CN117645781A - Thin-wall injection molding product with large length-width ratio - Google Patents

Thin-wall injection molding product with large length-width ratio Download PDF

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CN117645781A
CN117645781A CN202311662128.XA CN202311662128A CN117645781A CN 117645781 A CN117645781 A CN 117645781A CN 202311662128 A CN202311662128 A CN 202311662128A CN 117645781 A CN117645781 A CN 117645781A
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hydroxybutyrate
thin
molded article
poly
injection molded
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张洪生
贾翠丽
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Zhangjiagang Lyuzhou New Material Technology Co ltd
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Zhangjiagang Lyuzhou New Material Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/46Applications of disintegrable, dissolvable or edible materials
    • B65D65/466Bio- or photodegradable packaging materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention discloses a thin-wall injection molding product with a large length-width ratio. The injection molding product comprises polylactic acid, poly-3-hydroxybutyrate-co-4-hydroxybutyrate and an auxiliary agent, wherein the auxiliary agent comprises ultrahigh molecular weight polymethyl methacrylate, the mass percentage of the poly-3-hydroxybutyrate-co-4-hydroxybutyrate in the raw material is 5-40%, and the mass percentage of the auxiliary agent is less than 5%; the mass percentage of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate is more than or equal to 20%. The injection molding product can be biodegradable, has better strength and impact resistance, has higher light transmittance and processability, and has the function of blocking ultraviolet rays.

Description

Thin-wall injection molding product with large length-width ratio
The present application is a divisional application of patent application of invention with application number 2023112650809 filed on 28 th 9 th 2023.
Technical Field
The invention belongs to the field of semitransparent toughened modified polylactic acid materials, relates to a thin-wall high-aspect ratio injection molding product made of a toughened modified polylactic acid composite material, and particularly relates to a toughened modified polylactic acid ribbon.
Background
Polylactic acid (PLA) is an important novel polyester bio-based polymer, and because the raw materials are usually made of fermented plant starch, such as corn, cassava, sugarcane or beet pulp, and the product made of the polylactic acid has the advantages of good biocompatibility, glossiness, transparency, good hand feeling, degradation through the means of industrial composting after being abandoned, and the like; on the other hand, polylactic acid has good thermal stability, good mechanical property, physical property and solvent resistance, and can meet the requirements of extrusion, spinning, biaxial stretching, injection blow molding and the like for processing in various modes. Through years of development, the application field of polylactic acid has been very wide, and relates to packaging, consumer products, textiles, agriculture, automobiles, buildings, coatings, electronic appliances, medicines and the like.
The bio-based polymer material represented by polylactic acid forms a complete closed loop through biomass-bio-based product-recycling or combustion-carbon dioxide-biomass, thereby achieving the purpose of reducing greenhouse gas emission and simultaneously realizing the purpose of fundamentally solving the environmental problem caused by white pollution.
In the field of new bio-based polymer materials, polylactic acid has remarkable advantages and obvious disadvantages such as ultraviolet intolerance, poor flexibility, impact strength, elongation at break (less than 10%) and barrier property lower than common resins. In recent years, toughening modification of polylactic acid has become a hot spot for many researches. In order to improve the toughness of polylactic acid, many methods such as copolymerization modification, plasticization blending modification, and toughening blending modification have been studied by the scholars. In comparison, the copolymerization modification process is complex, the cost is high, and the contribution value of the polylactic acid in the aspect of reducing the carbon footprint is reduced; although good in effect, most of plasticizers are small molecular organic compounds, and potential risks of food or medicine pollution caused by migration and precipitation exist in the use process; the toughening blending modification effect is good, but most toughening modifiers are from petroleum-based polymers, the use amount is usually more than 5%, and GB/T39514-2020 has clear regulations on the use of non-degradable plastic components.
The disadvantages of poor toughness and large brittleness of polylactic acid greatly limit the application of the polylactic acid, and take plastic suction molding as an example, the process of plastic suction molding from a polylactic acid sheet material into a product needs to undergo a trimming process, and the problem of increased cracking rate of the edge of the product and reduced yield is caused by the brittleness of the polylactic acid. Polylactic acid has little transparency and glossiness of other bio-based or biodegradable plastics, can be equivalent to PET, is suitable for visual packaging, and has good packaging effect. While the blending toughening modification technology solves the problem of brittleness of polylactic acid, the transparency of the polylactic acid is almost completely sacrificed. In addition, the fluidity of the modified material has obvious influence on the appearance of the material, and in the example of injection molding products, the melt index is high, so that the modified material is more suitable for manufacturing products with fine structures.
Disclosure of Invention
The invention provides a thin-wall injection molding product with a large length-width ratio, in particular to a toughening modified polylactic acid ribbon.
The invention adopts the following technical scheme:
the injection molding product comprises the raw materials of polylactic acid, poly-3-hydroxybutyrate-co-4-hydroxybutyrate and an auxiliary agent, wherein the auxiliary agent comprises ultrahigh molecular weight polymethyl methacrylate, the mass percentage of the poly-3-hydroxybutyrate-co-4-hydroxybutyrate in the raw materials is 5-40%, and the mass percentage of the auxiliary agent is less than 5%; the mass percentage of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate is more than or equal to 20%.
Preferably, the auxiliary agent further comprises a lubricant selected from one or more of pentaerythritol stearate, zinc stearate, amino silicone oil, saponified montan wax, glycerol monooleate.
Preferably, the adjuvant further comprises a compatibilizer selected from the group consisting of one or more of ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-n-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate random copolymer, ethylene-butyl acrylate copolymer, and maleic anhydride grafted ethylene-octene copolymer.
Preferably, the auxiliary agent further comprises one or more of a crystallization accelerator, a chain extender and an antioxidant; the crystallization accelerator is selected from pentaerythritol and/or dipentaerythritol, and the antioxidant is selected from one or more of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tri (2, 4-di-tert-butylphenyl) phosphite 2, 6-di-tert-butyl-p-potassium phenol.
Preferably, the mass percentage of poly-3-hydroxybutyrate-co-4-hydroxybutyrate in the raw materials is 5-30%.
Preferably, the mass percentage of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate is 33+ -5%.
Preferably, the raw materials of the injection molding product are polylactic acid, poly-3-hydroxybutyrate-co-4-hydroxybutyrate and auxiliary agents.
Preferably, the injection molded article comprises a tie.
According to one aspect of the invention, the raw materials of the toughened and modified polylactic acid composite material comprise polylactic acid, poly-3-hydroxybutyrate-co-4-hydroxybutyrate and an auxiliary agent, wherein the auxiliary agent comprises a lubricant and a compatibilizer, the mass percentage of the poly-3-hydroxybutyrate-co-4-hydroxybutyrate in the raw materials is 5-40%, and the mass percentage of the auxiliary agent is less than 5%; the mass percentage of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate is more than or equal to 20%.
Preferably, the bio-based polymer source material comprises greater than 95% by weight of the total material. Good biodegradability is maintained.
Preferably, the mass percentage of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate is greater than 20%; more preferably, the mass percentage of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate is 25-40%.
Preferably, the auxiliary agent further comprises pentaerythritol or dipentaerythritol. Is beneficial to improving the processing performance of the material, improving the melt index and simultaneously has the effect of promoting the crystallization of polylactic acid.
Preferably, the mass percentage of pentaerythritol or dipentaerythritol in the raw materials is 0.1-1%.
Preferably, the lubricant is selected from one or more of pentaerythritol stearate, calcium stearate, zinc stearate, sodium stearate, barium stearate, amino silicone oil, saponified montan wax, glycerol monooleate, oxidized polyethylene wax, polyethylene-vinyl acetate wax, N-ethylene bis-stearamide, montan acid ester, silicone powder.
Preferably, the compatibilizer comprises a polymer block capable of reacting with a polyhydroxyalkanoate end group or a polylactic acid end group, and the monomer of the reactive polymer block is one or more than two of maleic anhydride, glycidyl methacrylate, an acrylic ester compound, an oxazole compound and an isocyanate compound. More preferably, the compatibilizer is selected from the group consisting of one or more of ethylene methyl acrylate-glycidyl methacrylate copolymer, ethylene n-butyl acrylate-glycidyl methacrylate copolymer, ethylene methyl acrylate random copolymer, ethylene butyl acrylate copolymer, and maleic anhydride grafted ethylene octene copolymer.
Preferably, the auxiliary agent further comprises one or more of a crystallization accelerator, a chain extender and an antioxidant. The crystallization promoter is selected from pentaerythritol and/or dipentaerythritol. The antioxidant is one or more selected from pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tri (2, 4-di-tert-butylphenyl) phosphite 2, 6-di-tert-butyl-p-potassium phenol.
Preferably, the auxiliary agent further comprises ultrahigh molecular weight methyl methacrylate. Is used for promoting the melting of resin, improving the rheological property of melt and endowing lubricating function.
Preferably, the auxiliary agent comprises a nucleating agent. The nucleating agent is one or more selected from sodium montmorillonite, talcum powder, mica, zeolite, vermiculite, wollastonite, sepiolite, aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide, calcium carbonate, barium carbonate and barium sulfate.
Preferably, the mass percentage of poly-3-hydroxybutyrate-co-4-hydroxybutyrate in the raw material is 5 to 30%, more preferably 10 to 25%.
Preferably, the mass percentage of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate is 33+ -5%. In a specific and preferred embodiment, the mass percent of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate is 33%. In other preferred embodiments, the mass percent of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate may be within a deviation of 33% to + -5%.
Preferably, the polylactic acid composite material is composed of polylactic acid, poly-3-hydroxybutyrate-co-4-hydroxybutyrate and auxiliary agents.
According to another aspect of the present invention, a method for preparing the toughened and modified polylactic acid composite material as described above, the method comprising: weighing the raw materials according to the proportion, uniformly mixing, and extruding and molding to obtain the toughening modified polylactic acid particles.
According to a further aspect of the invention, a use of the toughened modified polylactic acid composite material as described above in sheets, films and injection molded articles.
Preferably, the sheet, film and injection molded article comprise packaging materials for food or pharmaceutical products.
The invention also relates to a semitransparent packaging material which is prepared from the toughened modified polylactic acid composite material. Including materials including, but not limited to: packaging film, packaging bag, packaging box, packaging plate, packaging bottle, packaging can, packaging barrel, etc.
Optionally, the translucent packaging material is a food packaging material, such as a sandwich pack, an edible oil packaging can, or the like.
Alternatively, the translucent packaging material is a pharmaceutical packaging material, in particular a packaging material for uv-light sensitive pharmaceutical products.
The invention also relates to a thin-wall high-length-width ratio product which is made of the toughened and modified polylactic acid composite material. Typically, the thin-walled high aspect ratio article is a tie. The product can be biodegradable, and has good strength and impact resistance.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the thin-wall high-aspect ratio injection molding product of the invention mainly uses polylactic acid and poly-3-hydroxybutyrate-co-4-hydroxybutyrate as raw materials, and the content of 4-hydroxybutyrate is more than 20%, so that the injection molding product has better elongation at break, IZOD (IZOD) non-notch impact strength and IZOD notch impact strength, and also has certain visible light transmittance, namely, the material can maintain transparency or translucency, the melt index is higher than that of a pure polylactic acid material, and the injection molding product has better processability, and can meet the manufacturing requirements of thin-wall products, especially thin-wall high-aspect ratio products (such as bands); the injection molding product can be biodegradable, and has better strength and impact resistance. In addition, the ultraviolet light blocking film also has the function of blocking ultraviolet light.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a comparative photograph of the color plate of comparative example 1 and example 2.
Fig. 2 is a comparative photograph of the color plates of comparative example 1 and example 5.
Fig. 3 is a comparative photograph of the color plaques of comparative example 1 and example 12.
Fig. 4 is a DSC curve for the material of comparative example 1.
Fig. 5 is a DSC curve for the material of example 12.
Fig. 6 is a DSC curve for the material of example 13.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the attached drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The application relates to semitransparent toughening modification of a polylactic acid composite material, which comprises the following raw materials in percentage by weight:
60-95 wt% of polylactic acid (PLA);
5 to 40 percent of poly-3-hydroxybutyrate-co-4-hydroxybutyrate (P34 HB).
Wherein the mass percentage of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate (P34 HB) is more than or equal to 20wt%. For example, the mass percent of the hydroxybutyrate in P34HB is 20%, 22%, 25%, 30%, 33%, 35%, 40% or 50%.
Further, the weight percentage of poly-3-hydroxybutyrate-co-4-hydroxybutyrate in the raw material is preferably 5 to 30%, more preferably 10 to 25%. For example, the weight percent of poly-3-hydroxybutyrate-co-4-hydroxybutyrate is 5%, 10%, 15%, 20%, 25% or 30%.
The weight percentage of the bio-based source material in the raw material is more than 95 percent. For example, the weight percent of the bio-based source feedstock is 95%, 95.5%, 95.8%, 96%, 98%, or 100%.
Further, the raw materials also comprise 0 to 0.5 weight percent of auxiliary agent. The auxiliary agent comprises one or a combination of a plurality of lubricants, crystallization promoters, chain extenders, compatibilizers, antioxidants, nucleating agents and fluorescent whitening agents. The lubricant comprises one or more selected from pentaerythritol stearate, calcium stearate, zinc stearate, sodium stearate, barium stearate, amino silicone oil, saponified montan wax, glycerol monooleate, oxidized polyethylene wax, polyethylene-vinyl acetate wax, N-ethylene bis-stearamide, montan acid ester and silicone powder. The nucleating agent comprises one or a combination of more selected from talcum powder, pentaerythritol and dipentaerythritol. The chain extender includes Joncryl 4468. The compatibilizer comprises a polymer block which can react with a polyhydroxyalkanoate end group or a polylactic acid end group, and the monomer of the reactive polymer block is one or more than two of maleic anhydride, glycidyl methacrylate, acrylic ester compounds, oxazole compounds and isocyanate compounds; which may include a combination of one or more selected from the group consisting of ethylene-methyl acrylate-glycidyl methacrylate copolymer, ethylene-n-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate random copolymer, ethylene-butyl acrylate copolymer, and maleic anhydride grafted ethylene-octene copolymer. The antioxidant is selected from one or more of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tri (2, 4-di-tert-butylphenyl) phosphite 2, 6-di-tert-butyl-p-potassium phenol. The nucleating agent is one or more selected from sodium montmorillonite, talcum powder, mica, zeolite, vermiculite, wollastonite, sepiolite, aluminum oxide, magnesium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide, calcium carbonate, barium carbonate and barium sulfate. Further, the auxiliary agent also comprises ultrahigh molecular weight methyl methacrylate for enhancing the melt strength, improving the melt rheological property and imparting lubrication function. For non-food or pharmaceutical contact applications, fluorescent whitening agents can be used to adjust the product appearance, increasing the degree of freedom in downstream product design.
The components are uniformly mixed according to the proportion, and the mixture is granulated by a double-screw extruder. The processing temperature of the twin-screw extruder is 145-1050C, preferably 155-1900C; the main screw speed is 200 to 500 rpm, preferably 250 to 350 rpm. When in use, the product can be formed by injection molding, and the injection molding temperature is 160-200 ℃, preferably 160-180 ℃; the molding cycle is 30 to 75 seconds, preferably 40 to 55 seconds.
The raw materials used in the following examples and comparative examples are shown in Table 1.
TABLE 1 raw materials and sources thereof
Wherein the content of 4-hydroxybutyrate in P34HB (PHACT A1000P) is 33wt%; the content of 4-hydroxybutyrate in P34HB (YL 1092) was 11% by weight.
The performance test method comprises the following steps:
tensile Property test method reference is made to ISO 527-2:1993 determination of tensile Properties of plastics, second part: molding and extrusion plastic test conditions;
test method for impact strength reference is made to ISO 180:2000 determination of impact strength of plastic-hard material cantilever beam.
Flexural Performance test method reference ISO 178:2001 Plastic flexural Performance test;
melt index test method the melt index test is carried out according to GB/T3862-2000 standard, the test temperature is 190 ℃, and the load is 2.16kg.
The light transmittance test method refers to GB/T2410-2008 standard.
The tie article ring pull strength and low temperature impact resistance tests were tested against UL62275 standards.
In the tables below, "-means a value of 0 or no test.
Comparative example 1 and examples 1 to 5
The raw materials were weighed according to table 2, and after mixing uniformly, extruded with a screw extruder, granulated, and a color plate was produced. The performance of each panel was tested and the test results are shown in table 2 below. The thickness of each panel for testing was 1mm.
TABLE 2
A comparison of the panels of comparative example 1 and example 2 is shown in fig. 1, and a comparison of the panels of comparative example 1 and example 5 is shown in fig. 2. The panels shown in the figures are all 1mm thick and are placed on A4 white paper printed with the "sample" lettering. Where a is the panel of comparative example 1, b is the panel of example 2, and c is the panel of example 3.
With the addition of P34HB (PHACT A1000P), the elongation, the unnotched/IZOD notched impact strength and the melt index (MFR) of the polylactic acid composite material are improved, wherein the IZOD unnotched impact is increased from 21.9 to 99, the IZOD notched impact is increased from 3 to 6.5, and the ductility is increased from 4.9% to 23.2%; it was found that toughness was greatly improved. Although the transparency is also reduced, the glass still has certain transparency at the thickness of 1mm, and the visible light transmittance is maintained to be more than 50 percent, so that the glass meets the requirements of packaging materials.
Examples 6 to 12
The raw materials were weighed according to table 3, and after mixing uniformly, extruded with a screw extruder, granulated, and a color plate was produced. The performance of each panel was tested and the test results are shown in table 3 below. The thickness of each panel for testing was 1mm. The prepared plastic particles were used to prepare a band having a width of 3.6mm and a length of 250mm, the properties of which are shown in Table 3 below.
TABLE 3 Table 3
In the table above: "NB" means that the sample IZOD impact test was continued.
The comparative photographs of the panels of comparative example 1 and example 12 are shown in FIG. 3, in which the thickness of the panels is 1mm, and the panels are placed on A4 white paper printed with the "sample" pattern. Where a is the color plate of comparative example 1 and d is the color plate of example 12.
Comparative examples 2 to 5
The raw materials were weighed according to table 4, and after mixing uniformly, extruded with a screw extruder, granulated, and made into a color plate. The performance of each panel was tested and the test results are shown in table 4 below. The thickness of each panel for testing was 1mm. The prepared plastic granules were used to prepare a tie having a width of 3.6mm and a length of 250mm, the properties of which are shown in Table 4 below.
TABLE 4 Table 4
As shown in the combination of tables 3 and 4, PLA, P34HB and processing aid are compounded, the elongation at break, IZOD notch impact strength and IZOD notch impact strength of the material are improved more obviously, and the melt index is higher than that of the pure polylactic acid material; in particular, the ultraviolet transmittance of the color plates of examples 9 to 12 was reduced to 20% or less, while the visible light transmittance and the infrared light transmittance were not greatly reduced (30% or more and 50% or more, respectively), and in particular, the visible light transmittance of example 12 was 4 times or more the ultraviolet light transmittance. The material of the embodiment is transparent or semitransparent and has better ultraviolet blocking property. Although the ultraviolet light transmittance of comparative examples 2 to 5 was 20% or less, the visible light transmittance was also greatly reduced, and the transparency of the material was poor and even opaque.
For transparency of the material, the thickness of the color plate used in the test herein is 1mm, which is greater than that of a general packaging material (the thickness of the packaging film or the packaging bag is usually between 0.01 and 0.5 mm). A 1mm thick plaque, either visually or based on measured light transmittance, has better light transmittance, which is better when it is made into a thinner packaging material.
The high-energy short-wave ultraviolet rays can destroy most organic matters, especially foods and medicines. The color change, the nutrition loss and even the deterioration of the food are caused, the nutrition and the safety of the food are seriously threatened, and the storage and the sales of the product are influenced. The polylactic acid composite materials of examples 8 to 12 are capable of blocking ultraviolet rays without affecting transparency and coloring of packaging materials, and are suitably used as packaging materials for foods or medicines. For example: can protect fruit juice and milk beverage from damage of ultraviolet rays to vitamins and colors, and maintain nutrition and appearance; the edible oil product is protected from being damaged by ultraviolet rays on amino acid, fatty acid, linolenic acid and the like, and the nutrition and the appearance are maintained; the photosensitive medicine is protected from ultraviolet irradiation, is deteriorated and fails, replaces an iron ion palm bottle, and does not influence the observation of the content; and other applications for packaging photosensitive chemicals.
The inventor also finds that polyhydric alcohols such as pentaerythritol or dipentaerythritol and the like are beneficial to improving the processability of polylactic acid in the research process, and the design experiment is as follows: the raw materials of the modified polylactic acid comprise polylactic acid and pentaerythritol or polyalcohol, wherein the mass content of the polyalcohol is 1-10%. Specifically as in examples 13 and 14.
Example 13
99.5 parts by weight of polylactic acid and 0.5 part by weight of pentaerythritol are weighed, mixed, extruded by a screw extruder and granulated.
Example 14
99.5 parts by weight of polylactic acid and 0.5 part by weight of dipentaerythritol are weighed, mixed, extruded by a screw extruder, and granulated.
Crystallization Performance test
DSC thermograms were performed on the materials of comparative example 1, examples 13 and 14, and the DSC curves of comparative example 1, example 13 and example 14 are shown in sequence in fig. 4 to 6. Referring to fig. 4 to 6, the pure polylactic acid material has no crystallization temperature, the crystallization temperature of the composite material of example 13 is 108.4 ℃, and the crystallization temperature of the composite material of example 14 is 112.1 ℃. Pentaerythritol or dipentaerythritol can promote the crystallization of PLA material, improve the melt fluidity of polylactic acid material and improve the processability of polylactic acid material.
As used in this specification and in the claims, the terms "comprises" and "comprising" merely indicate that the steps and elements are explicitly identified, and do not constitute an exclusive list, as other steps or elements may be included in a method or apparatus. The term "and/or" as used herein includes any combination of one or more of the associated listed items.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. If a definition used herein contradicts or is inconsistent with a definition set forth in other publications, the definition used herein should prevail.
The above-described embodiments are provided for illustrating the technical concept and features of the present invention, and are intended to be preferred embodiments for those skilled in the art to understand the present invention and implement the same according to the present invention, not to limit the scope of the present invention. All equivalent changes or modifications made according to the principles of the present invention should be construed to be included within the scope of the present invention.

Claims (10)

1. The injection molding product is characterized in that the injection molding product comprises polylactic acid, poly-3-hydroxybutyrate-co-4-hydroxybutyrate and an auxiliary agent, wherein the auxiliary agent comprises ultrahigh molecular weight polymethyl methacrylate, the mass percentage of the poly-3-hydroxybutyrate-co-4-hydroxybutyrate in the raw material is 5-40%, and the mass percentage of the auxiliary agent is less than 5%; the mass percentage of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate is more than or equal to 20%.
2. The thin-walled high aspect ratio injection molded article of claim 1, wherein the bio-based polymeric source material comprises greater than 95 weight percent of the total material.
3. The thin-walled high aspect ratio injection molded article of claim 1, wherein the adjuvant further comprises pentaerythritol or dipentaerythritol in an amount of 0.1 to 1 mass percent.
4. The thin-walled high aspect ratio injection molded article of claim 1, wherein the adjuvant further comprises a lubricant selected from one or more of pentaerythritol stearate, zinc stearate, amino silicone oil, saponified montan wax, glycerol monooleate.
5. The thin-walled high aspect ratio injection molded article of claim 1, wherein the adjuvant further comprises a compatibilizer selected from the group consisting of one or more of ethylene methyl acrylate-glycidyl methacrylate copolymer, ethylene n-butyl acrylate-glycidyl methacrylate copolymer, ethylene methyl acrylate random copolymer, ethylene butyl acrylate copolymer, and maleic anhydride grafted ethylene octene copolymer.
6. The thin-walled high aspect ratio injection molded article of claim 1, wherein the adjuvant further comprises a combination of one or more of a crystallization promoter, a chain extender, an antioxidant; the crystallization accelerator is selected from pentaerythritol and/or dipentaerythritol, and the antioxidant is selected from one or more of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tri (2, 4-di-tert-butylphenyl) phosphite 2, 6-di-tert-butyl-p-potassium phenol.
7. The thin-walled high aspect ratio injection molded article of claim 1, wherein the mass percent of poly-3-hydroxybutyrate-co-4-hydroxybutyrate in the feedstock is 5-30%.
8. A thin-walled high aspect ratio injection molded article according to claim 1, characterized in that the mass percentage of 4-hydroxybutyrate in the poly-3-hydroxybutyrate-co-4-hydroxybutyrate is 33±5%.
9. The thin-walled high aspect ratio injection molded article of claim 1, wherein the injection molded article comprises polylactic acid, poly-3-hydroxybutyrate-co-4-hydroxybutyrate and an adjuvant.
10. The thin-walled high aspect ratio injection molded article of claim 1, wherein the injection molded article comprises a tie.
CN202311662128.XA 2023-09-28 2023-09-28 Thin-wall injection molding product with large length-width ratio Pending CN117645781A (en)

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