定方法是:
量取200克玻璃珠将其放入500mL烧杯中,在烧杯内倒入约3/4烧杯的水,将该烧杯放入设置好温度的恒温水浴锅中,插入温度计,当烧杯中的温度达到所需温度时,往烧杯中插入刀叉勺,等待5秒后,使用勺子不断舀烧杯中的玻璃珠,重复该动作20次,观察刀叉勺搅拌过程中及搅拌后刀叉勺状态。若刀叉勺在搅拌过程变软无法顺畅搅动,或者搅拌后严重变形,则可终止试验,判断该刀叉勺无法耐受此温度。若刀叉勺仍能保持原始状态,判断该刀叉勺可耐此温度。实验温度达到100℃,勺子仍能耐温,则判定该刀叉勺的最高耐温可达100℃以上。实施例中选用塑料汤勺(勺头加勺柄总长140mm,勺柄90mm)作为测试刀叉勺耐温性的样品。
4、实施例中刀叉勺耐弯曲断裂的测定方法是:
用查狄伦(Chatillon CS225型)测力计,配以样品手动机械夹具,接弧面直径10mm,长50mm的弯曲压头,选用塑料汤勺(勺头加勺柄总长140mm,勺柄90mm)作为测试刀叉勺耐弯曲断裂的样品。其测试方法如下:将勺柄最薄弱点(距勺头100mm)固定在夹具处,勺肚凹面朝上,弯曲压头(几乎接触)压在距离勺头70mm处的勺柄上面(即夹具边缘到压头距离30mm处),以300mm/min的速度下压至勺柄弯折60度角(下压距离大致50mm),观察勺柄是否断裂以及断裂时勺柄的弯折角度(下压距离)。若下压勺柄弯曲不出现折断,则判定此勺耐弯曲脆断;若下压勺柄弯曲折断,则判定此勺不耐弯曲脆断。
本发明实施例中的原料来源如表1-1所示:
表1-1 原料及来源
化合物 | 牌号或规格 | 来源 |
PLA | 201、210、290 | 海正生物 |
PBAT | KHB21AP11 | 康辉新材料 |
PBS | 803S | 新疆蓝山屯 |
滑石粉 | 1250目 | 市售 |
柠檬酸三丁酯(TBC) | LM30 | 雷蒙新材料 |
硬脂酸钙 | 一级品 | 杭州油脂化工 |
表1-2 PLA刀叉勺原料配方、密度和耐温性
配方编号 | PLA(%) | PBAT(%) | PBS(%) | 填料(%) | TBC(%) | 硬脂酸钙(%) | 密度(g/cm 3) | 耐温性(最高耐温)(℃) |
01 | 50 | 20 | 30 | 1 | 1 | 1.488 | 50 | |
02 | 60 | 10 | 30 | 1 | 1 | 1.491 | 50 | |
03 | 60 | 20 | 20 | 0.5 | 1 | 1.414 | 50 | |
04 | 80 | 10 | 10 | 0.2 | 1 | 1.327 | 50 | |
05 | 70 | 30 | 1 | 1.471 | 50 | |||
06 | 65 | 5 | 30 | 1 | 1.477 | 50 | ||
07 | 65 | 5 | 30 | 1 | 1.477 | 50 | ||
08 | 60 | 5 | 5 | 30 | 1 | 1.484 | 50 | |
09 | 70 | 30 | 1 | 1.490 | 55 | |||
010 | 68 | 2 | 30 | 1 | 1.478 | 50 |
表1-3 刀叉勺原料配方中PLA组成
配方编号 | 201PLA(%) | 210PLA(%) | 290PLA(%) | PLA(%) |
01 | 50 | 50 | ||
02 | 60 | 60 | ||
03 | 60 | 60 | ||
04 | 80 | 80 | ||
05 | 45 | 25 | 70 | |
06 | 40 | 25 | 65 | |
07 | 40 | 25 | 65 | |
08 | 60 | 60 | ||
09 | 70 | 70 | ||
10 | 68 | 68 |
实施例中按照以下方法制备PLA刀叉勺样品。
(1)PLA刀叉勺样胚的制备:
按照表1-2和表1-3中的配方组成,分别以一种或两种共混的PLA为主料,以PBAT或PBS或PBAT与PBS的共混物为辅料(也可以不添加辅料),以滑石粉为填料,以TBC(增塑剂)和硬脂酸钙(润滑剂)为改性剂,制备得到01-10共十种配方的PLA刀叉勺样胚。其制备过程是:经过挤出机共混造粒工艺,制备出各种配方的原料粒子。用这些原料粒子再经过注塑机注塑成型工艺流程,制备出预定形状、尺寸大小和重量的PLA刀叉勺样胚。这些PLA刀叉勺样胚是不耐温的(最高耐温<60℃)。
(2)PLA刀叉勺样品的制备:
将PLA刀叉勺样胚放置在恒温恒压的二氧化碳密闭容器(模具)中浸泡预定时间,然后快速卸压开模,取出样品,在室温下冷却,即得PLA刀叉勺产品。不同配方的PLA刀叉勺的二氧化碳处理加工条件如表2所示。
表2 PLA刀叉勺的二氧化碳处理加工工艺条件及性能测试
实施例# | 配方# | 保压温度(℃) | 保压压力(MPa) | 保压时间(min) | 卸压速度(MPa/s) | 产品密度(g/cm 3) | 密度下降(%) | 耐温性(最高耐温)(℃) | 耐弯曲脆断(mm) |
1 | 01 | 70 | 4.5 | 60 | 16 | 1.492 | -0.3 | 65 | 50 |
02 | 70 | 4.5 | 60 | 16 | 1.499 | -0.5 | 70 | 50 | |
03 | 70 | 4.5 | 60 | 16 | 1.411 | 0.2 | 70 | 50 | |
04 | 70 | 4.5 | 60 | 16 | 1.335 | -0.6 | 65 | 50 | |
2 | 01 | 85 | 4 | 20 | 14 | 1.486 | 0.1 | 65 | 50 |
02 | 85 | 4 | 20 | 14 | 1.498 | -0.5 | 80 | 50 | |
03 | 85 | 4 | 20 | 14 | 1.408 | 0.4 | 75 | 50 | |
04 | 85 | 4 | 20 | 14 | 1.326 | 0.1 | 65 | 50 | |
3 | 05 | 65 | 4.5 | 40 | 16 | 1.474 | -0.2 | 90 | 50 |
06 | 65 | 4.5 | 40 | 16 | 1.480 | -0.2 | 80 | 50 | |
07 | 65 | 4.5 | 40 | 16 | 1.482 | -0.3 | 90 | 50 | |
08 | 65 | 4.5 | 40 | 16 | 1.491 | -0.5 | 80 | 50 | |
09 | 65 | 4.5 | 40 | 16 | 1.487 | 0.2 | 95 | 50 | |
010 | 65 | 4.5 | 40 | 16 | 1.476 | 0.1 | 90 | 50 | |
4 | 05 | 105 | 4.5 | 10 | 16 | 1.477 | -0.4 | 95 | 23.2 |
06 | 105 | 4.5 | 10 | 16 | 1.482 | -0.3 | 90 | 31.5 | |
07 | 105 | 4.5 | 10 | 16 | 1.480 | -0.2 | 95 | 31.2 | |
08 | 105 | 4.5 | 10 | 16 | 1.487 | -0.2 | 90 | 50 | |
09 | 105 | 4.5 | 10 | 16 | 1.485 | 0.3 | >100 | 20.3 | |
5 | 05 | 50 | 10 | 60 | 34 | 1.045 | 29.0 | 70 | 50 |
09 | 50 | 10 | 60 | 34 | 1.106 | 25.8 | 70 | 50 | |
6 | 05 | 60 | 9.5 | 15 | 33 | 1.288 | 12.4 | 70 | 50 |
06 | 60 | 9.5 | 15 | 33 | 1.254 | 15.1 | 65 | 50 | |
07 | 60 | 9.5 | 15 | 33 | 1.310 | 11.3 | 65 | 50 | |
09 | 60 | 9.5 | 15 | 33 | 1.357 | 8.9 | 75 | 50 | |
010 | 60 | 9.5 | 15 | 33 | 1.320 | 10.7 | 70 | 50 | |
7 | 05 | 70 | 8 | 30 | 28 | 1.340 | 8.9 | 70 | 50 |
05 | 70 | 9.5 | 30 | 33 | 1.135 | 22.8 | 75 | 50 | |
05 | 70 | 11 | 30 | 38 | 1.036 | 29.6 | 75 | 50 | |
8 | 05 | 85 | 9.5 | 8 | 33 | 1.335 | 9.3 | 95 | 34.3 |
07 | 85 | 9.5 | 8 | 33 | 1.356 | 8.2 | 85 | 29.6 | |
9 | 06 | 85 | 10 | 6 | 34 | 1.361 | 7.9 | 75 | 50 |
09 | 85 | 10 | 6 | 34 | 1.335 | 10.4 | 95 | 20.8 | |
010 | 85 | 10 | 6 | 34 | 1.122 | 20.1 | 90 | 23.6 |
表3 PLA刀叉勺的热烘箱处理后产品密度、耐温性和耐弯曲脆断性
实施例1
取配方组成为编号01-04的PLA刀叉勺样胚,放置在70℃模具容器中,注入4.5MPa的二氧化碳,恒温恒压浸泡60 min,以16MPa/s速度快速卸压,开模取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表2所示。经二氧化碳处理后,样品密度几乎没有多少变化,样品镜面外观光亮消失,样型没明显变化,01和04的刀叉勺耐温≤65℃,而02和03的刀叉勺耐温≤70℃;样品耐弯曲测试不折断。
实施例2
取配方组成为编号01-04的PLA刀叉勺样胚,放置在85℃模具容器中,注入4MPa的二氧化碳,恒温恒压浸泡20 min,以14MPa/s速度快速卸压,开模取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表2所示。经二氧化碳处理后,样品密度几乎没有多少变化,样品镜面外观光亮消失,除04样品外,样型都没有明显变化,01和04的刀叉勺耐温≤65℃,而02和03的刀叉勺耐温分别为≤80℃和≤75℃;样品耐弯曲测试不折断。
对比例1
取配方组成为编号01-04的PLA刀叉勺样胚,放置在110℃烘箱中,恒温通风处理10 min,开烘箱取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表3所示。经通风烘箱处理后,样品密度稍有一点增加(<1%),样型有明显变形;01和04的刀叉勺耐温≤65℃,而02和03的刀叉勺耐温分别为≤80℃和≤75℃;02样品耐弯曲测试折断,其他样品耐弯曲测试都不折断。
由上面实施例1、实施例2和对比例1可知,PLA刀叉勺样品的耐温性依赖配方组成,可在65-80℃之间变化,本发明的样品与传统热处理的样品可达到同样的耐温效果,但本发明的样品可以保持样型基本不变,也可耐弯曲脆断。
实施例3
取配方组成为编号05-010的PLA刀叉勺样胚,放置在65℃模具容器中,注入4.5MPa的二氧化碳,恒温恒压浸泡40 min,以16MPa/s速度快速卸压,开模取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表2所示。经二氧化碳处理后,样品密度几乎没有多少变化,样品镜面外观光亮消失,样型没明显变化,06和08的刀叉勺耐温≤80℃,05,07和010的刀叉勺耐温≤90℃,09的刀叉勺耐温≤95℃;05-010所有样品耐弯曲测试都不折断。
实施例4
取配方组成为编号05-09的PLA刀叉勺样胚,放置在105℃模具容器中,注入4.5MPa的二氧化碳,恒温恒压浸泡10 min,以16MPa/s速度快速卸压,开模取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表2所示。经二氧化碳处理后,样品密度几乎没有多少变化,样品镜面外观光亮消失,样型没明显变化,06和08的刀叉勺耐温≤90℃,05和07的刀叉勺耐温≤95℃,09的刀叉勺耐温>100;08样品耐弯曲测试不折断,而05-07和09样品耐弯曲测试都折断。
对比例2
取配方组成为编号05-010的PLA刀叉勺样胚,放置在110℃烘箱中,恒温通风处理10 min,开烘箱取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表3所示。经通风烘箱处理后,样品密度几乎没变化,样品镜面外观光亮消失,样型没明显变化,05和09的刀叉勺耐温>100℃,06和08的刀叉勺耐温≤90℃,07和010的刀叉勺耐温≤95℃;除08样品耐弯曲测试不折断外,其他样品耐弯曲测试都脆断。
由上面实施例3、实施例4和对比例2可知,在相同的配方下,提高保压温度可以提高产品的耐温性,甚至可以生产出耐温性>100℃的产品,与传统热处理的样品可达到同样的耐温效果,但本发明的样品可以保持样型基本不变;当提高保压温度使产品耐温性增强后,其耐弯曲脆断性能降低,但依然好于对比例2,对比例中的产品相比实施例4所对应的折断样品,其折断下压距离更小,即耐弯曲脆断性能更差。
实施例5
取配方组成为编号05和09的PLA刀叉勺样胚,放置在50℃模具容器中,注入10MPa的二氧化碳,恒温恒压浸泡60 min,以34MPa/s速度快速卸压,开模取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表2所示。经二氧化碳处理后,样品外观白色,05和09密度分别下降了29.0% 和25.8%,耐温≤70℃;样品耐弯曲测试不折断。
实施例6
取配方组成为编号05-07,09和010的PLA刀叉勺样胚,放置在60℃模具容器中,注入9.5MPa的二氧化碳,恒温恒压浸泡15 min,以33MPa/s速度快速卸压,开模取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表2所示。经二氧化碳处理后,样品外观白色,05-07,09和010的密度分别下降了12.4%,15.1%,11.3%,8.9%和10.7%;05和010的刀叉勺耐温≤70℃,06和07的刀叉勺耐温≤65℃,09的刀叉勺耐温≤75℃;样品耐弯曲测试不折断。
实施例7
取配方组成为编号05的PLA刀叉勺样胚,放置在70℃模具容器中,分别注入8MPa,9.5MPa和11MPa的二氧化碳,恒温恒压浸泡30 min,分别以28MPa/s, 33MPa/s和38MPa/s速度快速卸压,开模取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表2所示。经二氧化碳处理后,样品外观白色,密度分别下降了8.9%,22.8%和29.6%,耐温分别为≤70℃,≤75℃和≤75℃;样品耐弯曲测试不折断。
实施例8
取配方组成为编号05和07的PLA刀叉勺样胚,放置在85℃模具容器中,注入9.5MPa的二氧化碳,恒温恒压浸泡8 min,以33MPa/s速度快速卸压,开模取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表2所示。经二氧化碳处理后,样品外观白色,05和07密度分别下降了9.3%和8.2%,耐温分别为≤95℃和≤85℃;样品耐弯曲测试折断。
实施例9
取配方组成为编号06,09和010的PLA刀叉勺样胚,放置在85℃模具容器中,注入10MPa的二氧化碳,恒温恒压浸泡6 min,以34MPa/s速度快速卸压,开模取出样品,在室温下冷却,得到PLA刀叉勺产品。测试样品密度、耐温性和耐弯曲脆断性,结果如表2所示。经二氧化碳处理后,样品外观白色,06,09和010密度分别下降了7.9%,10.4%和20.1%,耐温分别为≤75℃,≤95℃和≤90℃;06样品耐弯曲测试不折断,09和010样品耐弯曲测试折断。
由实施例5-9可知,经高压二氧化碳浸泡处理后,PLA刀叉勺的密度可下降8-29%,其耐温性可在65-95℃之间随配方组成或者随处理工艺条件而变化;相比烘箱热处理样品,本发明的样品基本上都耐弯曲脆断或者耐弯曲脆裂性有所改善。
Claims (10)
- 一种耐温PLA刀叉勺的制备方法,其特征在于,所述方法包括以下步骤:(1)PLA刀叉勺原料经注塑机注塑成型,制备得到刀叉勺样胚,刀叉勺样胚中含有未能完成结晶的PLA;(2)刀叉勺样胚经过恒温恒压的二氧化碳浸泡处理,使刀叉勺样胚中未结晶的PLA完成结晶,制备得到耐温性≥65℃的PLA刀叉勺产品。
- 根据权利要求1所述的一种耐温PLA刀叉勺的制备方法,其特征在于,步骤(2)中所述二氧化碳浸泡的方式是:PLA刀叉勺样胚放置在耐高温高压的可调温密闭容器中,所述密闭容器中注入二氧化碳,恒温保压浸泡。
- 根据权利要求2所述的一种耐温PLA刀叉勺的制备方法,其特征在于,步骤(2)中保压温度为45-110℃,保压压力为4-12MPa,保压时间为6-60min,泄压速度为5-45MPa/s。
- 根据权利要求2所述的一种耐温PLA刀叉勺的制备方法,其特征在于,所述二氧化碳为超临界二氧化碳流体或者亚临界二氧化碳流体。
- 根据权利要求3所述的一种耐温PLA刀叉勺的制备方法,其特征在于,通过调整配方和浸泡参数,可以获得不同耐温性的刀叉勺产品,分别为:耐温刀叉勺产品:耐温性≥65℃且<100℃中的任一温度;高耐温刀叉勺产品,耐温性>100℃。
- 根据权利要求3所述的一种耐温PLA刀叉勺的制备方法,其特征在于,通过调整浸泡参数,可以获得低密度的刀叉勺产品;所述保压压力≥7 MPa且<12 MPa,泄压速度≥24 MPa/s;优选的,所述保压压力≥9 MPa且<10.5 MPa,泄压速度≥31 MPa/s;所获得刀叉勺产品密度比刀叉勺样胚密度降低,降低的百分比为0-30%且不含0。
- 根据权利要求1所述的一种耐温PLA刀叉勺的制备方法,其特征在于,步骤(1)中所述PLA刀叉勺原料以质量计包括以下组分:料50-80%辅料0-20%填料10-30%改性剂0-5%;所述主料为PLA;所述辅料为PBAT、PBS或PBAT与PBS的共混物;所述填料选自滑石粉、碳酸钙、二氧化硅、膨润土、咖啡渣粉和竹粉中的任一种或多种组合;所述改性剂选自成核剂、抗氧剂、抗静电剂、抗菌剂、色母、相容剂、增韧剂、润滑剂、脱模剂、扩链剂或交联剂中的任一种或多种组合。
- 根据权利要求7所述的一种耐温PLA刀叉勺的制备方法,其特征在于,所述PLA选自单一牌号或者多个牌号的共混物。
- 根据权利要求7所述的一种耐温PLA刀叉勺的制备方法,其特征在于,所述PLA刀叉勺原料使用经过挤出共混造粒工艺制备而成的粒料。
- 一种耐温PLA刀叉勺,其特征在于,所述刀叉勺为微发泡产品,所述刀叉勺的密度相对于刀叉勺样胚降低5-30%,所述刀叉勺具有65℃以上的耐温性。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210700306.2 | 2022-06-20 | ||
CN202210700306.2A CN114874482B (zh) | 2022-06-20 | 2022-06-20 | 一种耐温pla刀叉勺及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023246221A1 true WO2023246221A1 (zh) | 2023-12-28 |
Family
ID=82680668
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2023/085163 WO2023246221A1 (zh) | 2022-06-20 | 2023-03-30 | 一种耐温pla刀叉勺及其制备方法 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN114874482B (zh) |
WO (1) | WO2023246221A1 (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114854079B (zh) * | 2022-06-20 | 2023-05-23 | 台州玉米环保科技有限公司 | 一种耐温pla吸塑餐饮具的制备方法 |
CN114874482B (zh) * | 2022-06-20 | 2023-07-21 | 台州玉米环保科技有限公司 | 一种耐温pla刀叉勺及其制备方法 |
WO2023246219A1 (zh) * | 2022-06-20 | 2023-12-28 | 台州玉米环保科技有限公司 | 一种耐温pla吸管及其制备方法 |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102241830A (zh) * | 2011-04-28 | 2011-11-16 | 中国科学院宁波材料技术与工程研究所 | 一种生物降解聚合物发泡片材制品的制备方法 |
TW201425399A (zh) * | 2012-12-20 | 2014-07-01 | Univ Far East | 發泡聚乳酸之製造方法 |
CN104277237A (zh) * | 2013-07-10 | 2015-01-14 | 宁波大学 | 一种聚合物发泡材料的制备方法 |
US20150240044A1 (en) * | 2012-09-05 | 2015-08-27 | Biopolymer Network Limited | Manufacture of polylactic acid foams using liquid carbon dioxide |
WO2018040624A1 (zh) * | 2016-08-31 | 2018-03-08 | 杭州博适特新材料科技有限公司 | 一种制备热塑性聚合物发泡珠粒的方法 |
CN109354847A (zh) * | 2018-10-29 | 2019-02-19 | 北京工商大学 | 一种聚乳酸纳米泡孔发泡材料及其制备方法 |
CN109776848A (zh) * | 2019-01-08 | 2019-05-21 | 恒天纤维集团有限公司 | 聚乳酸聚合熔体直接制备聚乳酸发泡制品的方法及装置 |
CN111040403A (zh) * | 2019-12-31 | 2020-04-21 | 恒天生物基材料工程技术(宁波)有限公司 | 一种耐热聚乳酸发泡热成型体及其制备方法 |
CN112778726A (zh) * | 2021-01-06 | 2021-05-11 | 中船重工鹏力(南京)塑造科技有限公司 | 一种pla耐热刀叉勺及生产方法 |
US20220161467A1 (en) * | 2020-11-24 | 2022-05-26 | Taichi NEMOTO | Foamed sheet, product, and method for producing foamed sheet |
CN114854079A (zh) * | 2022-06-20 | 2022-08-05 | 台州玉米环保科技有限公司 | 一种耐温pla吸塑餐饮具的制备方法 |
CN114874482A (zh) * | 2022-06-20 | 2022-08-09 | 台州玉米环保科技有限公司 | 一种耐温pla刀叉勺及其制备方法 |
CN114986836A (zh) * | 2022-06-20 | 2022-09-02 | 台州玉米环保科技有限公司 | 一种耐温pla吸管及其制备方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3672869B2 (ja) * | 2001-12-27 | 2005-07-20 | 鈴木総業株式会社 | 土壌浄化用の樹脂発泡体およびその製造方法 |
NL2016774B1 (nl) * | 2016-05-13 | 2017-11-16 | Synbra Tech B V | Een op polymelkzuur gebaseerde samenstelling. |
-
2022
- 2022-06-20 CN CN202210700306.2A patent/CN114874482B/zh active Active
-
2023
- 2023-03-30 WO PCT/CN2023/085163 patent/WO2023246221A1/zh unknown
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102241830A (zh) * | 2011-04-28 | 2011-11-16 | 中国科学院宁波材料技术与工程研究所 | 一种生物降解聚合物发泡片材制品的制备方法 |
US20150240044A1 (en) * | 2012-09-05 | 2015-08-27 | Biopolymer Network Limited | Manufacture of polylactic acid foams using liquid carbon dioxide |
TW201425399A (zh) * | 2012-12-20 | 2014-07-01 | Univ Far East | 發泡聚乳酸之製造方法 |
CN104277237A (zh) * | 2013-07-10 | 2015-01-14 | 宁波大学 | 一种聚合物发泡材料的制备方法 |
WO2018040624A1 (zh) * | 2016-08-31 | 2018-03-08 | 杭州博适特新材料科技有限公司 | 一种制备热塑性聚合物发泡珠粒的方法 |
CN109354847A (zh) * | 2018-10-29 | 2019-02-19 | 北京工商大学 | 一种聚乳酸纳米泡孔发泡材料及其制备方法 |
CN109776848A (zh) * | 2019-01-08 | 2019-05-21 | 恒天纤维集团有限公司 | 聚乳酸聚合熔体直接制备聚乳酸发泡制品的方法及装置 |
CN111040403A (zh) * | 2019-12-31 | 2020-04-21 | 恒天生物基材料工程技术(宁波)有限公司 | 一种耐热聚乳酸发泡热成型体及其制备方法 |
US20220161467A1 (en) * | 2020-11-24 | 2022-05-26 | Taichi NEMOTO | Foamed sheet, product, and method for producing foamed sheet |
CN112778726A (zh) * | 2021-01-06 | 2021-05-11 | 中船重工鹏力(南京)塑造科技有限公司 | 一种pla耐热刀叉勺及生产方法 |
CN114854079A (zh) * | 2022-06-20 | 2022-08-05 | 台州玉米环保科技有限公司 | 一种耐温pla吸塑餐饮具的制备方法 |
CN114874482A (zh) * | 2022-06-20 | 2022-08-09 | 台州玉米环保科技有限公司 | 一种耐温pla刀叉勺及其制备方法 |
CN114986836A (zh) * | 2022-06-20 | 2022-09-02 | 台州玉米环保科技有限公司 | 一种耐温pla吸管及其制备方法 |
Non-Patent Citations (2)
Title |
---|
HUANG FENG, LIU WEI, LAI JUN, WU JIANMING, HUANG AN, GENG LIHONG, PENG XIANGFANG: "Enhanced Heat Resistance and Expansion Ratio of Biodegradable Poly (Lactic Acid)/Poly (Butylene Adipate-Co-Terephthalate) Composite Foams via Synergistic Effect of Nucleating Agent and Chain Extension", JOURNAL OF POLYMER ENGINEERING, WALTER DE GRUYTER GMBH, DE, vol. 43, no. 4, 14 March 2023 (2023-03-14), DE , pages 297 - 309, XP009551267, ISSN: 0334-6447, DOI: 10.1515/polyeng-2022-0284 * |
YE JIAN-MIN, ZHU WEN-LI, HUANG HUANG, YAO ZE-HAO: "Crystallization of Polylactide under Supercritical Carbon Dioxide and Its Effects on Cell Structure", CHINA PLASTICS INDUSTRY, vol. 44, no. 10, 1 January 2016 (2016-01-01), pages 64 - 68, 75, XP093118829, ISSN: 1005-5770, DOI: 10.3969/j.issn.1005-5770.2016.10.017 * |
Also Published As
Publication number | Publication date |
---|---|
CN114874482A (zh) | 2022-08-09 |
CN114874482B (zh) | 2023-07-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2023246221A1 (zh) | 一种耐温pla刀叉勺及其制备方法 | |
CN102241830B (zh) | 一种生物降解聚合物发泡片材制品的制备方法 | |
JP4063856B2 (ja) | 生分解性ポリエステル樹脂組成物の製造方法 | |
CN101522798B (zh) | 聚乳酸类组合物构成的成型品 | |
CN100354367C (zh) | 生物降解性聚酯树脂组合物及其制造方法和用它形成的泡沫体及成形物 | |
TWI443140B (zh) | 聚丁二酸丁二酯(pbs)及改質聚丁二酸丁二酯(mpbs)製成之熱成形物件 | |
JP2003128901A (ja) | 生分解性ポリエステル樹脂組成物、その製造方法、及びそれより得られる発泡体、成形体 | |
CN107619584A (zh) | 聚乳酸复合材料、餐具及其制备方法 | |
CN104910596A (zh) | 一种聚乳酸微发泡材料及其制备方法 | |
CN110804287A (zh) | 一种耐热改性聚乳酸复合材料 | |
CN113748157B (zh) | 用于商业可行的一步式模内退火注塑工艺的聚乳酸基母料 | |
WO2023246222A1 (zh) | 一种耐温pla吸塑餐饮具的制备方法 | |
CN108017872A (zh) | 一种可用于增材制造的abs/pc合金改性材料 | |
CN111040403B (zh) | 一种耐热聚乳酸发泡热成型体及其制备方法 | |
KR101780794B1 (ko) | 내열성 폴리락타이드계 발포체, 그의 제조방법 및 그로 이루어진 생분해성 내열 성형품 | |
JP5113508B2 (ja) | 生分解性ポリエステル樹脂組成物及びそれより得られる発泡体、成形体 | |
JPS621909B2 (zh) | ||
JP2020049922A (ja) | シート成形品の製造方法 | |
WO2023246219A1 (zh) | 一种耐温pla吸管及其制备方法 | |
CN108659482A (zh) | 生物基聚呋喃二甲酸丁二醇酯改性聚乳酸合金及其应用 | |
CN114986836B (zh) | 一种耐温pla吸管及其制备方法 | |
TWI714111B (zh) | 聚乳酸樹脂組成物及其製備方法 | |
CN114430760B (zh) | 聚合物组合物和由该聚合物组合物制成的发泡聚丙烯珠 | |
JP2006241227A (ja) | 生分解性ポリエステル樹脂組成物、その製造方法及びそれからなる発泡体、成形体 | |
EP2147050B1 (en) | Controlled gloss blends of monovinylidene aromatic and ethylene polymers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23825876 Country of ref document: EP Kind code of ref document: A1 |