Polyhydroxyalkanoate material, its preparation method and application
By compounding poly(3-hydroxybutyrate) and other polyhydroxy fatty acid esters, along with additives, the problems of poor stiffness, easy breakage, and non-degradability of PLA polymer products have been solved, resulting in injection-molded products with high toughness and degradability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- BEIJING PHABUILDER BIOTECHNOLOGY CO LTD
- Filing Date
- 2026-01-30
- Publication Date
- 2026-05-29
AI Technical Summary
Injection-molded products made from existing PLA polymer materials suffer from problems such as poor stiffness, easy breakage, non-degradability, and high cost. Furthermore, the molds are not suitable for PHA materials, leading to product burning and flash.
A variety of polymer materials are compounded and the proportions of each component are controlled, including poly(3-hydroxybutyrate) (PHB) and other polyhydroxy fatty acid esters. Nucleating agents, compatibilizers, plasticizers, fillers, etc. are added to form polyhydroxy fatty acid ester materials, which are then extruded through a screw extruder.
It achieves good stiffness, toughness and easy degradation of polyhydroxyalkanoate materials, solves the problems of product breakage and high cost, extends shelf life and reduces production costs.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of polymer materials technology, and in particular to a polyhydroxyalkanoate material, its preparation method and application. Background Technology
[0002] In the prior art, injection-molded products are generally made of PLA polymer material. However, PLA polymer material has the following shortcomings: (1) PLA cannot be composted at home, let alone degraded in the ocean, which is detrimental to the environment; (2) PLA molds in the prior art are not suitable for injection molding PHA material, which will result in product burning and flash; (3) Products made of PLA polymer material have too thick walls, too heavy weight, and too high cost; (4) Existing products either have poor stiffness or are easy to break after bending, have short shelf life, and cannot meet customer requirements.
[0003] Considering the problems encountered in the application of PLA polymer materials, existing technologies use polyhydroxyalkanoates (PHAs) to replace PLA materials. PHA is a biosynthetic thermoplastic polymer. As a substitute for traditional plastics, PHA can be manufactured and processed using the same processes; moreover, the product can rapidly degrade into carbon dioxide and water in the natural environment, avoiding the white pollution problem associated with disposable products, and it can naturally degrade into carbon dioxide and water without polluting the environment.
[0004] However, due to the limitations of PHA materials, existing injection-molded products (such as injection-molded knives, forks and spoons made of PHB materials) cannot achieve the appropriate stiffness to prevent breakage after bending, or have the appropriate toughness and stiffness but cannot degrade. Summary of the Invention
[0005] To address the problem that products made from existing polymer materials cannot simultaneously possess good stiffness, toughness, and degradability, this invention provides a polyhydroxyalkanoate material that combines good stiffness and toughness with degradability, along with its preparation method and applications.
[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a polyhydroxyalkanoate material, wherein, by weight, the raw materials for preparing the polyhydroxyalkanoate material include the following components: 40-90 parts of a first polymer and 10-20 parts of a second polymer; The first polymer is composed of two or more polyhydroxy fatty acid esters, and the two or more polyhydroxy fatty acid esters include at least 8%-22.5% by mass of poly3-hydroxybutyrate (PHB). The second polymer is selected from at least one of polylactic acid, poly-ε-caprolactone, polybutylene succinate, polybutylene adipate, polybutylene terephthalate, and polyglycolic acid.
[0007] PHB, as a polyhydroxyalkanoate, has good biodegradability and biocompatibility, but it is brittle and has poor impact resistance. Therefore, although the molded products made from existing PHB materials have suitable stiffness, they are prone to breakage after bending.
[0008] The polyhydroxyalkanoate (PHB) material of this invention combines multiple polymeric materials, with each material controlled within a suitable proportion range. If the PHB content is too high, the PHB material will have excessive hardness and low toughness; if the PHB content is too low, the PHB material will have poor stiffness. Only when the proportions of each polymer are controlled within the range specified in this invention does the resulting PHB material possess both good stiffness and toughness, and is also easily degradable.
[0009] As a preferred embodiment of the polyhydroxy fatty acid ester material of the present invention, 40-90 parts of the first polymer include at least 5-20 parts by weight of poly-3-hydroxybutyrate (PHB).
[0010] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the first polymer is composed of 5-20 parts by weight of polyhydroxyalkanoate A and 35-70 parts by weight of polyhydroxyalkanoate B; wherein the polyhydroxyalkanoate A is poly-3-hydroxybutyrate (PHB). In the polyhydroxyalkanoate material of the present invention, the weight parts of PHB can be 5 parts, 8 parts, 10 parts, 11 parts, 12 parts, 15 parts, 18 parts, or 20 parts, etc.; the weight parts of polyhydroxyalkanoate B can be 35 parts, 40 parts, 50 parts, 60 parts, 65 parts, 68 parts, or 70 parts, etc.
[0011] In a more preferred embodiment of the polyhydroxyalkanoate material of the present invention, the poly(3-hydroxybutyrate) is 5-12 parts by weight, and the polyhydroxyalkanoate B is 40-70 parts by weight. Particularly preferred is the poly(3-hydroxybutyrate) being 8-12 parts by weight, and the polyhydroxyalkanoate B being 50-68 parts by weight. The amount of polymer in the polyhydroxyalkanoate material affects the performance of the product. Studies have found that when the poly(3-hydroxybutyrate) is 5-12 parts by weight and the polyhydroxyalkanoate B is 40-70 parts by weight, the stiffness, toughness, and degradability of the polyhydroxyalkanoate material are all better; especially when the poly(3-hydroxybutyrate) is 8-12 parts by weight and the polyhydroxyalkanoate B is 50-68 parts by weight, the stiffness, toughness, and degradability of the polyhydroxyalkanoate material are further improved.
[0012] In a preferred embodiment of the polyhydroxy fatty acid ester material of the present invention, the polyhydroxy fatty acid ester B is selected from at least one of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx), poly(3-hydroxybutyrate-co-4-hydroxybutyrate-co-3-hydroxyvalerate) (P3HB4HB3HV), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate-co-5-hydroxyvalerate) (P3HB4HB5HV). Polyhydroxyalkanoate B can be selected from P3HB4HB, PHBV, PHBHHx, P3HB4HB3HV, or P3HB4HB5HV, or a mixture thereof. For example, polyhydroxyalkanoate B can be a mixture of PHBHHx and PHBV, a mixture of P3HB4HB and PHBV, a mixture of P3HB4HB and P3HB4HB3HV, or a mixture of P3HB4HB and P3HB4HB5HV. Selecting polyhydroxyalkanoate B in this way yields high-toughness polyhydroxyalkanoate materials and corresponding products.
[0013] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the polyhydroxyalkanoate B is poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB). P3HB4HB has good toughness, and its combination with PHB can balance the stiffness and toughness of the polyhydroxyalkanoate material. When the proportion of P3HB4HB added is too high, it will affect the product's shape and quality, resulting in poor product stiffness, easy flash, and a long molding cycle; when the proportion added is too low, it will affect the product's degradation cycle, and the product is prone to breakage after about 30 days of post-crystallization, which cannot meet customer requirements.
[0014] As a preferred embodiment of the polyhydroxy fatty acid ester material of the present invention, the molar percentage of the 4HB monomer unit in the poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB) is 55%-75%, preferably 60-65%.
[0015] As a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the raw materials for preparing the polyhydroxyalkanoate material further include the following components: 1-5 parts of nucleating agent, 1-5 parts of compatibilizer, 1-5 parts of plasticizer, and 0-30 parts of filler.
[0016] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the filler is 5-25 parts by weight. Adding a filler to the polyhydroxyalkanoate material not only improves the material's mechanical properties but also reduces production costs.
[0017] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the nucleating agent is selected from at least one of inorganic powder, dibenzyl sorbitol and its derivatives, aromatic phosphate salts, carboxylic acid metal salts, organophosphates, and sorbitol benzylidene derivatives; preferably, the inorganic powder is selected from at least one of talc, magnesium silicate, bentonite, calcined kaolin, calcium carbonate, silicon dioxide, alum, titanium dioxide, calcium oxide, magnesium oxide, carbon black, and mica; the carboxylic acid metal salt is selected from sodium succinate, sodium glutarate, sodium hexanoate, and 4-methyl... The material contains at least one of sodium valerate, aluminum adipic acid, aluminum tert-butylbenzoate, aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate, and sodium β-naphthoate; the organophosphate is selected from at least one of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and phosphonium aluminum salt (NA-21); more preferably, the nucleating agent is selected from at least one of talc, calcium carbonate, silica, dibenzyl sorbitol, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, and phosphonium aluminum salt (NA-21). The nucleating agent helps improve the crystallinity, strength, and thermal stability of polyhydroxyalkanoate materials.
[0018] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the compatibilizer is selected from at least one of glycidyl methacrylate (GMA), oligomeric epoxy chain extenders, ethanolamine, tetrabutyl titanate, BASF ADR4400, BASF ADR4300, ethylene-maleic anhydride copolymer (e.g., Vertellus E60P), trimethylolpropane, and N,N'-ethylene bis-stearamide (e.g., EK-145); more preferably, the compatibilizer is BASF ADR4300. The compatibilizer helps improve the compatibility of the mixture.
[0019] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the plasticizer is selected from at least one of epoxidized soybean oil, triethyl citrate, tributyl citrate, and acetylated tributyl citrate; more preferably, the plasticizer is triethyl citrate. The plasticizer helps to increase the flexibility of the matrix material.
[0020] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the filler is selected from at least one of fiber filler materials, nano-montmorillonite, nano-calcium carbonate, nano-titanium boride, nano-titanium carbide, talc, titanium dioxide, bentonite, magnesium silicate, kaolin, and boron nitride; more preferably, the filler is a fiber filler material; particularly preferably, the fiber filler material is selected from at least one of cellulose, hemicellulose, lignin, and coconut fiber.
[0021] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the polyhydroxyalkanoate material further includes at least one of a heat stabilizer, an antioxidant, and a lubricant. The heat stabilizer helps to prevent PHA thermal degradation.
[0022] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the heat stabilizer is 0.1-3 parts by weight, preferably 0.2-2 parts by weight, and more preferably 0.5-2 parts by weight.
[0023] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the antioxidant is 0.1-3 parts by weight, preferably 0.1-2 parts by weight, and more preferably 0.5-2 parts by weight.
[0024] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the heat stabilizer is selected from at least one of phosphites and polyols.
[0025] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the antioxidant is selected from at least one of phosphite compounds, hindered phenolic compounds, and thioether compounds.
[0026] In a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the lubricant is selected from at least one of fatty acid salts and fatty amides; preferably, the fatty acid salt is selected from at least one of calcium stearate, zinc stearate, calcium laurate, magnesium laurate, zinc 2-ethylhexanoate, and magnesium 2-ethylhexanoate.
[0027] As a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the raw materials for preparing the polyhydroxyalkanoate material include the following components: 40-90 parts of the first polymer, 10-20 parts of the second polymer, 1-5 parts of the nucleating agent, 1-5 parts of the compatibilizer, 1-5 parts of the plasticizer, 0-30 parts of the filler, 0.1-3 parts of the heat stabilizer, 0.1-3 parts of the antioxidant, and 0.1-0.5 parts of the lubricant; The first polymer is composed of 5-20 parts by weight of polyhydroxy fatty acid ester A and 35-70 parts by weight of polyhydroxy fatty acid ester B; wherein polyhydroxy fatty acid ester A is poly3-hydroxybutyrate, and polyhydroxy fatty acid ester B is at least one of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3HB4HB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate-co-3-hydroxyvalerate) (P3HB4HB3HV); The second polymer is at least one of polylactic acid (PLA), poly-ε-caprolactone (PCL), and polybutylene succinate (PBS); The nucleating agent is at least one of silicon dioxide, dibenzyl sorbitol, and aluminum phosphine salt; The compatibilizer is at least one of glycidyl methacrylate and BASF ADR4300; The plasticizer is at least one of triethyl citrate, acetylated tributyl citrate, and tributyl citrate; The filler is at least one of cellulose, hemicellulose, and lignin; The heat stabilizer is a phosphite; The antioxidant is at least one of hindered phenolic compounds, phosphite compounds, and thioether compounds; The lubricant is at least one of calcium stearate, zinc stearate, and calcium laurate.
[0028] As a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the polyhydroxyalkanoate material has a weight-average molecular weight of 450,000 to 550,000; and / or, the polyhydroxyalkanoate material has a melt flow rate of 10-20 g / 10 min, which is measured according to ASTM D1238 using 2.16 kg weight and at a temperature of 180°C.
[0029] As a preferred embodiment of the polyhydroxyalkanoate material of the present invention, the polyhydroxyalkanoate material has a weight-average molecular weight of 453,000 to 535,000; and / or, the polyhydroxyalkanoate material has a melt flow rate of 10.8 to 15 g / 10 min, which is measured according to ASTM D1238 using a weight of 2.16 kg at a temperature of 180°C.
[0030] Secondly, the present invention provides a method for preparing the above-mentioned polyhydroxy fatty acid ester material, which includes: mixing the components in the raw materials according to the proportions and then feeding them into a screw extruder for extrusion molding.
[0031] Thirdly, the present invention provides the application of the above-mentioned polyhydroxyalkanoate material or the polyhydroxyalkanoate material prepared by the above method in the preparation of molded articles.
[0032] In a preferred embodiment of the application described in this invention, the molded article is an injection-molded article. More preferably, the injection-molded article is a knife, fork, or spoon.
[0033] Fourthly, the present invention provides a molded article prepared using the above-described polyhydroxyalkanoate material or a polyhydroxyalkanoate material obtained by the above-described method. For example, using the polyhydroxyalkanoate material of the present invention as a raw material, it is injection molded in an injection molding machine to obtain an injection molded article.
[0034] In a preferred embodiment of the molded article of the present invention, the molded article is an injection-molded article; more preferably, the injection-molded article is a knife, fork, or spoon.
[0035] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention combines multiple polymer materials and controls them within appropriate proportions, thereby balancing the rigidity, toughness, and degradability of each polymer material to obtain a polyhydroxyalkanoate material that possesses both good stiffness and toughness and is easily degradable. Therefore, this invention (1) improves the problem of incompatibility between stiffness and toughness in products such as knives, forks, and spoons; (2) improves the problem of products becoming brittle after crystallization, solving the post-crystallization problem; and (3) improves the shelf life of products, extends their service life, reduces costs, and increases customer profits.
[0036] This invention also uses additives to neutralize the formula, which can increase the toughness and compatibility of the formula, and ensure that the material density does not exceed the standard and the weight of the finished product meets the customer's requirements.
[0037] The polyhydroxyalkanoate material of this invention is a marine biodegradable material, and the processing temperature can reach 160℃-170℃. The reduced processing temperature results in a shorter processing cycle and lower equipment wear. Detailed Implementation
[0038] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.
[0039] In the following embodiments, the meanings and origins of the abbreviations are as follows: PHB: Poly(3-hydroxybutyrate), sourced from Beijing Microstructure Factory Biotechnology Co., Ltd., model number PB3000, with a weight-average molecular weight of 800,000; PHBV: Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) is sourced from Beijing Microstructure Workshop Biotechnology Co., Ltd., with a weight-average molecular weight of 600,000. P3HB4HB: Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is sourced from Beijing Microstructure Workshop Biotechnology Co., Ltd., with a weight-average molecular weight of 600,000. P3HB4HB3HV: Poly(3-hydroxybutyrate-co-4-hydroxybutyrate-co-3-hydroxyvalerate), sourced from Beijing Microstructure Workshop Biotechnology Co., Ltd., with a weight-average molecular weight of 600,000; PLA: Polylactic acid, sourced from Anhui Fengyuan Biotechnology Co., Ltd., model number FY201; PCL: Poly-ε-caprolactone, sourced from Ningbo Inno Chemical Co., Ltd.
[0040] PBS: Polybutylene succinate, sourced from PTT Chemicals in Thailand, model number FZ71PB.
[0041] Example 1 One embodiment of the polyhydroxyalkanoate material and its preparation method of the present invention, wherein the raw materials for preparing the polyhydroxyalkanoate material in this embodiment are as follows: First polymer: 10 parts PHB, 60 parts P3HB4HB (the molar percentage of 4HB monomer units in P3HB4HB is 62%). Second polymer: 15 parts of polylactic acid (PLA); Nucleating agent: 1 part silicon dioxide; Compatibilizer: 1 part glycidyl methacrylate; Plasticizer: 1 part triethyl citrate; Filler: 25 parts cellulose; Heat stabilizer: 1 part phosphite; Antioxidant: 1 part hindered phenolic compound; Lubricant: 0.5 parts calcium stearate.
[0042] The preparation method of the polyhydroxyalkanoate material in this embodiment is as follows: the raw materials for preparing the polyhydroxyalkanoate material are mixed evenly according to the ratio, and then added to the screw extruder for extrusion molding.
[0043] Example 2 This invention relates to an embodiment of a polyhydroxyalkanoate material and its preparation method. The only difference between the raw materials used in this embodiment and those in Example 1 is that in this embodiment, PHB is 8 parts by weight, P3HB4HB is 50 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. All other aspects are the same as in Example 1.
[0044] The preparation method of the polyhydroxy fatty acid ester material in this embodiment is the same as that in Example 1.
[0045] Example 3 This invention relates to an embodiment of a polyhydroxyalkanoate material and its preparation method. The only difference between the raw materials used in this embodiment and those in Example 1 is that in this embodiment, PHB is 12 parts by weight, P3HB4HB is 68 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. All other aspects are the same as in Example 1.
[0046] The preparation method of the polyhydroxy fatty acid ester material in this embodiment is the same as that in Example 1.
[0047] Example 4 This invention relates to an embodiment of a polyhydroxyalkanoate material and its preparation method. The only difference between the raw materials used in this embodiment and those in Example 1 is that in this embodiment, PHB is 5 parts by weight, P3HB4HB is 50 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. All other aspects are the same as in Example 1.
[0048] The preparation method of the polyhydroxy fatty acid ester material in this embodiment is the same as that in Example 1.
[0049] Example 5 This invention relates to an embodiment of a polyhydroxyalkanoate material and its preparation method. The only difference between the raw materials used in this embodiment and those in Example 1 is that in this embodiment, PHB is 11 parts by weight, P3HB4HB is 70 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. All other aspects are the same as in Example 1.
[0050] The preparation method of the polyhydroxy fatty acid ester material in this embodiment is the same as that in Example 1.
[0051] Example 6 This invention relates to an embodiment of a polyhydroxyalkanoate material and its preparation method. The only difference between the raw materials used in this embodiment and those in Example 1 is that in this embodiment, PHB is 8 parts by weight, P3HB4HB is 40 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. All other aspects are the same as in Example 1.
[0052] The preparation method of the polyhydroxy fatty acid ester material in this embodiment is the same as that in Example 1.
[0053] Example 7 This invention relates to an embodiment of a polyhydroxyalkanoate material and its preparation method. The only difference between the raw materials used in this embodiment and those in Example 1 is that in this embodiment, PHB is 15 parts by weight, P3HB4HB is 65 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. All other aspects are the same as in Example 1.
[0054] The preparation method of the polyhydroxy fatty acid ester material in this embodiment is the same as that in Example 1.
[0055] Example 8 This invention relates to an embodiment of a polyhydroxyalkanoate material and its preparation method. The only difference between the raw materials used in this embodiment and those in Example 1 is that in this embodiment, PHB is 20 parts by weight, P3HB4HB is 35 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. All other aspects are the same as in Example 1.
[0056] The preparation method of the polyhydroxy fatty acid ester material in this embodiment is the same as that in Example 1.
[0057] Comparative Example 1 The only difference between the raw materials used in this comparative example of polyhydroxyalkanoate material and those in Example 1 is that in this comparative example, PHB is 3 parts by weight, P3HB4HB is 50 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. Everything else is the same as in Example 1.
[0058] The preparation method of this comparative polyhydroxy fatty acid ester material is the same as that in Example 1.
[0059] Comparative Example 2 The only difference between the raw materials used in this comparative example of polyhydroxyalkanoate material and those in Example 1 is that in this comparative example, PHB is 25 parts by weight, P3HB4HB is 50 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. Everything else is the same as in Example 1.
[0060] The preparation method of this comparative polyhydroxy fatty acid ester material is the same as that in Example 1.
[0061] Comparative Example 3 The only difference between the raw materials used in this comparative example of polyhydroxyalkanoate material and those in Example 1 is that in this comparative example, PHB is 10 parts by weight, P3HB4HB is 30 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. Everything else is the same as in Example 1.
[0062] The preparation method of this comparative polyhydroxy fatty acid ester material is the same as that in Example 1.
[0063] Comparative Example 4 The only difference between the raw materials used in this comparative example of polyhydroxyalkanoate material and those in Example 1 is that in this comparative example, PHB is 10 parts by weight, P3HB4HB is 75 parts by weight, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. Everything else is the same as in Example 1.
[0064] The preparation method of this comparative polyhydroxy fatty acid ester material is the same as that in Example 1.
[0065] Comparative Example 5 The only difference between the raw materials used in this comparative example of polyhydroxyalkanoate material and those in Example 1 is that the first polymer in this comparative example is 70 parts of PHB, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. Everything else is the same as in Example 1.
[0066] The preparation method of this comparative polyhydroxy fatty acid ester material is the same as that in Example 1.
[0067] Comparative Example 6 The only difference between the raw materials used in this comparative example of polyhydroxyalkanoate material and those in Example 1 is that the first polymer in this comparative example is 70 parts of P3HB4HB, and the molar percentage of the 4HB monomer unit in P3HB4HB is 62%. Everything else is the same as in Example 1.
[0068] The preparation method of this comparative polyhydroxy fatty acid ester material is the same as that in Example 1.
[0069] Comparative Example 7 The only difference between the raw materials used in this comparative example of polyhydroxy fatty acid ester material and those used in Example 1 is that the raw materials used in this comparative example of polyhydroxy fatty acid ester material do not contain the second polymer; otherwise, they are the same as those used in Example 1.
[0070] The preparation method of this comparative polyhydroxy fatty acid ester material is the same as that in Example 1.
[0071] Example 9 One embodiment of the polyhydroxyalkanoate material and its preparation method of the present invention, wherein the raw materials for preparing the polyhydroxyalkanoate material in this embodiment are as follows: First polymer: 20 parts PHB, 60 parts PHBV; Second polymer: 10 parts of poly-ε-caprolactone (PCL); Nucleating agent: 1 part dibenzyl sorbitol; Compatibilizer: 1 part BASF ADR4300; Plasticizer: 1 part acetylglucosyl tributyl ester; Filler: 7 parts hemicellulose; Heat stabilizer: 0.1 parts of phosphite; Antioxidant: 0.1 parts of phosphite compounds; Lubricant: 0.1 parts zinc stearate.
[0072] The preparation method of the polyhydroxyalkanoate material in this embodiment is as follows: the raw materials for preparing the polyhydroxyalkanoate material are mixed evenly according to the ratio, and then added to the screw extruder for extrusion molding.
[0073] Example 10 One embodiment of the polyhydroxyalkanoate material and its preparation method of the present invention, wherein the raw materials for preparing the polyhydroxyalkanoate material in this embodiment are as follows: First polymer: 5 parts PHB, 35 parts P3HB4HB3HV; Second polymer: 20 parts of polybutylene succinate (PBS); Nucleating agent: 1.5 parts of phosphonium aluminum salt; Compatibilizer: 1.5 parts glycidyl methacrylate; Plasticizer: 5 parts tributyl citrate; Filler: 30 parts lignin; Heat stabilizer: 3 parts phosphite; Antioxidant: 3 parts of thioether compounds; Lubricant: 0.5 parts calcium laurate.
[0074] The preparation method of the polyhydroxyalkanoate material in this embodiment is as follows: the raw materials for preparing the polyhydroxyalkanoate material are mixed evenly according to the ratio, and then added to the screw extruder for extrusion molding.
[0075] Example of effect 1 This example tested the weight-average molecular weight (Mw) and melt flow rate (MFI) of the polyhydroxyalkanoate materials in Examples 1-10. The weight-average molecular weight was measured using gel permeation chromatography, and the melt flow rate was measured according to ASTM D1238 using a weight of 2.16 kg at 180°C. The test results are shown in Table 1 below.
[0076] Table 1
[0077] Example 2 This example tested the flexural modulus, flexural strength, toughness, and degradation properties of the polyhydroxyalkanoate materials in Examples 1-10 and Comparative Examples 1-7. The test methods are as follows: The test method for flexural modulus / flexural strength is as follows: test according to ISO 178 standard, with a sample size of 80mm×10mm×4mm and a test speed of 2mm / min; The toughness test method is as follows: Izod impact strength test (unnotched), according to ISO 180 standard, with a sample size of 80mm×10mm×4mm; The degradation performance test method is as follows: According to ASTM D6400 standard, the degradation rate is tested for 60 days under composting conditions (58℃, 55% humidity), and the standard value is ≥90%.
[0078] The test results are shown in Table 2 below.
[0079] Table 2
[0080] As shown in Table 2, when poly(3-hydroxybutyrate) is 5-12 parts by weight and poly(hydroxyalkanoate) B is 40-70 parts by weight, the stiffness, toughness and degradability of the poly(hydroxyalkanoate) material are better; especially when poly(3-hydroxybutyrate) is 8-12 parts by weight and poly(hydroxyalkanoate) B is 50-68 parts by weight, the stiffness, toughness and degradability of the poly(hydroxyalkanoate) material are further improved.
[0081] Example 3 The polyhydroxyalkanoate (PHA) material of this invention and the traditional PHA material were heated and melted using an injection molding machine, and then injected into a mold via a screw. Under the same conditions, they were injection molded into knives, forks, or spoons. The injection molding parameters of the injection molding machine are shown in Table 3 below.
[0082] Table 3 Dipping forks were immersed in an ice-water mixture for 5-10 minutes. The results showed that forks made from the polyhydroxyalkanoate (PHA) material of this invention did not break when bent after immersion, while forks made from traditional PHA material broke after bending. This demonstrates that the PHA material of this invention has superior toughness compared to traditional PHA material.
[0083] After being stored for a year, the knives, forks, and spoons made from the polyhydroxyalkanoate material of this invention can still be repeatedly folded without breaking. This demonstrates that the products made from the polyhydroxyalkanoate material of this invention possess good toughness.
[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A polyhydroxyalkanoate material, characterized in that, The raw materials for preparing the polyhydroxyalkanoate material, by weight, include the following components: 40-90 parts of the first polymer and 10-20 parts of the second polymer; The first polymer is composed of two or more polyhydroxy fatty acid esters, and the two or more polyhydroxy fatty acid esters include at least 8%-22.5% by mass of poly3-hydroxybutyrate. The second polymer is selected from at least one of polylactic acid, poly-ε-caprolactone, polybutylene succinate, polybutylene adipate, polybutylene terephthalate, and polyglycolic acid.
2. The polyhydroxyalkanoate material according to claim 1, characterized in that, The first polymer is composed of 5-20 parts by weight of polyhydroxyalkanoate A and 35-70 parts by weight of polyhydroxyalkanoate B; wherein polyhydroxyalkanoate A is poly-3-hydroxybutyrate. Preferably, the polyhydroxyalkanoate A is 5-12 parts by weight, and the polyhydroxyalkanoate B is 40-70 parts by weight; More preferably, the polyhydroxyalkanoate A is 8-12 parts by weight, and the polyhydroxyalkanoate B is 50-68 parts by weight.
3. The polyhydroxyalkanoate material according to claim 2, characterized in that, The polyhydroxy fatty acid ester B is selected from at least one of poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate-co-5-hydroxyvalerate); preferably poly(3-hydroxybutyrate-co-4-hydroxybutyrate).
4. The polyhydroxyalkanoate material according to any one of claims 1-3, characterized in that, The raw materials for preparing the polyhydroxyalkanoate material also include the following components: 1-5 parts of nucleating agent, 1-5 parts of compatibilizer, 1-5 parts of plasticizer, and 0-30 parts of filler; Preferably, the filler is 5-25 parts by weight.
5. The polyhydroxyalkanoate material according to claim 4, characterized in that, The raw materials for preparing the polyhydroxy fatty acid ester material satisfy at least one of the following (A)-(D): (A) The nucleating agent is selected from at least one of inorganic powders, dibenzyl sorbitol and its derivatives, aromatic phosphate salts, carboxylic acid metal salts, organophosphates, and sorbitol benzylidene derivatives; preferably, the inorganic powder is selected from at least one of talc, magnesium silicate, bentonite, calcined kaolin, calcium carbonate, silicon dioxide, alum, titanium dioxide, calcium oxide, magnesium oxide, carbon black, and mica; the carboxylic acid metal salt is selected from sodium succinate, sodium glutarate, sodium hexanoate, sodium 4-methylvalerate, and adipic acid. The product contains at least one of aluminum, aluminum tert-butylbenzoate, aluminum benzoate, potassium benzoate, lithium benzoate, sodium cinnamate, and sodium β-naphthoate; the organophosphate is selected from at least one of sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and aluminum phosphine; more preferably, the nucleating agent is selected from at least one of talc, calcium carbonate, silica, dibenzyl sorbitol, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, and aluminum phosphine (NA-21). (B) The compatibilizer is selected from at least one of glycidyl methacrylate, oligomeric epoxy chain extender, ethanolamine, tetrabutyl titanate, BASF ADR4400, BASF ADR4300, ethylene-maleic anhydride copolymer, trimethylolpropane, and N,N'-ethylene bis-stearamide; preferably, the compatibilizer is BASF ADR4300; (C) The plasticizer is selected from at least one of epoxidized soybean oil, triethyl citrate, tributyl citrate, and acetylated tributyl citrate; preferably, the plasticizer is triethyl citrate. (D) The filler is selected from at least one of fiber filler materials, nano montmorillonite, nano calcium carbonate, nano titanium boride, nano titanium carbide, talc, titanium dioxide, bentonite, magnesium silicate, kaolin, and boron nitride; preferably, the filler is a fiber filler material; more preferably, the fiber filler material is selected from at least one of cellulose, hemicellulose, lignin, and coconut fiber.
6. The polyhydroxyalkanoate material according to any one of claims 1-5, characterized in that, The raw materials for preparing the polyhydroxy fatty acid ester material also include at least one of heat stabilizer, antioxidant, and lubricant; Preferably, the heat stabilizer is 0.1-3 parts by weight; and / or, the antioxidant is 0.1-3 parts by weight; Preferably, the raw materials for preparing the polyhydroxyalkanoate material satisfy at least one of the following (I)-(III): (I) The heat stabilizer is selected from at least one of phosphites and polyols; (II) The antioxidant is selected from at least one of phosphite compounds, hindered phenolic compounds, and thioether compounds; (III) The lubricant is selected from at least one of fatty acid salts and fatty amides; preferably, the fatty acid salt is selected from at least one of calcium stearate, zinc stearate, calcium laurate, magnesium laurate, zinc 2-ethylhexanoate, and magnesium 2-ethylhexanoate.
7. The polyhydroxyalkanoate material according to any one of claims 1-6, characterized in that, The weight-average molecular weight of the polyhydroxyalkanoate material is 450,000-550,000; And / or, the melt flow rate of the polyhydroxyalkanoate material is 10-20 g / 10 min, which is measured according to ASTM D1238 using 2.16 kg weight and at a temperature of 180 °C.
8. A method for preparing the polyhydroxyalkanoate material according to any one of claims 1-7, characterized in that, include: After the components in the raw materials are mixed evenly according to the formula, they are fed into the screw extruder and extruded into shape.
9. The use of the polyhydroxyalkanoate material according to any one of claims 1-7 or the polyhydroxyalkanoate material obtained by the method of claim 8 in the preparation of molded articles; preferably, the molded article is an injection-molded article; more preferably, the injection-molded article is a knife, fork or spoon.
10. A molded article, characterized in that, The molded article is prepared using the polyhydroxyalkanoate material according to any one of claims 1-7 or the polyhydroxyalkanoate material prepared by the method according to claim 8; preferably, the molded article is an injection molded article; more preferably, the injection molded article is a knife, fork or spoon.