Composition, article thereof, and preparation method therefor
Aqueous dispersions can be prepared at room temperature using a simple composition of polyhydroxyalkanoates and fatty acids or their salts, which solves the problems of complexity and high cost in the production of aqueous polyhydroxyalkanoate dispersions and enables high-performance dispersions and products.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- KEMIRA OY
- Filing Date
- 2025-12-24
- Publication Date
- 2026-07-02
AI Technical Summary
In the existing technology, waterborne polyhydroxyalkanoate dispersions require complex formulations with multiple components, resulting in high production costs, complex processes, and interactions between components that affect the performance of the dispersion.
An aqueous dispersion can be prepared by mixing a simple composition containing polyhydroxyalkanoates and fatty acids or their salts or fatty alcohols having 12-36 carbon atoms at room temperature, reducing the number of components and simplifying the production process.
It reduces production costs, achieves effective dispersion of polyhydroxyalkanoate dispersions, and improves the performance of dispersions and their products, such as film-forming properties, barrier properties, heat-sealing properties, and adhesion. Moreover, the process is simple and does not require heating.
Smart Images
Figure CN2025145258_02072026_PF_FP_ABST
Abstract
Description
Compositions, articles thereof and methods of preparation Technical Field
[0001] This invention relates to a composition, articles thereof, and a method for their preparation, and more particularly to a composition containing a polyhydroxyalkanoate, articles thereof, and a method for their preparation. Background Technology
[0002] Polyhydroxyalkanoates (PHAs) are a class of natural high-molecular-weight biomaterials. They can be biosynthesized and are biodegradable, making them more environmentally friendly than fossil-based materials. Current technologies require the use of organic solvents to stabilize PHA particles in the dispersion, as dispersions of PHAs cannot be formed using only inorganic solvents (such as water). However, the presence of organic solvents can negatively impact the final product (e.g., environmental friendliness), thus reducing its appeal.
[0003] For aqueous polyhydroxyalkanoate dispersions, existing technologies typically employ complex formulations containing multiple components to achieve effective dispersion. However, the introduction of multiple components further increases the cost of the dispersion and the complexity of the production process (e.g., the need for heating during processing). Moreover, the more components introduced, the greater the potential for adverse interactions between them, which in turn impairs the performance of the aqueous polyhydroxyalkanoate dispersion and its products. Summary of the Invention
[0004] To address the problems in the prior art, the present invention provides a composition, the product thereof, and a preparation method that reduces the number of components in the aqueous polyhydroxyalkanoate dispersion, simplifies the production process, improves the performance of the polyhydroxyalkanoate dispersion and the product thereof, and reduces production costs.
[0005] In one aspect of the invention, a composition is provided comprising a first component and a second component. Optionally, the composition further comprises water.
[0006] In one embodiment, the first component comprises (preferably) a polyhydroxyalkanoate.
[0007] In one embodiment, the second component comprises (preferably) a fatty acid having 12-36 carbon atoms or a salt thereof, or a fatty alcohol having 12-36 carbon atoms or a derivative thereof.
[0008] In one embodiment, the second component comprises (preferably) stearate.
[0009] In one embodiment, the stearate includes one or more of calcium stearate, zinc stearate, or magnesium stearate.
[0010] In one aspect of the invention, a composition is provided comprising a first component, a second component, and optionally, water, wherein:
[0011] The content of the first component is greater than 0 parts by weight and not more than 60 parts by weight, for example, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, 40, 45, 50, 55 or 60 parts by weight, or a subrange consisting of any value in these ranges;
[0012] The content of the second component is at least 5 parts by weight, for example, at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 or 65 parts by weight, or a subrange consisting of any value in these ranges.
[0013] In one aspect of the invention, a composition is provided comprising a first component, a second component, and optionally, water, wherein:
[0014] The content of the first component is greater than 0% by weight and not more than 60% by weight, for example, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, 40, 45, 50, 55 or 60% by weight, or a subrange consisting of any value in these ranges;
[0015] The content of the second component is at least 5% by weight, for example, at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 or 65% by weight, or a subrange consisting of any value in these ranges.
[0016] In one embodiment, the first component is a polyhydroxyalkanoate.
[0017] In one embodiment, the polyhydroxyalkanoate has the following repeating units:
[0018] Wherein, n is 1, 2, or 3, preferably 1 or 2; R1 is hydrogen or straight-chain or branched C1-C. 15 Alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), preferably hydrogen or straight-chain or branched C1-C8 alkyl groups.
[0019] In one embodiment, the polyhydroxyalkanoate contains repeating units derived from 3-hydroxybutyrate.
[0020] In one embodiment, the polyhydroxyalkanoate contains only repeating units derived from 3-hydroxybutyrate.
[0021] In one embodiment, the polyhydroxyalkanoate contains a repeating unit derived from 3-hydroxybutyrate and at least one repeating unit derived from 3-hydroxypropionate, 3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonanoate, 3-hydroxydecanoate, 3-hydroxyundecanoate and / or 4-hydroxybutyrate.
[0022] In a preferred embodiment, the polyhydroxyalkanoate comprises repeating units derived from 3-hydroxybutyrate and repeating units derived from 3-hydroxyhexanoate. More preferably, the polyhydroxyalkanoate is composed of repeating units derived from 3-hydroxybutyrate and repeating units derived from 3-hydroxyhexanoate.
[0023] In a more specific embodiment, the 3-hydroxybutyrate-derived repeating unit constitutes a molar percentage of 50-100 mol% in the polyhydroxyalkanoate, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 mol%, or a subrange consisting of any values within these ranges. Preferably, the 3-hydroxybutyrate-derived repeating unit constitutes a molar percentage of 80-98 mol% in the polyhydroxyalkanoate. More preferably, the 3-hydroxybutyrate-derived repeating unit constitutes a molar percentage of 80-95 mol% in the polyhydroxyalkanoate.
[0024] In a more specific embodiment, the repeating units other than the 3-hydroxybutyrate repeating unit (e.g., those derived from 3-hydroxypropionate, 3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonanoate, 3-hydroxydecanoate, 3-hydroxyundecanoate, and / or 4-hydroxybutyrate repeating units) constitute a molar percentage of 0-50 mol% in the polyhydroxyalkanoate, for example, 0, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 mol%, or a subrange consisting of any values within these ranges. Preferably, the repeating units other than the 3-hydroxybutyrate repeating unit constitute a molar percentage of 2-20 mol% in the polyhydroxyalkanoate. More preferably, the repeating units other than the 3-hydroxybutyrate repeating unit constitute a molar percentage of 5-20 mol% in the polyhydroxyalkanoate.
[0025] In a preferred embodiment, the polyhydroxyalkanoate contains 0-50 mol% (e.g., 0, 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50 mol%, or a subrange consisting of any values in these ranges, preferably 2-20 mol%, more preferably 5-20 mol%) of repeating units derived from 3-hydroxyhexanoate.
[0026] In a preferred embodiment, the polyhydroxyalkanoate contains 80-98 mol% repeating units derived from 3-hydroxybutyrate and 2-20 mol% repeating units derived from 3-hydroxyhexanoate.
[0027] In one embodiment, the polyhydroxyalkanoate comprises at least one selected from poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate). Preferably, the polyhydroxyalkanoate comprises poly(3-hydroxybutyrate-co-3-hydroxyhexanoate). Most preferably, the polyhydroxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).
[0028] In one embodiment, the polyhydroxyalkanoate has a weight-average molecular weight of 100,000 to 1,000,000, for example, 100,000, 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, 800,000, 900,000, or 1,000,000, or a subrange consisting of any values within these ranges. Preferably, the polyhydroxyalkanoate has a weight-average molecular weight of 200,000 to 900,000. Most preferably, the polyhydroxyalkanoate has a weight-average molecular weight of 300,000 to 800,000.
[0029] In one embodiment, the second component is a fatty acid or a salt thereof having 12-36 carbon atoms (e.g., 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35 or 36, preferably 12-24, most preferably 18), or a fatty alcohol or a derivative thereof having 12-36 carbon atoms (e.g., C...). 12-36 Alkyl glycosides, including C 12-36 Alkyl monosaccharides (i.e., molecules containing only one sugar unit) and C 12-36 Alkyl polysaccharide (i.e., the molecule contains at least two sugar units).
[0030] In one embodiment, the fatty acid or its salt having 12-36 carbon atoms is a branched-chain fatty acid or its salt, or a straight-chain fatty acid or its salt. In a preferred embodiment, the fatty acid or its salt having 12-36 carbon atoms is a straight-chain fatty acid or its salt.
[0031] In one embodiment, the fatty alcohol or its derivative having 12-36 carbon atoms is a branched fatty alcohol or its derivative, or a straight-chain fatty alcohol or its derivative, for example, C 12-36 Alkyl glycosides, including C 12-36 Alkyl monosaccharides (i.e., molecules containing only one sugar unit) and C 12-36 Alkyl polysaccharide (i.e., a molecule containing at least two sugar units). In a preferred embodiment, the fatty alcohol or its derivative having 12-36 carbon atoms is a straight-chain fatty alcohol or its derivative.
[0032] In a preferred embodiment, fatty acids having 12-36 carbon atoms or their salts include dodecanoic acid (or lauric acid) or its salt, tridecanoic acid or its salt, tetradecanoic acid (or myristic acid) or its salt, pentadecanoic acid or its salt, hexadecanoic acid (or palmitic acid, palmitic acid) or its salt, heptadecanoic acid or its salt, octadecanoic acid (or stearic acid) or its salt, nonadecanoic acid or its salt, eicosanoic acid (or arachidic acid) or its salt, dodecanoic acid or its salt, tridecanoic acid or its salt, tetradecanoic acid or its salt, pentadecanoic acid or its salt, hexadecanoic acid or its salt, heptadecanoic acid or its salt, octadecanoic acid or its salt, nonadecanoic acid or its salt, triacontanoic acid (or... The preferred salts are: beeswax acid (or lauric acid) or its salts, tridecanoic acid or its salts, dodecanoic acid or its salts, tridecanoic acid or its salts, tetradecanoic acid or its salts, pentadecanoic acid or its salts, or hexadecanoic acid or its salts, preferably dodecanoic acid (or lauric acid) or its salts, tridecanoic acid or its salts, tetradecanoic acid (or myristic acid) or its salts, pentadecanoic acid or its salts, hexadecanoic acid (or palmitic acid, palmitic acid) or its salts, heptadecanoic acid or its salts, octadecanoic acid (or stearic acid) or its salts, nonadecanoic acid or its salts, eicosanoic acid (or arachidic acid) or its salts, dodecanoic acid or its salts, dodecanoic acid or its salts, tridecanoic acid or its salts, or tetradecanoic acid or its salts, with octadecanoic acid (or stearic acid) or its salts being the most preferred.
[0033] In one embodiment, the salt comprises a metal salt, preferably a divalent metal (e.g., zinc, magnesium, or calcium) salt.
[0034] In a preferred embodiment, the second component is selected from one or more of zinc stearate, magnesium stearate, or calcium stearate.
[0035] In a preferred embodiment, the fatty alcohol having 12-36 carbon atoms or its derivatives includes dodecyl alcohol (or lauryl alcohol), tridecyl alcohol, tetradecyl alcohol (or myristyl alcohol), pentadecyl alcohol, hexadecyl alcohol (or palmitol), heptadecanol, octadecyl alcohol (or stearyl alcohol), nonadecanol, eicosyl alcohol (or peanut alcohol), dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecanol, octadecyl alcohol, nonadecanol, triacontanol (or beeswax alcohol), triacontanol, tridodecyl alcohol, triacontanol, tritetradecyl alcohol, tripentacontanol, hexadecyl alcohol, or its derivatives (e.g., C1). 2-36 Alkyl glycosides, including C 12-36 Alkyl monosaccharides and C 12-36Alkyl polysaccharide glycosides, preferably dodecyl alcohol (or lauryl alcohol), tridecyl alcohol, tetradecyl alcohol (or myristyl alcohol), pentadecyl alcohol, hexadecyl alcohol (or palmitol), heptadecanol, octadecyl alcohol (or stearyl alcohol), nonadecanol, eicosyl alcohol (or arachidyl alcohol), dodecyl alcohol, docosyl alcohol, tridecyl alcohol, tetradecyl alcohol, or derivatives thereof (e.g., C 12-24 Alkyl glycosides, including C 12-24 Alkyl monosaccharides and C 12-24 Alkyl polysaccharide glycosides, most preferably octadecanoic acid alcohol (or stearyl alcohol) or its derivatives (e.g., C164-C ... 18 Alkyl glycosides, including C 18 Alkyl monosaccharides and C 18 Alkyl polysaccharide).
[0036] In one embodiment, the composition further includes water, such as distilled water, for example, double-distilled water.
[0037] In one embodiment, the water content in the composition is greater than or equal to 10 parts by weight and less than or equal to 95 parts by weight, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95 parts by weight, or a subrange consisting of any values in these ranges.
[0038] In one embodiment, the water content in the composition is greater than or equal to 10% by weight and less than or equal to 95% by weight, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95% by weight, or a subrange consisting of any values in these ranges.
[0039] In one embodiment, the composition may contain inorganic fillers, such as clay, talc, or kaolin. In another embodiment, the composition does not contain any inorganic fillers, such as clay, talc, or kaolin.
[0040] In one embodiment, the composition may contain polysaccharides or derivatives thereof, such as starch, pectin, chitosan, cellulose, or derivatives thereof. More specifically, cellulose derivatives include, but are not limited to: cellulose ether derivatives (e.g., methylcellulose (MC), hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose (HEC), sodium carboxymethyl cellulose (CMC-Na), ethyl cellulose (EC), hydroxypropyl cellulose (HPC)) and cellulose ester derivatives (e.g., cellulose acetate (CA), cellulose acetate butyrate (CAB)).
[0041] In another aspect of the invention, a method for preparing a dispersion is provided, comprising mixing the components of the foregoing aspects of the invention to obtain an aqueous polyhydroxyalkanoate dispersion, said composition comprising at least the first component, the second component, and water.
[0042] In one embodiment, the method does not include a heating step. In another embodiment, the method may include a heating step.
[0043] In one embodiment, the method is operated at room temperature (e.g., 15-28°C, such as 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 or 28°C, or a subrange consisting of any values in these ranges).
[0044] In another aspect of the invention, a dispersion is provided, which is prepared by the composition and / or method of the foregoing aspects of the invention, said dispersion being an aqueous polyhydroxyalkanoate dispersion.
[0045] In one embodiment, the aqueous polyhydroxyalkanoate dispersion can be stored as a master dispersion.
[0046] In one embodiment, a component selected from the following may be added to the parent dispersion:
[0047] i) The aforementioned first component;
[0048] ii) Inorganic fillers, such as clay, talc, or kaolin; and
[0049] iii) Polysaccharides or their derivatives, such as starch, pectin, chitosan, cellulose, or their derivatives.
[0050] In a more specific embodiment, a component selected from the following may be added to the parent dispersion:
[0051] i) The aforementioned first component;
[0052] ii) Inorganic fillers selected from clay, talc, or kaolin; and
[0053] iii) Cellulose or its derivatives selected from cellulose ether derivatives (e.g., methylcellulose (MC), hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose (HEC), sodium carboxymethyl cellulose (CMC-Na), ethyl cellulose (EC), hydroxypropyl cellulose (HPC)) and cellulose ester derivatives (e.g., cellulose acetate (CA), cellulose acetate butyrate (CAB)).
[0054] In a more specific embodiment, 0-40% (e.g., 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%, or a subrange of any values within these ranges) of inorganic filler may be added relative to the weight of the parent dispersion.
[0055] In a more specific embodiment, 0-40% (e.g., 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%, or a subrange of any value in these ranges) of polysaccharide or its derivatives may be added relative to the weight of the parent dispersion.
[0056] In one embodiment, the dispersion can be applied to various existing food packaging, such as paper cups (e.g., molded paper cups), celluloid, greaseproof paper, paper bowls (e.g., molded paper bowls), etc.
[0057] In one embodiment, the dispersion can be coated onto food packaging in one or more layers (e.g., two, three, or four layers). In one specific embodiment, each layer can have the same or different thicknesses. In a more specific embodiment, each layer can independently have a coating weight of 10-40 g / m² (e.g., 10, 15, 20, 25, 30, 35, or 40 g / m², or a subrange of any value within these ranges). In another specific embodiment, each layer can have the same or different components.
[0058] In another aspect of the invention, a molded article is provided, comprising a first component and a second component as defined in the foregoing aspects of the invention.
[0059] In one embodiment, the molded body is in the form of a film. In a more specific embodiment, the film can be produced by any existing process, such as a coating process.
[0060] In one embodiment, the molded body can be applied to various existing food packaging, such as paper cups (e.g., molded paper cups), celluloid, greaseproof paper, paper bowls (e.g., molded paper bowls), etc.
[0061] In one embodiment, the molded body on food packaging can be one or more layers, such as two, three, four, etc. In a specific embodiment, each layer can have the same or different thicknesses. In a more specific embodiment, each layer can independently have a coating weight of 10-40 g / m² (e.g., 10, 15, 20, 25, 30, 35, or 40 g / m², or a subrange of any values within these ranges). In another specific embodiment, each layer can have the same or different components.
[0062] In this invention, depending on the specific context, "film" and "coating" can be used interchangeably, both referring to the layered structure formed by the polyhydroxyalkanoate dispersion.
[0063] In one embodiment, the composition described herein is used to formulate an aqueous polyhydroxyalkanoate dispersion. Specifically, the aqueous polyhydroxyalkanoate dispersion contains water.
[0064] In one embodiment, the parts by weight described herein are calculated based on 100 parts by weight of the total parts by weight of the system to be formulated, comprising the first component, the second component, optional other components, and water, even if the composition does not contain optional water. In one embodiment, the system refers to an aqueous polyhydroxyalkanoate dispersion.
[0065] This invention significantly reduces production costs by decreasing the content and variety of polyhydroxyalkanoates in the system. Furthermore, the aqueous polyhydroxyalkanoate dispersion prepared by this invention not only achieves effective dispersion but also exhibits excellent properties (e.g., good film-forming properties), and its preparation process is simpler; for example, the preparation process does not require heating and can be carried out at room temperature. In addition, related molded articles (e.g., films) prepared from the aqueous polyhydroxyalkanoate dispersion of this invention possess excellent properties, such as excellent barrier properties, heat-sealing properties, and adhesion. Moreover, the inventors have discovered that screening the specific substances of the first component (e.g., the type and molar ratio of repeating units of the polyhydroxyalkanoate), the specific substances of the second component (e.g., specific carbon chain length, specific salt type), and their weight percentages can advantageously improve the performance of this invention. Attached Figure Description
[0066] Figure 1 shows the adhesion test results of the films prepared from samples 2 and 4.
[0067] Figure 2 shows the results of the dyeing test on the films prepared from samples 1-7. Detailed Implementation
[0068] To better understand the present invention, the following embodiments further illustrate the content of the invention, but the content of the invention is not limited to the following embodiments. Unless otherwise specified, the experimental operations described in the following embodiments are routine operations; the reagents and materials described are commercially available unless otherwise specified.
[0069] 1. Preliminary study on the composition and content of the composition
[0070] The polyhydroxyalkanoate (PHA) (specifically poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), with a weight-average molecular weight of 600,000, wherein the repeating units derived from 3-hydroxybutyrate account for 90% of the molar percentage of PHA and the repeating units derived from 3-hydroxyhexanoate account for 10% of the molar percentage of PHA) and other components (the content of each component is calculated according to the weight percentage of each component in the dispersion) in Table 1 below were stirred at room temperature to prepare aqueous polyhydroxyalkanoate dispersion samples numbered 1-7 (among which, sample 8 could not form a stable dispersion and therefore could not be tested later).
[0071] Table 1. Composition of Aqueous Polyhydroxyalkanoate Dispersions
[0072] The above-mentioned aqueous polyhydroxyalkanoate dispersion samples were coated onto cardboard according to the parameters in Table 2 below.
[0073] 2
[0074] After the dispersion forms a film on the paperboard, subsequent tests are conducted on the coated paperboard. The specific tests are as follows.
[0075] Test Example 1: Hydrophobicity Test
[0076] This test aims to detect the hydrophobic properties of the membrane. The specific test method is as follows:
[0077] Test according to the TAPPI T 441 standard method, test time 300s.
[0078] The measured results are shown in Table 3.
[0079] Table 3. Hydrophobicity Test Results
[0080] As shown in Table 3, the membranes prepared from samples 1, 2, 5 and 7 have the best hydrophobic properties, while the membrane prepared from sample 4 has the worst hydrophobic properties.
[0081] Test Example 2: Heat Sealability Test
[0082] This test aims to evaluate the heat-sealing performance of the membrane. The specific test method is as follows:
[0083] Tested according to the standard method of GB / T 25436-2010, with a test temperature of 180℃, a pressure of 600kPa, and a time of 2s.
[0084] The measured results are shown in Table 4.
[0085] Table 4 Results of heat-sealing test
[0086] As shown in Table 4, the two heat-sealing parameters of the film prepared by sample 3 are both 0 N / mm, so it has no heat-sealing performance and cannot meet the requirements of post-processing; while the heat-sealing parameters of the films prepared by other samples all meet the requirements (i.e., for coating-coating, greater than 0.3 N / mm; for coating-paperboard, greater than 0.2 N / mm), and can meet the requirements of post-processing.
[0087] Test Example 3 Adhesion Test
[0088] This test aims to detect the adhesion performance of the film to the paperboard. The specific test method is as follows:
[0089] Tested according to the ASTM F2252 / F2252M-13(2018) standard method.
[0090] The measured results are shown in Table 5 and Figure 1.
[0091] Table 5 Adhesion Test Results
[0092] Adhesion properties demonstrate the bonding strength between the film and the fibers in the paperboard. The film prepared from sample 4 exhibited the worst adhesion, as shown in Table 5 and Figure 1B (in the figure, a significant amount of film adhered to the test tape, indicating poor adhesion between the film and the paperboard). Films prepared from other samples showed better bonding strength with the fibers in the paperboard, as shown in Table 5 and Figure 1A (the figure shows the test results for the film prepared from sample 2; the test tape was very clean, indicating good adhesion between the film and the paperboard).
[0093] Test Example 4: Oil Separation Test
[0094] This test aims to detect the oil-repellent performance of the membrane. The specific test method is as follows:
[0095] Tested according to ASTM F119-82 standard method, at a test temperature of 40℃.
[0096] The measured results are shown in Table 6.
[0097] Table 6 Results of oil-repellency test
[0098] As shown in Table 6, the membranes prepared from samples 1 and 2 exhibited the best performance in blocking oil at 40°C, with a duration of more than 7 hours. In contrast, the membrane prepared from sample 4 showed the worst performance in blocking oil at 40°C, with a duration of less than 5 minutes.
[0099] Test Example 5: Staining Test
[0100] This test aims to evaluate the coating quality. The specific test method is as follows: After dropping a saturated solution of methyl red ethanol onto the substrate with a dropper, immediately use a cotton swab or degreased cotton to evenly spread the droplet on the surface of the substrate with a diameter of about 5-10 cm; after the surface dries, take a picture to record the surface condition and evaluate the coating quality, including pinhole density, etc.
[0101] The measured results are shown in Table 7 and Figure 2.
[0102] Table 7 Results of staining tests
[0103] As shown in Table 7 and Figure 2, no dye penetration points were found in the membranes prepared from samples 1, 2, and 5, meaning the membranes were free of pinholes, with a uniform surface and no defects. However, the membranes prepared from samples 3, 4, 6, and 7 all showed varying degrees of pinhole distribution. Specifically, the membranes prepared from samples 3 and 6 showed a small number of penetration points and relatively few surface defects; the membrane prepared from sample 7 showed uneven penetration points and more surface defects; and the membrane prepared from sample 4 had the most surface defects and the most severe penetration.
[0104] The results of tests 1-5 show that the films prepared from samples 1, 2, and 5 exhibit the best hydrophobicity, heat-sealing properties, adhesion, oil-blocking properties, and the least surface pinhole distribution. In other words, the aqueous polyhydroxyalkanoate dispersion prepared from the composition of this invention has good film-forming properties, and the resulting films exhibit excellent hydrophobicity, heat-sealing properties, adhesion, oil-blocking properties, and the least surface pinhole distribution.
[0105] 2. Further research on the composition and content of the composition.
[0106] To further investigate the effects of each component and its content in the composition on the properties of the dispersion and its product, the compositions in Table 8 below were prepared and stirred at room temperature to form a dispersion (among which, sample 23 could not form a stable dispersion and therefore could not be tested later).
[0107] Table 8. Composition and content of the composition (in weight %) Note: 1. PHBHHX (1 mol% HHx) refers to poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a weight-average molecular weight of 800,000, in which repeating units derived from 3-hydroxybutyrate account for 99% of the molar percentage of PHA, and repeating units derived from 3-hydroxyhexanoate account for 1% of the molar percentage of PHA; PHBHHX (5 mol% HHx) refers to poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a weight-average molecular weight of 600,000, in which repeating units derived from 3-hydroxybutyrate account for 95% of the molar percentage of PHA, and repeating units derived from 3-hydroxyhexanoate account for 5% of the molar percentage of PHA; PHBHHX (11 mol% HHx) refers to poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a weight-average molecular weight of 700,000, in which repeating units derived from 3-hydroxybutyrate account for 89% of the molar percentage of PHA, and repeating units derived from 3-hydroxyhexanoate account for 11% of the molar percentage of PHA; PHBHHX (25 mol% HHx) refers to poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a weight-average molecular weight of 800,000, in which repeating units derived from 3-hydroxybutyrate account for 75% of the molar percentage of PHA, and repeating units derived from 3-hydroxyhexanoate account for 25% of the molar percentage of PHA. 2. P34HB (5 mol% 4HB) refers to poly(3-hydroxybutyrate-co-4-hydroxybutyrate), with a weight-average molecular weight of 800,000. The repeating units derived from 3-hydroxybutyrate constitute 95% of the molar percentage of PHA, and the repeating units derived from 4-hydroxybutyrate constitute 5%. P34HB (11 mol% 4HB) refers to poly(3-hydroxybutyrate-co-4-hydroxybutyrate), with a weight-average molecular weight of 1,000,000. The repeating units derived from 3-hydroxybutyrate constitute 89% of the molar percentage of PHA, and the repeating units derived from 4-hydroxybutyrate constitute 11%. 3. PHB refers to poly(3-hydroxybutyrate), with a weight-average molecular weight of 800,000. 4. Polylactic acid has a weight-average molecular weight of 200,000.
[0108] The above dispersion samples were coated onto paperboard according to the parameters in Table 9 below. After the dispersion formed a film on the paperboard, the coated paperboard was subjected to subsequent tests, the specific tests being the same as those in Test Examples 1 and 4 above. The results are shown in Table 9 below.
[0109] Table 9 Performance test results of the dispersion
[0110] Comparing the test results of samples 11 and 18-24, it can be seen that using PHA as the first component yields better dispersion performance compared to other polymers, especially poly(3-hydroxybutyrate-co-3-hydroxyhexanoate). In particular, the best performance is achieved when the repeating units derived from 3-hydroxyhexanoate account for 5%-11% of the molar percentage in poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).
[0111] Comparing the test results of samples 11 and 16-17, it can be seen that when the weight percentage of PHA is between 20-35%, the dispersions can achieve excellent hydrophobic and oil-separating properties. When the weight percentage of PHA is further increased from 20%, the performance of the dispersions (especially the hydrophobic properties) is further improved.
[0112] The test results of samples 9-14 and 25 show that stearates or stearate esters can achieve better dispersion performance compared to other compounds, especially zinc stearate and calcium stearate.
[0113] The test results of samples 11 and 15 show that when the content of stearate or stearate ester is further increased, the performance of the dispersion (especially the hydrophobic properties) is further improved.
[0114] 3. Application Scenario Research
[0115] The aqueous polyhydroxyalkanoate dispersion prepared by this invention can be stored as a master dispersion, and other components can be added to the master dispersion according to the application scenario to meet the specific needs of various application scenarios.
[0116] Unless otherwise specified, "parent dispersion" in the following text refers to an aqueous polyhydroxyalkanoate dispersion containing the following components:
[0117] 20 wt% poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a weight average molecular weight of 800,000, wherein repeating units derived from 3-hydroxybutyrate account for 89% of the molar percentage of PHA and repeating units derived from 3-hydroxyhexanoate account for 11% of the molar percentage of PHA.
[0118] 10 wt% calcium stearate;
[0119] 2 wt% sorbitol;
[0120] 0.2 wt% carboxymethyl cellulose, and
[0121] The remaining water.
[0122] Unless otherwise specified, the subsequent testing process is as described in the aforementioned test examples.
[0123] Oil-proof paper
[0124] The master dispersion (sample 26) and an experimental dispersion containing 25% (by weight of the master dispersion) of other components were coated onto greaseproof paper, and subsequent tests were performed. The greaseproof paper and dispersion coating parameters, as well as the test results, are shown in Table 10 below.
[0125] Table 10. Coating parameters and test results for oleophobic paper and dispersion.
[0126] Note: In the table, the polysaccharide is pullulan polysaccharide, 99wt% purity; the main components of clay are aluminum oxide (Al2O3), silicon dioxide (SiO2), magnesium oxide (MgO) and potassium oxide (K2O); microcrystalline cellulose (MCC) is 99wt% purity.
[0127] The test results show that the dispersion can still achieve good barrier properties even after adding 25% of polysaccharides, clay or cellulose derivatives.
Claims
1. A composition comprising a first component, a second component, and optionally, water, wherein: The first component comprises a polyhydroxyalkanoate having the following repeating units: In formula I, n is 1, 2, or 3; R1 is hydrogen or straight-chain or branched C1-C. 15 Alkyl groups, and the content of the polyhydroxyalkanoate is greater than 0 parts by weight and not more than 60 parts by weight; The second component comprises stearate or a derivative thereof, and the content of the second component is at least 5 parts by weight.
2. A composition comprising a first component, a second component, and optionally, water, wherein: The first component comprises a polyhydroxyalkanoate having the following repeating units: In formula I, n is 1, 2, or 3; R1 is hydrogen or straight-chain or branched C1-C. 15 Alkyl groups, and the content of the polyhydroxyalkanoate is greater than 0% by weight and not more than 60% by weight; The second component comprises stearate or a derivative thereof, and the content of the second component is at least 5% by weight.
3. The composition according to any one of the preceding claims, wherein, In Formula I, n is 1 or 2; R1 is hydrogen or a straight-chain or branched C1-C8 alkyl group.
4. The composition according to any one of the preceding claims, wherein, The polyhydroxyalkanoate contains repeating units derived from 3-hydroxybutyrate.
5. The composition according to claim 4, wherein, The polyhydroxyalkanoate contains only repeating units derived from 3-hydroxybutyrate; and / or The polyhydroxyalkanoate contains a repeating unit derived from 3-hydroxybutyrate, and at least one repeating unit derived from 3-hydroxypropionate, 3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonanoate, 3-hydroxydecanoate, 3-hydroxyundecanoate and / or 4-hydroxybutyrate.
6. The composition according to any one of the preceding claims, wherein, The polyhydroxyalkanoate includes at least one of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate).
7. The composition according to claim 4, wherein, The polyhydroxyalkanoate contains 80-98 mol% of repeating units derived from 3-hydroxybutyrate.
8. The composition according to claim 5, wherein, The polyhydroxyalkanoate contains repeating units derived from 3-hydroxybutyrate and repeating units derived from 3-hydroxyhexanoate.
9. The composition according to claim 8, wherein the polyhydroxyalkanoate contains 80-98 mol% repeating units derived from 3-hydroxybutyrate and 2-20 mol% repeating units derived from 3-hydroxyhexanoate.
10. The composition according to any one of the preceding claims, wherein the stearate comprises one or more of calcium stearate, zinc stearate, or magnesium stearate.
11. The composition according to any one of the preceding claims, wherein, The water content in the composition is greater than or equal to 10 parts by weight and less than or equal to 95 parts by weight; or the water content in the composition is greater than or equal to 10% by weight and less than or equal to 95% by weight.
12. A method for preparing a dispersion comprising mixing a first component, a second component as defined in any one of claims 1-11, and optionally water, to obtain an aqueous polyhydroxyalkanoate dispersion, said composition comprising at least the first component, the second component, and water.
13. A dispersion prepared from the composition of any one of claims 1-11 and / or the method of claim 12, wherein the dispersion is an aqueous polyhydroxyalkanoate dispersion.
14. A molded article comprising a first component and a second component as defined in any one of claims 1-11.
15. The molded article according to claim 14, wherein, The molded body can be in the form of a film.