CN117820830A - Polyhydroxyalkanoate composition and preparation method and application thereof - Google Patents
Polyhydroxyalkanoate composition and preparation method and application thereof Download PDFInfo
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- CN117820830A CN117820830A CN202311783872.5A CN202311783872A CN117820830A CN 117820830 A CN117820830 A CN 117820830A CN 202311783872 A CN202311783872 A CN 202311783872A CN 117820830 A CN117820830 A CN 117820830A
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- Prior art keywords
- pha
- antioxidant
- terpolymer
- polyhydroxyalkanoate
- polyhydroxyalkanoate composition
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- 229920000903 polyhydroxyalkanoate Polymers 0.000 title claims abstract description 113
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 title claims abstract description 112
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920001897 terpolymer Polymers 0.000 claims abstract description 34
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
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- 239000000843 powder Substances 0.000 claims description 9
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- 239000000126 substance Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 2
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 claims description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- JJAIIULJXXEFLV-UHFFFAOYSA-N pentane-2,3,4-triol Chemical compound CC(O)C(O)C(C)O JJAIIULJXXEFLV-UHFFFAOYSA-N 0.000 claims description 2
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides a polyhydroxyalkanoate composition, a preparation method and application thereof, wherein the polyhydroxyalkanoate composition comprises a PHA terpolymer, the PHA terpolymer is P3HB4HB3HV and/or P3HB4HB5HV, the molar content of a repeating unit 3HB is more than 94%, and the weight average molecular weight of the PHA terpolymer is more than 30 ten thousand. The polyhydroxyalkanoate composition containing the specific PHA terpolymer can realize the properties of ocean degradability, high crystallinity, high strength, certain toughness, high load deformation temperature, low melting point and the like under the condition of little or no auxiliary agent, and can be applied to products such as injection molding, 3D printing, plastic sucking, suction pipes, fibers, sheets and the like.
Description
Technical Field
The invention relates to the field of biodegradable high polymer materials, in particular to a polyhydroxyalkanoate composition, a preparation method and application thereof.
Background
As white pollution becomes increasingly serious, there is an increasing demand for environmentally friendly degradable materials. Particularly, some people who pay attention to ocean health and have low carbon sustainability are more in need of bio-based materials capable of being subjected to ocean degradation and home composting. At this time, PLA, PBS, PBAT is not satisfactory, and only PCL, PGA, starch, cellulose, PHA and other materials remain.
However, PCL has a too low melting point, and the practical application scene is limited; PGA is strong and poor in toughness, but aging and degradation are too fast and shelf life is too short; the properties of starch, cellulose and the like are not so outstanding that it is difficult to use them as a main component. Therefore, PHA is the degradable material with the most application prospect.
However, most types of PHAs still face problems of high melting point, narrow hot working window, and poor performance during processing applications. For example, PHB HAs a melting point of about 175 ℃, and as a P3HA (poly 3-hydroxy fatty acid ester), the molecular chain breaking process starts from 160 ℃, so that after one hot working, the effect on the performance is great, even the molecular weight is halved after pelleting, the strength is reduced by 5-30%, and the stable and effective application is difficult. PHBV also has the same problem. While PHBHHx is often insufficient in strength due to insufficient crystallinity, and has limited application in injection molding, fiber, 3D printing, sheet, straw, and other scenes.
In this regard, a method of introducing 4HA (4-hydroxy fatty acid) or 2HA (2-hydroxy fatty acid) monomer is adopted, so that the thermal stability of the material is improved, the molecular chain of the material is not broken prematurely, such as P34HB, P (HA-LA) and the like, but the proportion of 4HB and LA needs to be higher to improve the thermal stability obviously, and at the moment, the copolymer tends to be semi-crystalline or amorphous, and the strength is reduced obviously.
Therefore, there is a need to develop a material with high strength, high crystallinity and low melting point, which is degradable in ocean, so as to meet the requirements of environmental protection, low carbon and practical application.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a polyhydroxyalkanoate composition, a preparation method and application thereof, wherein the polyhydroxyalkanoate composition can meet the requirements of marine degradation, high strength, high crystallinity and low melting point, and an environment-friendly low-carbon product with good performance is obtained.
In a first aspect, the present invention provides a polyhydroxyalkanoate composition comprising a PHA terpolymer of P3HB4HB3HV and/or P3HB4HB5HV, wherein the molar content of the repeating unit 3HB in the PHA terpolymer is 94% or more, and the PHA terpolymer has a weight average molecular weight of 30 ten thousand or more.
The polyhydroxyalkanoate composition of the invention selects PHA terpolymer with specific type and copolymerization unit proportion, namely P3HB4HB3HV and/or P3HB4HB5HV, wherein the molar content of the repeated unit 3HB is more than 94%, and the weight average molecular weight is more than 30 ten thousand. Experiments prove that the PHA terpolymer with the composition has high crystallinity and high load deformation temperature because of the high 3HB ratio and the material property tending to the crystalline polymer; the composition has toughness due to 3 comonomers; the molecular weight is moderate and is upward, so that higher strength is maintained, and compared with P34HB, the third monomer 3HV or 5HV is introduced, the molar content is limited to be less than 6%, and the melting point of the polymer is unexpectedly found to be reduced, so that the occurrence of thermal degradation phenomena such as molecular chain breakage and the like caused by excessively high processing temperature during hot processing is avoided, and the high performance retention rate of the material before and after processing is ensured.
The PHA terpolymer provided by the invention is biodegradable in the ocean, high in crystallinity, high in strength, high in load deformation temperature and low in melting point, and the basic performance of the PHA terpolymer can meet the requirements of molded products such as molded products, extruded products, wiredrawing products, fiber products, 3D printing products and sheet/plate products, so that the PHA terpolymer can meet the application requirements of products without adding additives. Therefore, the invention can simplify the formula, reduce the cost and is beneficial to environmental protection on the premise of ensuring the quality and the stability of the product.
The PHA terpolymer of the present invention may be composed of P3HB4HB3HV and P3HB4HB5HV in any ratio; the compound may be P3HB4HB3HV alone or P3HB4HB5HV alone. In the case of pure P3HB4HB3HV, it may be a single substance, i.e., the molar contents of the three repeating units 3HB, 4HB, 3HV in P3HB4HB3HV are fixed uniquely; the composition may be a terpolymer of two or more species having different molar contents of the repeating units 3HB, 4HB and 3HV, for example, a composition comprising P3HB4HB3HV having 94% by mole of 3HB, 3% by mole of 4HB, 3% by mole of 3HV, and P3HB4HB3HV having 96% by mole of 3HB, 2% by mole of 4HB, and 2% by mole of 3HV. Similarly, the P3HB4HB5HV can be a single substance or composition.
In some embodiments of the invention, the PHA terpolymer has a crystallinity of 30% to 70% and a melting point below 155 ℃.
The melting point is lower than 155 ℃, so that the occurrence of thermal degradation phenomena such as molecular chain fracture and the like caused by setting the processing temperature higher than 160 ℃ due to high melting point in the hot processing is avoided. In order to meet the melting point requirement, the PHA terpolymer needs to have a weight average molecular weight of 30 to 300 tens of thousands.
In some embodiments of the present invention, the polyhydroxyalkanoate composition may contain other PHA homopolymers or copolymers in addition to the PHA terpolymer, but in order to achieve good results, it is required that the PHA terpolymer is present in the polyhydroxyalkanoate composition at a mass ratio of 60% or more.
For example, the polyhydroxyalkanoate composition consists of P3HB4HB5HV and PHB, wherein the mass fraction of P3HB4HB5HV is above 70%. For another example, the polyhydroxyalkanoate composition is composed of P3HB4HB3HV and PHB, P34HB, wherein the mass fraction of P3HB4HB3HV is 60% or more.
In some embodiments of the invention, the polyhydroxyalkanoate composition has a strain on load temperature of 85 ℃ or higher according to GB/T1634.2 test standard.
In some embodiments of the invention, the polyhydroxyalkanoate composition has a tensile strength greater than 18MPa and an elongation at break greater than 5% according to GB/T1040.2 test standard.
It will be appreciated that to further enhance material properties, the polyhydroxyalkanoate composition may further comprise an adjuvant selected from one or more of a nucleating agent, a chain extender, an antioxidant, a plasticizer, and a filler.
As described above, the PHA terpolymer of the present invention has excellent properties, so that even if an auxiliary is added, the amount of the auxiliary required is small.
In some embodiments of the present invention, the nucleating agent is added in an amount of 0.01 to 2%, the chain extender is added in an amount of 0.1 to 2%, the antioxidant is added in an amount of 0.1 to 2%, the plasticizer is added in an amount of 0.1 to 2%, and the filler is added in an amount of 0.1 to 30% based on the mass of the polyhydroxyalkanoate composition.
In some embodiments of the invention, the nucleating agent is selected from one or more of hexagonal crystal structure compounds (e.g., boron nitride, silicon nitride, titanium nitride, boron carbide, silicon carbide, titanium carbide, magnesium oxide, aluminum oxide), pyrimidines (e.g., uracil, thymine, cytosine), purines (e.g., adenine, guanine), dicarboxylic acid salicylhydrazides, melamine, sugar alcohol compounds (e.g., pentaerythritol, isosorbide, sorbitol, mannitol, maltitol, erythritol), fatty acid amides (e.g., EBS, erucamide, oleamide, linoleate, palmitamide), mountain and western institute TMC300 and TMC 306.
In some embodiments of the invention, the chain extender is selected from one or more of isocyanates (e.g., toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI), lysine Diisocyanate (LDI), 1, 5-Naphthalene Diisocyanate (NDI)), basf Joncryl ADR-4400/ADR-4468, the institute of chemical industry, shanxi KL-E series, japanese catalyst eporos RPS1005, 1, 3-bis (2-oxazolinyl) benzene (MPBO), 2' - (1, 3-phenylene) -bisoxazoline, trimethylolpropane chain extender.
In some embodiments of the invention, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant BHT, antioxidant 1098, antioxidant 245, antioxidant 168, antioxidant DSTP, antioxidant 412S, antioxidant DLTP, antioxidant PEPQ, carbodiimide, polymeric carbodiimide, hyMax1010, TNK-01, KSJ-936, duPont 132F NC010, germany Laseg STABILIZER 7000, rhynchon Stabaxol P, dufulin chemical Doverphos S-9228, stearate.
In some embodiments of the invention, the plasticizer is selected from one or more of isosorbide dioctate, acetylated ricinoleic acid dimethyl glycerol, epoxytetrahydrophthalate, castor oil, polyethylene glycol series, polypropylene glycol series, acetyl tributyl citrate, epoxysoybean oil, glycerol, glyceryl triacetate, fatty acids (e.g., dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosylic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid), fatty alcohols (e.g., dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, triacontanol).
In some embodiments of the invention, the filler is selected from one or more of clay, calcium carbonate, talc, kaolin, montmorillonite, bentonite, silica, chitin, titanium pigment, cellulose, pregelatinized starch.
In a second aspect, the present invention provides a process for preparing the polyhydroxyalkanoate composition described above.
The preparation method provided by the invention comprises the step of mixing the PHA terpolymer with the rest components. It will be appreciated that when the polyhydroxyalkanoate comprises only one PHA terpolymer, no other components such as adjuvants are included, no mixing is required.
In some embodiments of the invention, the PHA terpolymer is obtained from recombinant bacterial fermentation culture.
In particular, the preparation of the terpolymer P3HB4HB3HV can be referred to the applicant's prior application CN114134096A, and the preparation of the terpolymer P3HB4HB5HV can be referred to the applicant's prior application CN113684169A.
Applicants have studied in CN114134096a how to construct halophiles that synthesize P3HB4HB3HV and how to increase the 4HB ratio and/or the 3HV ratio, e.g., introducing dhaT and aldD genes into halophiles to increase the 4HB ratio; knocking out gabD and sad genes in halophiles to improve the 4HB ratio; knocking out sdhA gene in halophiles to improve 3HV proportion; the 4HB and 3HV ratios were adjusted during the batch fed-batch fermentation by adjusting the feed strategy. In summary, the applicant has, at the beginning, sought to investigate how to increase the 4HB proportion and/or the 3HV proportion in P3HB4HB3HV, did not prepare P3HB4HB3HV with 3HB content above 94% and characterized its performance. At that time, the prior art also does not suggest the applicant to prepare P3HB4HB3HV having a 3HB content of 94% or more. The applicant has unexpectedly found in the research and development that P3HB4HB3HV with the 3HB content of more than 94 percent and the weight average molecular weight of between 30 ten thousand and 300 ten thousand has good performance, and meets the requirements of marine degradation, high strength, high crystallinity and low melting point.
Similarly, the applicant studied how to construct halophiles that synthesize P3HB4HB5HV and how to obtain P3HB4HB5HV with different 4HB ratios and/or 5HV ratios in CN113684169a, but did not prepare P3HB4HB5HV with 3HB content above 94% and characterized its performance. The applicant has unexpectedly found in the research and development that P3HB4HB5HV with the 3HB content of more than 94 percent and the weight average molecular weight of between 30 ten thousand and 300 ten thousand has good performance, and meets the requirements of marine degradation, high strength, high crystallinity and low melting point.
In a third aspect, the present invention provides a PHA powder comprising the polyhydroxyalkanoate composition described above.
In some embodiments of the invention, the PHA powder composition is the polyhydroxyalkanoate composition described above.
PHA terpolymer prepared by microbial fermentation is in powder form, and PHA powder can be obtained by mixing the PHA terpolymer with optional auxiliary agents.
In a fourth aspect, the present invention provides a PHA pellet comprising the polyhydroxyalkanoate composition described above.
In some embodiments of the invention, the PHA pellets comprise the polyhydroxyalkanoate composition described above.
The PHA pellets can be obtained by granulation from PHA powder as a feedstock by methods conventional in the art, including but not limited to extrusion granulation.
In a fifth aspect, the present invention provides a PHA molded body comprising the polyhydroxyalkanoate composition described above.
In some embodiments of the invention, the PHA shaped body comprises the polyhydroxyalkanoate composition described above.
The step of preparing PHA shaped bodies in the art is generally to first prepare PHA granules from PHA powder and then prepare the PHA granules into the corresponding shaped bodies by a hot forming process or a non-hot forming process. Of course, the present invention also does not exclude the case of directly producing PHA molded bodies from PHA powder, for example, directly producing sheets from PHA powder.
In some embodiments of the invention, the PHA shaped body is a molded article, an extruded article, a drawn article, a fiber article, a 3D printed article, a foamed article, a sheet article, or a board article. It will be appreciated that the molded article is injection molded, suction molded or blow molded, the extruded article is extrusion molded, the 3D printed article is 3D printed molded, and the remainder are the same. The resulting PHA shaped bodies can include a variety of forms such as pellets, suction, blow molding, injection molding, hard bars, filaments, staple fibers, 3D printed wire, 3D printed, drawn, foamed, sheet, plate, and the like.
In some embodiments of the present invention, the method for preparing the polyhydroxyalkanoate pellets is specifically as follows:
weighing the components of the polyhydroxyalkanoate composition according to a set mass ratio, blending for 0.5-5min at room temperature by using a high-speed mixer at a speed of 50-500r/min, putting the mixture into a feed inlet of a screw extruder, setting the processing temperature within a range of 100-160 ℃, adjusting the feeding amount or the productivity according to the actual production state, and granulating by using a granulator.
The PHA molded body is prepared by putting the polyhydroxyalkanoate granules into a feed port of corresponding processing equipment, setting the processing temperature within the range of 110-175 ℃, and adjusting the feeding amount or the productivity according to the actual production state to prepare corresponding products.
The invention provides a polyhydroxyalkanoate composition, a preparation method and application thereof, and the polyhydroxyalkanoate composition contains more than 94% of 3HB mole content and more than 30 ten thousand of P3HB4HB3HV and/or P3HB4HB5HV with weight average molecular weight, so that the obtained polyhydroxyalkanoate composition can meet the requirements of marine degradation, high strength, high crystallinity and low melting point, and an environment-friendly low-carbon product with good performance is obtained.
Detailed Description
The terms "comprising" or "includes" are used in this specification to be open-ended, having the specified components or steps described, and other specified components or steps not materially affected.
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.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "detailed description," or "some embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the embodiments. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
The chinese language corresponding to english abbreviations appearing herein is referred to as follows:
PHA: polyhydroxyalkanoate
PHB: poly-3-hydroxybutyrate
PHBV: poly (3-hydroxybutyrate-co-3-hydroxyvalerate)
P3HB4HB or P34HB: poly (3-hydroxybutyrate-co-4-hydroxybutyrate)
PHBHHx: poly (3-hydroxybutyrate-co-3-hydroxycaproic acid ester)
P3HB4HB3HV: poly (3-hydroxybutyrate-co-4-hydroxybutyrate-co-3-hydroxyvalerate)
P3HB4HB5HV: poly (3-hydroxybutyrate-co-4-hydroxybutyrate-co-5-hydroxyvalerate).
In the following examples, the loading deformation temperature of polyhydroxyalkanoate pellets was tested according to the GB/T1634.2 standard; the polyhydroxyalkanoate pellets were tested for tensile strength and elongation at break according to GB/T1040.2 standard.
Example 1
99 parts by mass of P3HB4HB3HV (weight average molecular weight 96 ten thousand, 3HB mole content 97%,4HB mole content 1.5%,3HV mole content 1.5%, crystallinity 52.6%, melting point 149 ℃) and 1 part of pentaerythritol were blended with a high-speed mixer at room temperature using a speed of 300r/min for 1min, the above mixture was put into a feed port of a screw extruder, the processing temperature was set within the range of 120-150 ℃, the main machine rotation speed was 120-180r/min, and the feed amount or productivity was adjusted according to the actual production state; and (5) preparing granules by adopting a bracing cutting mode, namely polyhydroxy fatty acid ester granules.
The polyhydroxyalkanoate granules are put into a feed port of an injection molding machine, and injection molding parameters are set to be 148 ℃ in a first area, 144 ℃ in a second area and 140 ℃ in a third area (die port). The mold closing time is 2s, the mold opening time is 1s, the pressure maintaining time is 5s, the injection time delay is 2s, the cooling time is 10s, the cycle period is 10s, and the screw withdrawing time delay is 0s, so that an injection molding product is obtained.
Examples 2 to 12
Pellets of polyhydroxyalkanoate of examples 2-12 were prepared in the same manner as in example 1, wherein polyhydroxyalkanoate compositions were formulated as shown in tables 1 and 2, and the properties of the resulting pellets were as shown in tables 1 and 2, while various conventional molding methods were employed to prepare different articles (molded articles), as shown in tables 1 and 2.
TABLE 1
TABLE 2
Note that: the amounts of adjuvants in the above tables are based on the total mass of the composition.
Comparative examples 1 to 4
Pellets of polyhydroxyalkanoate of comparative examples 1 to 4 were prepared in the same manner as in example 1, wherein polyhydroxyalkanoate compositions were formulated as shown in Table 3, and the properties of the obtained pellets were shown in Table 3, while various conventional molding methods were employed to prepare various articles (molded articles) as shown in Table 3. In comparison with example 11, wherein the molar content of 3HB of comparative example 1 is low, the contents of 4HB and 5HV are high; the molecular weight of comparative example 2 is lower; 5HV of comparative example 3 was replaced with 3HHx; both 4HB and 5HV of comparative example 4 were replaced with 3HV.
TABLE 3 Table 3
From the above results, it can be seen that P3HB4HB3HV and P3HB4HB5HV having a 3HB molar content of 94% or more and a weight average molecular weight of 30 ten thousand or more have good properties, and thus polyhydroxyalkanoate compositions containing them can satisfy the demands of marine degradability, high strength, high crystallinity and low melting point, resulting in environmentally friendly low carbon and good properties.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The polyhydroxyalkanoate composition is characterized by comprising a PHA terpolymer, wherein the PHA terpolymer is P3HB4HB3HV and/or P3HB4HB5HV, the molar content of a repeating unit 3HB in the PHA terpolymer is more than 94%, and the PHA terpolymer has a weight average molecular weight of more than 30 ten thousand.
2. The polyhydroxyalkanoate composition of claim 1, wherein the PHA terpolymer has a crystallinity of 30% to 70% and a melting point of 155 ℃ or less.
3. The polyhydroxyalkanoate composition according to claim 1 or 2, wherein the PHA terpolymer is present in the polyhydroxyalkanoate composition in a mass ratio of 60% or more.
4. The polyhydroxyalkanoate composition of claim 1 or 2, wherein the polyhydroxyalkanoate composition has a load deflection temperature of 85 ℃ or higher according to GB/T1634.2 test standard;
according to GB/T1040.2 test standard, the polyhydroxy fatty acid ester composition has tensile strength of more than 18MPa and elongation at break of more than 5%.
5. The polyhydroxyalkanoate composition of claim 1 or 2, further comprising an adjuvant selected from one or more of a nucleating agent, a chain extender, an antioxidant, a plasticizer, a filler;
preferably, based on the mass of the polyhydroxyalkanoate composition, the addition amount of the nucleating agent is 0.01-2%, the addition amount of the chain extender is 0.1-2%, the addition amount of the antioxidant is 0.1-2%, the addition amount of the plasticizer is 0.1-2%, and the addition amount of the filler is 0.1-30%;
further preferably, the nucleating agent is selected from one or more of hexagonal crystal structure compounds, pyrimidines, purines, dicarboxylic acid salicylhydrazides, melamine, sugar alcohol compounds, fatty acid amides, TMC300 and TMC 306 of Shanxi institute of chemical industry;
and/or the chain extender is selected from one or more of isocyanates, pasteur Joncryl ADR-4400/ADR-4468, shanxi institute of chemical industry, KL-E series, japanese catalyst EPOCROS RPS1005, 1, 3-bis (2-oxazoline) benzene, 2' - (1, 3-phenylene) -dioxazoline and trimethylolpropane chain extender;
and/or the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant BHT, antioxidant 1098, antioxidant 245, antioxidant 168, antioxidant DSTP, antioxidant 412S, antioxidant DLTP, antioxidant PEPQ, carbodiimide, polymeric carbodiimide, hyMax1010, TNK-01, KSJ-936, duPont 132F NC010, lasie STABILIZER 7000, rhine chemical Stabaxol P, dufulu chemical Doverphoss-9228, stearate;
and/or the plasticizer is selected from one or more of isosorbide dioctate, acetylated ricinoleic acid dimethyl glycerol, epoxy tetrahydrophthalate, castor oil, polyethylene glycol series, polypropylene glycol series, acetyl tributyl citrate, epoxidized soybean oil, glycerol, glyceryl triacetate, fatty acids and fatty alcohols;
and/or the filler is selected from one or more of clay, calcium carbonate, talcum powder, kaolin, montmorillonite, bentonite, silicon dioxide, chitin, titanium pigment, cellulose and pregelatinized starch.
6. The process for the preparation of polyhydroxyalkanoate composition as claimed in any one of claims 1-5, comprising the step of mixing the PHA terpolymer with the remaining components;
preferably, the PHA terpolymer is obtained by fermentation culture of recombinant bacteria.
7. PHA powder comprising the polyhydroxyalkanoate composition of any one of claims 1-5.
8. PHA granules, characterized in that it comprises the polyhydroxyalkanoate composition of any one of claims 1-5.
9. A PHA molded article comprising the polyhydroxyalkanoate composition of any one of claims 1-5.
10. The PHA shaped body of claim 9, wherein the PHA shaped body is a molded article, an extruded article, a drawn article, a fiber article, a 3D printed article, a foamed article, a sheet article or a sheet article.
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| CN202311783872.5A CN117820830A (en) | 2023-12-22 | 2023-12-22 | Polyhydroxyalkanoate composition and preparation method and application thereof |
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