Fat aromatic copolyester foaming composition, fat aromatic copolyester foaming bead, preparation method of fat aromatic copolyester foaming bead and foaming bead forming body

Abstract

The invention belongs to the field of macromolecules, and relates to a fat aromatic copolyester foaming composition, fat aromatic copolyester foaming beads, a preparation method of the fat aromatic copolyester foaming beads and a foaming bead forming body. The composition comprises fat aromatic copolyester, a shrinkage inhibitor, a stiffening agent, a compatilizer and an auxiliary agent, based on 100 parts by weight of the fat aromatic copolyester, the content of the shrinkage inhibitor is 0.2-2 parts by weight, the content of the stiffening agent is 0.2-5 parts by weight, the content of the compatilizer is 0.1-2 parts by weight, and the content of the assistant is 0.01-2 parts by weight; the shrinkage inhibitor is selected from at least one of polysorbate, sucrose ester, sorbitan fatty acid ester, palmitic acid diglyceride and isosorbide dinitrate. The shrinkage inhibitor, the stiffening agent and the compatilizer are used and play a synergistic effect, so that the shrinkage rate of the fat aromatic copolyester-based foamed bead is obviously reduced, and the application fields of a molded body in electronic and electric appliance packaging, precision mechanical product packaging and the like are expanded.

Description

Technical Field

[0001] This invention belongs to the field of polymer science, specifically relating to a fatty aromatic copolyester foaming composition, fatty aromatic copolyester foaming beads, a method for preparing the same, and a molded foaming bead body. Background Technology

[0002] Fully biodegradable foam materials are a new type of environmentally friendly material that can be completely decomposed by microorganisms, resulting in a positive impact on the environment. This type of foam material can undergo hydrolysis under the biochemical action of microorganisms, enzyme catalysis, or acid-base catalysis, as well as free radical chain degradation caused by various other factors, ultimately decomposing into carbon dioxide (CO2) and water. The varieties and properties of fully biodegradable foam materials are also quite diverse. There are multiple methods for preparing fully biodegradable foam materials. The application prospects of fully biodegradable foam materials are broad, especially in food packaging, cushioning packaging materials, and disposable tableware. They can serve as environmentally friendly alternatives to traditional petroleum-based plastics, reducing environmental pollution and promoting sustainable development. With technological advancements and increased environmental awareness, the market demand for fully biodegradable foam materials is expected to continue to grow.

[0003] CN202110635457.X discloses a method for preparing a fully biodegradable foamed material. The method involves mixing polyglycolic acid, polybutylene adipate, maleic anhydride graft polymer, melt reinforcing agent and antioxidant, and then extruding and foaming with supercritical gas or intermittent supercritical gas to obtain a fully biodegradable foamed material with low shrinkage, high compression recovery and good resilience. However, the system has high rigidity, elongation at break is less than 100% and shrinkage is ≥7%.

[0004] CN202211393544.X discloses a biodegradable composite foam material and its preparation method. The foam material is obtained by foaming a foaming composition; the foaming composition includes polybutylene adipate / terephthalate and polyhydroxybutyrate-valerate copolyester, exhibiting high initial expansion ratio, low shrinkage, and good dimensional stability. However, the preparation cost of the polyhydroxybutyrate-valerate copolyester is relatively high, which is not conducive to industrial production.

[0005] CN202211393544.X discloses a PBAT microporous foam material and its preparation method. The PBAT composition comprises PBAT and a polyvinyl alcohol composition. When PBAT is foamed, the foaming efficiency is significantly improved, by more than 50%, and the foaming time is reduced by improving the foaming efficiency. However, when polyvinyl alcohol is used as the second component, since polyvinyl alcohol can only dissolve in water as oligomers, it cannot achieve full biodegradability.

[0006] CN202410314791.9 discloses a PBAT-based biodegradable foam material for footwear and its preparation method. It uses amide compounds such as N,N-bis(2-hydroxyethyl)oxalamide as nucleating agents, comprehensively improving the solution strength and crystallinity of the PBAT-based polymer. This promotes a high foaming ratio in the PBAT-based biodegradable foam material while further increasing its strength and elasticity. The resulting shoe midsole exhibits excellent biodegradability, lightweight, high elasticity, and high tear resistance. However, oxalamide has endocrine disrupting activity, interfering with hormone homeostasis in organisms, affecting gonadal development, and leading to reproductive toxicity. Multiple studies have confirmed that metolachlor can induce mutations in organisms and has potential carcinogenicity in mammals.

[0007] Aliphatic aromatic copolyesters, such as poly(butylene succinate-butylene terephthalate) (PBST), are biodegradable polymers that can be biodegraded by microorganisms in the natural environment. However, fully biodegradable copolyesters, including PBST, are linear semi-crystalline polymers with disadvantages such as low molecular weight, low matrix modulus, low crystallinity, and slow crystallization rate. When used for physical foaming, they suffer from insufficient melt strength, narrow foaming windows, difficulty in forming high-ratio foamed products, and severe shrinkage, resulting in slow elastic recovery and insufficient strength and toughness in the foamed material. Existing technologies improve the melt strength of fully biodegradable plastics such as PBST to prevent pore wall stretching during the foaming process, such as by modifying the material before foaming to increase rigidity. Modification methods include melt blending, chain extenders, and the addition of nucleating agents. However, due to the low molecular weight of fully biodegradable copolyesters such as PBST, the resulting foamed materials still suffer from high shrinkage and unstable mechanical properties. Summary of the Invention

[0008] The purpose of this invention is to overcome the above-mentioned problems existing in the prior art and to provide a fatty aromatic copolyester foaming composition, fatty aromatic copolyester foaming beads, and their preparation method and application. The foaming beads made from the fatty aromatic copolyester foaming composition provided by this invention have the advantages of being biodegradable, having dense pores, uniform pore size distribution, high mechanical properties and low shrinkage. They can be applied to packaging, household and sporting goods and other occasions where there are high requirements for lightweight plastic products, energy absorption and biodegradability.

[0009] To achieve the above objectives, the first aspect of the present invention provides a fatty aromatic copolyester foaming composition, the composition comprising a fatty aromatic copolyester, a shrinkage inhibitor, a stiffening agent, a compatibilizer, and an additive.

[0010] Based on 100 parts by weight of aliphatic aromatic copolyester, the shrinkage inhibitor content is 0.2-2 parts by weight, preferably 0.3-1 parts by weight; the stiffening agent content is 0.2-5 parts by weight, preferably 0.5-2 parts by weight; the compatibilizer content is 0.1-2 parts by weight, preferably 0.2-1 parts by weight; and the auxiliary agent content is 0.01-2 parts by weight, preferably 0.15-0.7 parts by weight.

[0011] The contraction inhibitor is selected from at least one of polysorbate, sucrose ester, sorbitan fatty acid ester, diglyceride palmitate, and isosorbide dinitrate;

[0012] The additives include chain extenders, antioxidants, and cell nucleating agents.

[0013] A second aspect of the present invention provides a fatty aromatic copolyester foamed beads, wherein the fatty aromatic copolyester foamed beads are obtained by foaming the fatty aromatic copolyester foaming composition.

[0014] A third aspect of the present invention provides a method for preparing fatty aromatic copolyester foamed beads, the method comprising: melting and pelletizing the fatty aromatic copolyester foaming composition to obtain fatty aromatic copolyester microparticles, and then foaming the microparticles.

[0015] A fourth aspect of the present invention provides a fatty aromatic copolyester foamed beads prepared by the aforementioned preparation method.

[0016] A fifth aspect of the present invention provides a fatty aromatic copolyester foamed bead molded body, wherein the fatty aromatic copolyester foamed bead molded body is made from the fatty aromatic copolyester foamed beads.

[0017] Through the above technical solutions, the fatty aromatic copolyester foaming composition, fatty aromatic copolyester foaming beads, their preparation method, and applications provided by the present invention achieve the following beneficial effects:

[0018] (1) The present invention uses shrinkage inhibitors, stiffening agents and compatibilizers. The three work together to significantly reduce the shrinkage rate of fatty aromatic copolyester foam beads and expand the application fields of molded bodies in electronic and electrical packaging, precision machinery product packaging and other fields.

[0019] (2) The fatty aromatic copolyester foamed beads obtained by the present invention can be degraded by household and industrial composting. After composting test using GB / T19277.1, the relative biodegradability rate is ≥90%.

[0020] (3) The foamed beads made from the foaming composition have the advantages of biocontrollable degradation, dense pores and uniform pore size distribution. They can be applied to electronic, food packaging and home sports products and other occasions with high requirements for lightweight plastic products, energy absorption and biodegradability. They can be degraded in landfill without causing secondary pollution and meet the requirements of circular economy.

[0021] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0022] Exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

[0023] Figure 1 This is a cross-sectional scanning electron microscope image of the foamed beads from Example 1 of the present invention, wherein the black arrow points to the cell nucleating agent V2CT. X . Detailed Implementation

[0024] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0025] To achieve the above objectives, the first aspect of the present invention provides a fatty aromatic copolyester foaming composition, the composition comprising a fatty aromatic copolyester, a shrinkage inhibitor, a stiffening agent, a compatibilizer, and an additive.

[0026] Based on 100 parts by weight of aliphatic aromatic copolyester, the shrinkage inhibitor content is 0.2-2 parts by weight, preferably 0.3-1 parts by weight; the stiffening agent content is 0.2-5 parts by weight, preferably 0.5-2 parts by weight; the compatibilizer content is 0.1-2 parts by weight, preferably 0.2-1 parts by weight; and the auxiliary agent content is 0.01-2 parts by weight, preferably 0.15-0.7 parts by weight.

[0027] The contraction inhibitor is selected from at least one of polysorbate, sucrose ester, sorbitan fatty acid ester, diglyceride palmitate, and isosorbide dinitrate;

[0028] The additives include chain extenders, antioxidants, and cell nucleating agents.

[0029] In this invention, the use of a high content of shrinkage inhibitors can effectively reduce the shrinkage rate of fatty aromatic copolyester foam materials to below 1%, thus expanding the application scenarios of fatty aromatic copolyester foam materials.

[0030] According to the present invention, preferably, based on 100 parts by weight of aliphatic aromatic copolyester, the content of the chain extender is 0.03 to 1 part by weight, preferably 0.05 to 0.3 parts by weight, the content of the antioxidant is 0.02 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight, and the content of the cell nucleating agent is 0.02 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight.

[0031] According to the present invention, preferably, the contraction inhibitor is sorbitan fatty acid ester and / or palmitic acid diglyceride.

[0032] According to the present invention, preferably, the stiffening agent is selected from at least one of polylactic acid, polyglycolic acid, PLGA and polyhydroxy fatty acids.

[0033] According to the present invention, preferably, the compatibilizer is selected from at least one of polytrimethylene carbonate, polyhydroxytrimethylene carbonate, polyvalerone, polyoctyl lactone, polydecyl lactone and polynonyl lactone, and more preferably polyhydroxytrimethylene carbonate and / or polydecyl lactone.

[0034] According to the present invention, preferably, the chain extender is a carbonate-type chain extender, preferably selected from at least one of tert-butyl peroxide-2-ethylhexyl carbonate, di(hexadecyl) peroxide, ditetradecyl peroxide, tert-butyl peroxide isopropyl carbonate, diisobutyl peroxide, bis(4-tert-butylcyclohexyl) peroxide, and tert-butyl peroxide isopropyl carbonate, more preferably di(hexadecyl) peroxide and / or ditetradecyl peroxide.

[0035] In this invention, a carbonate-based chain extender with controllable molecular weight is used, which is characterized by high efficiency, safety and environmental friendliness, and can effectively control the molecular weight of the foaming composition.

[0036] According to the present invention, preferably, the antioxidant is selected from 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]decane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 3,5-bis-(1,1-dimethylethyl)-4-hydroxy At least one of branched or straight-chain alkyl esters of phenylpropionate and oxaloyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate (diimino-2,1-ethylidene ester), preferably 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]decane and / or oxaloyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate (diimino-2,1-ethylidene ester).

[0037] According to the present invention, preferably, the cell nucleating agent is MXene material with the general formula M n+1 X n T x M is a transition metal atom, preferably zirconium, chromium, hafnium, molybdenum, titanium, niobium, tantalum, vanadium, scandium, or tungsten, more preferably titanium, vanadium, molybdenum, or niobium; X represents carbon and / or nitrogen; T x It is selected from at least one of -OH, -COOH, -Br, =O, -F and -Cl, preferably -COOH and / or -F; n is 1, 2, 3 or 4.

[0038] More preferably, the cell nucleating agent is V2CT. x and / or Ti3CNT x .

[0039] According to the present invention, preferably, the melt index of the fatty aromatic copolyester at 190°C and a load of 2.16 kg is 0.1–80 g / 10 min, more preferably 1–5 g / 10 min, and the weight-average molecular weight is 8–12 × 10⁻⁶. 4 Preferably 4~12×10 4 Preferably, it is 4.5 to 10×10 4 The molecular weight distribution is 1-3.5, preferably 2.2-3, and the terminal carboxyl group content is 8-12 mol / t, preferably 8.5-11 mol / t.

[0040] In this invention, the aliphatic aromatic copolyester can be obtained by copolymerization of monomers a, b, c and optionally d under conventional copolymerization reaction conditions in the prior art.

[0041] According to the present invention, preferably, the fatty aromatic copolyester is obtained by monomer a, monomer b, monomer c and optionally monomer d under the action of a catalyst through a process of diesterization, atmospheric pressure esterification, pre-condensation, final condensation and liquid phase thickening; preferably, the catalyst includes a first catalyst, a second catalyst and a third catalyst.

[0042] According to a specific embodiment of the present invention, the fatty aromatic copolyester of the present invention is prepared according to the method of CN116804078A, the preparation method comprising the following steps:

[0043] 1) In the presence of a first catalyst and / or a second catalyst, monomer a and monomer b are subjected to an esterification reaction in a first esterification reactor, which is a vertical esterification reactor with stirring. When the esterification rate in the first esterification reactor reaches 90-95%, the next reaction step is introduced.

[0044] (2) The product of the first esterification vessel, the first catalyst and / or the second catalyst, monomer c and optional monomer b and / or optional d are introduced into the second esterification vessel for esterification reaction. The second esterification vessel is a vertical esterification reactor with stirring. When the esterification rate in the second esterification vessel reaches 90-95%, the next reaction step is introduced.

[0045] (3) In the presence of a third catalyst, the product of the second esterification vessel is introduced into the third esterification vessel for esterification reaction. The third esterification vessel is a vertical esterification reactor with stirring. When the esterification rate in the third esterification vessel reaches more than 98%, the next reaction step is introduced.

[0046] (4) The product of the third esterification reactor is introduced into the prepolymerization reactor for prepolymerization. The prepolymerization reactor is a vertical stirred tank. When the degree of polymerization reaches 20-30, the product is introduced into the next reaction step.

[0047] (5) The product of the prepolymerization reactor is introduced into the final polymerization reactor for final polymerization. The final polymerization reactor is a horizontal cage-type film-forming final polymerization reactor. When the degree of polymerization reaches 100-150, the product is introduced into the next reaction step.

[0048] (6) The product from the final polycondensation reactor is introduced into a thickening reactor for melt thickening, so that the melt index of the reaction product reaches 0.1-20 g / 10 min. The thickening reactor is a biaxial horizontal liquid phase thickening reactor.

[0049] According to the present invention, monomer a is selected from terephthalic acid and / or dimethyl terephthalate; monomer b is selected from 1,3-propanediol and / or 1,4-butanediol; monomer c is selected from at least one of succinic acid, dimethyl succinate, adipic acid and dimethyl adipic acid; and monomer d is selected from at least one of pyromellitic dianhydride, glycerol and pentaerythritol.

[0050] According to the present invention, the molar ratio of monomer a, monomer b, monomer c and monomer d satisfies the following conditions: (a+c):b is 1:0.8-3; (a+c):d is 100-2000:1; a:c is 60:40-0.1:100.

[0051] According to the present invention, the first catalyst is selected from oxides of M, M(OR1) n and M(-OOCR2) n At least one compound, wherein M is titanium, antimony, or zinc, n is the valence state of M, and R1 is C1-C 10 Alkyl group, R2 is C1-C 30 Alkyl groups.

[0052] The second catalyst is an organotin compound.

[0053] The third catalyst is at least one of a compound with the chemical formula RE(R3)3, wherein RE is a rare earth metal element, and R3 is selected from halogens, alkoxy groups, aryloxy groups, acetylacetonyl groups, and R4COO. - At least one of the groups, R4 is C1-C 30 Alkyl groups.

[0054] According to the present invention, the total amount of catalyst added is in a molar ratio of 1:1000-20000 to monomer (a+c), preferably 1:4000-12000.

[0055] According to the present invention, the molar ratio of the first catalyst: the second catalyst: the third catalyst is 0.1-20:0.1-10:1, preferably 0.1-1.5:0.1-0.5:1.

[0056] Furthermore, the fatty aromatic copolyester foaming composition may also contain any other existing additives commonly used in fatty aromatic copolyester resins and fatty aromatic copolyester foaming materials, and these other additives will not adversely affect the foaming properties, cell structure of the beads, or mechanical properties of the molded article provided by the present invention. These other additives include, but are not limited to, at least one of: slip agents, antistatic agents, and anti-sticking agents. Moreover, the amounts of these other additives can be conventionally selected in the art, as will be known to those skilled in the art, and will not be elaborated upon here.

[0057] A second aspect of the present invention provides a fatty aromatic copolyester foamed beads, wherein the fatty aromatic copolyester foamed beads are obtained by foaming the fatty aromatic copolyester foaming composition.

[0058] According to the present invention, preferably, the density of the foamed beads is 0.03-0.3 g / cm³. 3The preferred value is 0.05-0.25 g / cm³. 3 The foamed beads have a pore diameter of 10-200 μm, preferably 20-150 μm; a closed-cell rate of 80-98%, preferably 85-95%; and a pore density of 1×10⁻⁶. 9 -1×10 5 cm -3 Preferably 1.1×10 9 -0.98×10 6 cm -3 .

[0059] A third aspect of the present invention provides a method for preparing fatty aromatic copolyester foamed beads, the method comprising: melting and pelletizing the fatty aromatic copolyester foaming composition to obtain fatty aromatic copolyester microparticles, and then foaming the microparticles.

[0060] According to the present invention, the foaming is an in-pot immersion foaming method.

[0061] According to the present invention, the pelleting is underwater pelleting or strand pelleting, preferably underwater pelleting.

[0062] In this invention, the fatty aromatic copolyester microparticles can be produced using any method available in the prior art. For example, the fatty aromatic copolyester foam composition can be extruded into wires via one or more dies of a twin-screw or single-screw extruder and then cut to obtain the fatty aromatic copolyester microparticles. Preferably, the fatty aromatic copolyester microparticles are obtained using an underwater microparticle pelletizing system.

[0063] A specific embodiment of the preparation of fatty aromatic copolyester microparticles in this invention includes the following steps: A base resin, chain extender, stiffening agent, compatibilizer, shrinkage inhibitor, antioxidant, and cell nucleating agent are blended using a high-speed mixer, then extruded through a twin-screw extruder. After hot cutting, the mixture is introduced into water at 50°C or below, preferably 40°C or below, and more preferably 30-35°C for microparticle cutting, so that the length / diameter ratio of each particle is 0.5-2, preferably 0.9-1.1, and the average weight of the microparticles is 0.1-20 mg, preferably 0.2-10 mg, and more preferably 2-4 mg.

[0064] In this invention, the average weight of the microparticles refers to the average weight of 200 arbitrarily selected microparticles.

[0065] According to the present invention, the in-vessel impregnation foaming method includes the following steps:

[0066] (1) In a reaction vessel, fatty aromatic copolyester microparticles are mixed with a dispersion medium, surfactant, dispersant and dispersion enhancer to obtain a mixture;

[0067] (2) Feed the foaming agent into the reactor, remove the air from the reactor, and heat the mixture to a temperature 0.1-5℃ lower than the expansion temperature, preferably 0.5-1℃ lower, under stirring conditions;

[0068] (3) Continue stirring and foaming at foaming temperature and foaming pressure to obtain fatty aromatic copolyester foam beads.

[0069] (4) While discharging the fatty aromatic copolyester foam beads from the reactor, carbon dioxide gas is fed into the reactor and the pressure inside the reactor is maintained at the foaming pressure.

[0070] In this invention, the fatty aromatic copolyester foamed beads prepared by this method have the advantages of biocontrollable degradation, dense pores and uniform pore size distribution. They can be applied to food packaging and home and sporting goods, where there are high requirements for lightweight plastic products, energy absorption and biodegradability.

[0071] In this invention, the expansion temperature refers to the temperature at which the final pressure is released and foaming occurs in step (4).

[0072] According to the present invention, the stirring speed is 25-300 rpm, preferably 100-200 rpm.

[0073] According to the present invention, the foaming temperature is 0.1-10°C lower than the melting temperature of the fatty aromatic copolyester microparticles, preferably 5-7°C lower.

[0074] According to the present invention, the foaming pressure is 1-10 MPa, preferably 0.5-4 MPa.

[0075] According to the present invention, the impregnation time after foaming is 0-2 hours, preferably 0.05-0.5 hours, where 0 hours means that the material is unloaded and foamed directly after reaching the foaming temperature.

[0076] Unless otherwise specified, all pressures mentioned herein refer to gauge pressure.

[0077] In this invention, when using the reactor impregnation method for microparticle foaming, it is necessary to add a dispersion medium, surfactant, dispersant, dispersion enhancer and other additives and foaming agent.

[0078] According to the present invention, the volume ratio of the dispersion medium to the volume of the reaction vessel is (1-4):5, preferably (2.5-3.5):5. For example, relative to a reaction vessel volume of 5L, the amount of dispersion medium used is 1-4L, preferably 2.5-3.5L.

[0079] Any component that disperses fatty aromatic copolyester resin microparticles therein without dissolving the microparticles can be used as a dispersion medium. This dispersion medium can be water, ethylene glycol, glycerol, methanol, ethanol, or mixtures thereof. A water-based dispersion medium is preferred, water is more preferred, and deionized water is most preferred.

[0080] To promote the dispersion of microparticles in the dispersion medium, a surfactant is used, which may be stearic acid, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, quaternary ammonium compounds, lecithin, amino acids, betaine, fatty acid glycerides, fatty acid sorbitan, polysorbate, preferably anionic surfactant sodium dodecyl sulfate. The amount of the surfactant used is generally 0.001-1 parts by weight, preferably 0.01-0.5 parts by weight, and most preferably 0.1-0.3 parts by weight, relative to 100 parts by weight of the fatty aromatic copolyester microparticles.

[0081] To prevent the fatty aromatic copolyester microparticles from melting and agglomerating together during the foaming step, it is ideal to add a dispersant that is a fine organic or inorganic solid to the dispersion medium. For ease of handling, an inorganic powder is preferred. The dispersant can be a natural or synthetic clay mineral (e.g., kaolin, mica, pyrope garnet, and clay), bauxite, titanium dioxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate, montmorillonite, silica, zinc borate, and iron oxide, with montmorillonite being preferred. The amount of dispersant used is generally 0.01-5 parts by weight, preferably 0.1-3 parts by weight, and most preferably 0.5-2 parts by weight, relative to 100 parts by weight of the fatty aromatic copolyester microparticles.

[0082] To improve the dispersion efficiency of the dispersant, i.e., to retain its function of preventing microparticle melt adhesion while reducing the amount of the dispersant, a dispersion enhancer can be added to the dispersion medium. This dispersion enhancer is an inorganic compound that provides divalent or trivalent anions or cations and has a solubility of 1 mg in 100 mL of water at 40°C. Examples of such dispersion enhancers include magnesium nitride, magnesium nitrate, aluminum phosphate, magnesium sulfate, aluminum nitride, aluminum nitrate, aluminum sulfate, ferric chloride, ferric sulfate, and ferric nitrate, with magnesium sulfate being preferred. The use of this dispersion enhancer is beneficial for obtaining aliphatic aromatic copolyester foamed beads with an apparent density of 100 g / L or greater. The amount of the dispersion enhancer used is generally 0.0001-1 parts by weight, preferably 0.01-0.1 parts by weight, relative to 100 parts by weight of the aliphatic aromatic copolyester microparticles.

[0083] The blowing agent can be an organic physical blowing agent or an inorganic physical blowing agent. Organic physical blowing agents include aliphatic hydrocarbons such as propane, butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclobutane and cyclohexane; and halogenated hydrocarbons such as chlorofluoromethane, trifluoromethane, 1,2-difluoroethane, 1,2,2,2-tetrafluoroethane, methyl chloride, ethyl chloride, and dichloromethane. Examples of inorganic physical blowing agents include air, nitrogen, carbon dioxide, oxygen, and water. Water, used as a blowing agent, can be water used to disperse the aliphatic aromatic copolyester microparticles in the dispersion medium. These organic and inorganic blowing agents can be used alone or in mixtures of two or more. Due to the stability (uniformity) of the apparent density of aliphatic aromatic copolyester foam beads, reduced product shrinkage, low cost, and environmental friendliness, the blowing agent used above is a mixture of carbon dioxide, nitrogen, and argon in a volume fraction of 75:20:5.

[0084] The amount of foaming agent used can be determined according to the type of foaming agent, the foaming temperature, and the apparent density of the fatty aromatic copolyester foam beads to be produced. When nitrogen is used as the foaming agent and water is used as the dispersion medium, for example, when nitrogen is used as the foaming agent, the pressure inside the sealed container when the foaming device is depressurized, i.e., the pressure in the upper space of the sealed container (gauge pressure), is in the range of 1-12 MPa; if a mixture of carbon dioxide, nitrogen, and argon is used, the gauge pressure range is 1-7 MPa. Generally, the pressure in the upper space of the sealed container ideally increases as the apparent density of the desired fatty aromatic copolyester foam beads decreases.

[0085] According to a specific embodiment of the present invention, carbon dioxide, nitrogen and argon are used as foaming agents, which is safe and environmentally friendly. No explosion-proof treatment is required for the foaming equipment, and the time for the foaming agent to replace air is extended, which synergistically reduces the shrinkage rate. Compared with the use of organic foaming agents in the prior art, it has the advantages of being environmentally friendly and safe.

[0086] A fourth aspect of the present invention provides a fatty aromatic copolyester foamed beads prepared by the aforementioned preparation method.

[0087] A fifth aspect of the present invention provides a fatty aromatic copolyester foamed bead molded body, wherein the fatty aromatic copolyester foamed bead molded body is made from the fatty aromatic copolyester foamed beads.

[0088] According to the present invention, the molded body can be formed in various molding equipment in the prior art, and the molding conditions can be conventionally selected in the art, which will be known to those skilled in the art and will not be described in detail here.

[0089] The present invention will be further described below with reference to the embodiments, but the scope of the present invention is not limited to these embodiments.

[0090] The raw materials and instruments and equipment used in the following examples and comparative examples include:

[0091] Montmorillonite: ACROS, analytical grade;

[0092] Sodium dodecyl sulfate: Xilong Chemical, analytical grade;

[0093] Magnesium sulfate: Xilong Chemical, analytical grade;

[0094] Deionized water: Sinopec (Beijing) Chemical Research Institute Co., Ltd.;

[0095] PBST: Sinopec (Beijing) Chemical Research Institute Co., Ltd.

[0096] Chain extender A: Di(hexadecyl) peroxide, Norinone;

[0097] Chain extender B: ditetradecyl peroxide dicarbonate, Norinone;

[0098] Stiffening agent A: Polylactic acid, Mw = 9.6 × 10 4 PDI (Potential Distribution Difference) = 2.2;

[0099] Stiffening agent B: Polyglycolic acid, Mw = 8.7 × 10 4 PDI (molecular weight distribution width) = 1.8;

[0100] Compatibilizer A: Polyhydroxytrimethylene carbonate, Sinopec (Beijing) Chemical Research Institute Co., Ltd.;

[0101] Compatibilizer B: Polydecyl lactone, Sinopec (Beijing) Chemical Research Institute Co., Ltd.;

[0102] Contraction inhibitor A: Sorbitan fatty acid ester, Bailingwei;

[0103] Contraction inhibitor B: Diglyceride palmitate, Bailingwei;

[0104] Antioxidant A: 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxazolo[5.5]+ (CAS: 90498-90-1), BASF;

[0105] Antioxidant B: (3,5-di-tert-butyl-4-hydroxyphenyl)propionate oxaloyl (diimino-2,1-ethylidene ester), BASF;

[0106] Bubble nucleating agent A: V2CT X (Surface groups: -OH and -F, molar ratio 4:6), Beijing Sanhe Nanomaterials;

[0107] Cell nucleating agent B: Ti3CNT x (Surface group: -F), Beijing Sanhe Nanomaterials.

[0108] Production and testing equipment:

[0109] Underwater pelletizing system: Labline 1000, BKG GmbH, Germany;

[0110] Density tester: CPA225D, density accessory YDK01, Satorius GmbH, Germany;

[0111] Open / closed porosity tester: ULTRAFOAM 1200e, Quantachrome Instruments, USA.

[0112] The polymer-related data in the examples were obtained using the following test methods:

[0113] 1. The compressive strength of the foamed molded body shall be measured in accordance with the method of GB / T 8813-2008; ISO 844:2007, which is the determination of compressive properties of rigid foamed plastics.

[0114] 2. Melt Flow Index (MI): Determined according to the method specified in GB / T 3682-2000, wherein the test temperature is 190℃ and the load is 2.16kg.

[0115] 3. Foam Bead Density Test Method: Using the density attachment of a Satorius balance, the density of the PBST base resin and PBST foam beads was obtained by the water displacement method, measured according to the method described in GB / T6343-2009, the national standard for determination of apparent density of foamed plastics and rubber. The foaming ratio of the obtained PBST foam material was calculated using the formula: b = ρ1 / ρ2, where b is the foaming ratio, ρ1 is the density of the PBST base resin, and ρ2 is the apparent density of the foam material.

[0116] 4. Cell density: Where n is the number of bubbles in the scanning electron microscope image, M is the magnification, and A is the area of ​​the selected region in the scanning electron microscope image (unit: cm²). 2 ), It is the foaming ratio of fatty aromatic copolyester foam beads.

[0117] 5. Determination of PBST resin density: The density was determined according to the method specified in GB / T 1033.2-2010 using the density gradient column method.

[0118] 6. The molecular weight and molecular weight distribution of polymers were determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as solvent on a Waters-208 instrument (equipped with a Waters 2410RI detector, flow rate of 1.5 ml / min, 30 °C). The molecular weight was calibrated with styrene standard.

[0119] 7. Differential scanning calorimetry (DSC) was used to determine the crystallization temperature (Tc) and melting temperature (Tm) of the polymer. On a PerkinElmer Pyris 1 instrument, each sample was heated from -100°C to 250°C, and two heating scans were performed at a heating rate of 20°C / min.

[0120] Example 1

[0121] This embodiment illustrates the PBST composition, foamed beads, and foamed molded body provided by the present invention.

[0122] (I) Preparation of PBST1

[0123] (1) Prepare a PTA slurry by mixing 350 kg / h terephthalic acid and 285 kg / h 1,4-butanediol, and continuously feed it into the first esterification reactor. Add 0.1 kg / h tetraisopropyl titanate and carry out the esterification reaction at atmospheric pressure and temperature of 220°C until the esterification rate reaches 95%.

[0124] (2) The product from the first esterification reactor is introduced into the second esterification reactor. At the same time, 254 kg / h of succinic anhydride and 350 kg / h of 1,4-butanediol are mixed into a slurry and continuously fed into the second esterification reactor. 0.1 kg / h of tetraisopropyl titanate is added, and the esterification reaction is carried out at atmospheric pressure and a temperature of 220°C until the esterification rate reaches 95%.

[0125] (3) The product from the second esterification vessel is introduced into the third esterification vessel, and 0.5 g / h of lanthanum stearate is injected simultaneously. The esterification reaction is carried out at atmospheric pressure and temperature of 230°C until the esterification rate reaches 98%.

[0126] (4) The product from the third esterification reactor is introduced into the prepolymerization reactor and prepolymerized for 2 hours at an absolute pressure of 1 kPa and a temperature of 235°C. The degree of polymerization of the product reaches 25.

[0127] (5) The product from the prepolymerization reactor is introduced into the final polymerization reactor and subjected to final polymerization for 5 hours at an absolute pressure of 150 Pa and a temperature of 235 °C. The degree of polymerization of the product reaches 120.

[0128] (6) The product from the final polycondensation reactor was introduced into a thickening reactor, and a melt thickening reaction was carried out at an absolute pressure of 100 Pa and a temperature of 225 °C for 1.5 h to obtain poly(butylene terephthalate) ester (PBST1). The PBST1 had a melt index of 2.0 g / 10 min at 190 °C and a load of 2.16 kg, and a weight-average molecular weight of 9.4 × 10⁻⁶. 4 The molecular weight distribution width is 2.1, and the terminal carboxyl group content is 8.5 mol / t.

[0129] (II) Preparation of PBST 401 Composition

[0130] Based on 100 parts by weight of PBST1, 0.05 parts by weight of di(hexadecyl)dicarbonate peroxide, 1 part by weight of polylactic acid, 0.2 parts by weight of polyhydroxytrimethylene carbonate, 0.3 parts by weight of sorbitan fatty acid ester, 0.2 parts by weight of 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]decane (CAS: 90498-90-1), and 0.05 parts by weight of cell nucleating agent A are added to a high-speed mixer and mixed evenly. The mixed material is then added to the feeder of a twin-screw extruder manufactured by Nanjing Koperon Co., Ltd. The material enters the twin screw through the feeder. During the processing, the extrusion temperature of the screw is maintained at 180℃. After being melt-mixed evenly by screw extrusion, granulated underwater, and dried, PBST401 composition microparticles were obtained, and their melt index MI was measured to be 1.8 g / 10 min.

[0131] (III) Preparation of foamed beads:

[0132] Specific foaming process parameters:

[0133] (i) In an autoclave (effective volume of 5L), the microparticles of the PBST401 composition are added and mixed at one time with 3L of dispersion medium water, 0.3g of surfactant sodium dodecyl sulfate, 5g of dispersant montmorillonite, and 0.1g of dispersion enhancer magnesium sulfate to obtain a mixture.

[0134] (ii) Use an inert foaming agent to purge residual air from the reactor, and then tighten the reactor lid. Feed a mixture of carbon dioxide, nitrogen, and argon (volume ratio = 75:20:5) into the autoclave, and initially adjust the pressure until it stabilizes. Then stir the mixture in the autoclave. Heat it to 115°C at a constant stirring speed of 50 rpm.

[0135] (iii) Subsequently, the pressure inside the vessel was adjusted to reach the required foaming pressure. The temperature was increased to the foaming temperature of 118°C at an average heating rate of 0.1°C / min, and the foaming pressure was 3 MPa. Under the foaming temperature and pressure conditions, the vessel was continuously stirred and foamed for 0.5 hours.

[0136] (iv) Then, the outlet of the autoclave is opened to discharge the material in the reactor into the collection tank to obtain PBST foam beads.

[0137] (v) After collecting the beads, dehydrate and dry them, and then sieve them to obtain PBST foamed beads.

[0138] The density of the foamed beads was measured according to GB / T 1033.1-2008.

[0139] (iv) Preparation of foamed bead molded bodies:

[0140] After the PBST beads have been cured for about 12 hours, they are molded using a molding machine (Kurtz T-Line from Kurtz Ersa GmbH, Germany) at a molding pressure of 0.09 MPa to produce foamed bead molded bodies.

[0141] Example 2

[0142] This embodiment illustrates the PBST composition, foamed beads, and foamed bead molded body provided by the present invention.

[0143] (I) Preparation of PBST2:

[0144] (1) Prepare a PTA slurry by mixing 350 kg / h terephthalic acid and 285 kg / h 1,4-butanediol, and continuously feed it into the first esterification reactor. Add 0.1 kg / h tetraisopropyl titanate and carry out the esterification reaction at atmospheric pressure and temperature of 220°C until the esterification rate reaches 95%.

[0145] (2) The product from the first esterification vessel is introduced into the second esterification vessel. At the same time, 228 kg / h of succinic anhydride and 350 kg / h of 1,4-butanediol are mixed to form a slurry, which is continuously fed into the second esterification vessel. 0.1 kg / h of tetraisopropyl titanate is added, and the esterification reaction is carried out at atmospheric pressure and a temperature of 200°C until the esterification rate reaches 95%.

[0146] (3) The product from the second esterification vessel is introduced into the third esterification vessel, and 0.5 g / h of lanthanum stearate is injected simultaneously. The esterification reaction is carried out at atmospheric pressure and temperature of 230°C until the esterification rate reaches 98%.

[0147] (4) The product from the third esterification reactor was introduced into the prepolymerization reactor and prepolymerized for 2 hours at an absolute pressure of 1 kPa and a temperature of 235 °C. The degree of polymerization of the product reached 22.

[0148] (5) The prepolymerization product was introduced into the final polymerization kettle and subjected to final polymerization for 5 hours at an absolute pressure of 150 Pa and a temperature of 235 °C. The degree of polymerization of the product reached 110.

[0149] (6) The product from the final polycondensation reactor was introduced into a thickening reactor, and a melt thickening reaction was carried out at an absolute pressure of 100 Pa and a temperature of 225 °C for 1.5 h. The resulting poly(butylene terephthalate) ester (PBST2) was then subjected to melt cooling granulation. The PBST2 had a melt index of 2.1 g / 10 min at 190 °C and a load of 2.16 kg, and a weight-average molecular weight of 4.5 × 10⁻⁶. 4 The molecular weight distribution width is 2.2, and the terminal carboxyl group content is 9.3 mol / t.

[0150] (II) Preparation of PBST 402 composition:

[0151] Based on 100 parts by weight of PBST2, 0.1 parts by weight of ditetradecyl peroxide dicarbonate, 2 parts by weight of polyglycolic acid, 0.5 parts by weight of polydecyl lactone, 0.2 parts by weight of diglyceride palmitate, 0.15 parts by weight of oxaloyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate (diimino-2,1-ethylidene ester), and 0.1 parts by weight of cell nucleating agent B were added to a high-speed mixer and mixed evenly. The mixed material was then fed into the feeder of a twin-screw extruder manufactured by Nanjing Koperon Co., Ltd. The material entered the twin screws through the feeder, and the extrusion temperature of the screws was maintained at 180℃ during processing. After being melt-mixed evenly by the screws, extruded, underwater pelletized, and dried, PBST402 composition microparticles were obtained, with a melt index (MI) of 1.1 g / 10 min.

[0152] (III) Preparation of foamed beads:

[0153] The density of the foamed beads was measured according to GB / T 1033.1-2008.

[0154] Specific foaming process parameters:

[0155] (i) In an autoclave (effective volume of 5L), the microparticles of the PBST402 composition are added and mixed at one time with 3L of dispersion medium water, 0.3g of surfactant sodium dodecyl sulfate, 5g of dispersant montmorillonite, and 0.1g of dispersion enhancer magnesium sulfate to obtain a mixture.

[0156] (ii) Use an inert foaming agent to purge residual air from the reactor, and then tighten the reactor lid. Feed a mixture of carbon dioxide, nitrogen, and argon (volume ratio = 75:20:5) into the autoclave, and initially adjust the pressure until it stabilizes. Then stir the mixture in the autoclave. Heat it to 118°C at a constant stirring speed of 75 rpm.

[0157] (iii) Subsequently, the pressure inside the vessel was adjusted to reach the required foaming pressure. The temperature was increased to the foaming temperature of 120°C at an average heating rate of 0.1°C / min, and the foaming pressure was 2 MPa. Under the foaming temperature and pressure conditions, the vessel was continuously stirred and foamed for 0.25 hours.

[0158] (iv) Then, the outlet of the autoclave is opened to discharge the material in the reactor into the collection tank to obtain PBST foam beads.

[0159] (v) After collecting the beads, dehydrate and dry them, and then sieve them to obtain PBST foamed beads.

[0160] The density of the foamed beads was measured according to GB / T 1033.1-2008.

[0161] (iv) Preparation of foamed bead molded bodies:

[0162] After the PBST beads have been cured for about 12 hours, they are molded using a molding machine (Kurtz T-Line from Kurtz Ersa GmbH, Germany) at a molding pressure of 0.11 MPa to produce foamed bead molded bodies.

[0163] Example 14

[0164] The difference between this embodiment and Example 1 is only that (1) under the action of a catalyst, the long-branched aliphatic aromatic copolyester (PBST A3′) obtained by mixing monomer a terephthalic acid (PTA) 423.8g (2.55mol), monomer b 1,4-butanediol (BDO) 650g (7.21mol), monomer c succinic acid (SA) 330g (2.79mol) and monomer d glycerol 1g (0.01mol) for esterification reaction has a melt index of 23g / 10min and a weight average molecular weight of 6.33×10 at 190℃ and 2.16kg load. 4 The end carboxyl group content is 19.3 mol / t; the catalyst contains 0.245 g tetrabutyl titanate (purchased from Beijing Chemical Reagent Company), 0.31 g lanthanum stearate, 0.1 g dibutyltin oxide (purchased from Beijing Chemical Plant No. 3), and 0.14 g triphenyltin hydroxide (purchased from Beijing Chemical Reagent Company).

[0165] (2) 500g of the fatty aromatic copolyester obtained in step 1) and 3g of 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane were extruded in an extruder at 175℃ to prepare a copolyester. The resulting copolyester (PBST A3) had a melt index of 1.7g / 10min at 190℃ and a load of 2.16kg, and a weight-average molecular weight of 10.62×10⁻⁶. 4 The content of terminal carboxyl groups is 1.2 mol / t.

[0166] Example 15

[0167] The PBST used in Example 15 was the PBST before chain extension in Example 14. The copolyester had a melt index of 23 g / 10 min at 190°C and a load of 2.16 kg, and a weight-average molecular weight of 6.33 × 10⁻⁶. 4 The content of terminal carboxyl groups is 19.3 mol / t.

[0168] Examples 1-16 and Comparative Examples 1-7 are shown in Table 1 for specific composition formulations, Table 2 for foaming processes, and Table 3 for performance characteristics. Example 5 differs from Example 1 only in that the amount of stiffening agent added is increased to 2 parts by weight. Example 6 differs from Example 1 only in that the amount of compatibilizer added is increased to 1 part by weight. Example 7 differs from Example 1 only in that the amount of shrinkage inhibitor added is increased to 1 part by weight. Example 8 differs from Example 1 only in that the amount of antioxidant A added is reduced to 0.05 parts by weight. Example 9 differs from Example 1 only in that the amount of cell nucleating agent added is increased to 0.2 parts by weight. Example 10 is the same as Example 1 only, except that the antioxidant is an AB composite. Example 11 is the same as Example 1 only, except that the foaming agent uses only carbon dioxide and nitrogen. Example 12 is the same as Example 1 only, except that the foaming agent uses only carbon dioxide. Example 13 is the same as Example 1 only, except that the foaming agent uses only nitrogen. Example 14 used PBST obtained by chain extension method; Example 15 used the un-chain-extended PBST described in Example 14; Example 16 used only shrinkage inhibitor B, otherwise the same as Example 1. Comparative Example 1 had the same main components and proportions as Example 1 except for the absence of a compatibilizer; Comparative Example 2 had the same main components and proportions as Example 1 except for the absence of a stiffening agent; Comparative Example 3 had the same main components and proportions as Example 1 except for the absence of a shrinkage inhibitor; Comparative Example 4 had the same main components and proportions as Example 1 except for the absence of an antioxidant; Comparative Example 5 had the same main components and proportions as Example 1 except for the absence of a cell nucleating agent; Comparative Example 6 used epoxy chain extender ADR4468 instead of chain extender A, and the main components and proportions were the same as in Example 1; Comparative Example 7 used ordinary 1000-mesh talc instead of cell nucleating agent A, and the main components and proportions were the same as in Example 1. Comparative Example 8 used monoglycerides as a shrinkage inhibitor, and the main components and proportions were the same as in Example 1.

[0169]

[0170]

[0171] Table 2

[0172]

[0173]

[0174] Table 3

[0175]

[0176]

[0177] Note: ○ Uniform bubble structure, × Uneven bubble structure

[0178] Expansion ratio = PBST composition particle density / PBST foam bead density

[0179] 24-hour shrinkage rate % = (1 - 24h expansion ratio / 0h expansion ratio)

[0180] Examples 1-10 and 11-13 show that using a composite foaming agent effectively prolongs the rate of air exchange between the foaming agent and air, which can reduce the shrinkage rate to a certain extent. Examples 3 and 7 show that when 1 part by weight of shrinkage inhibitor A is used, the shrinkage rate of PBST foam beads can be as low as below 1%. Examples 3 and 9 show that when 0.2 parts by weight of cell nucleating agent is used, the cell density of PBST foam beads can reach 10. 9The above results show that the compressive strength of the molded body in Example 9 is more than 25% higher than that in Example 1, indicating that the cell nucleating agent A has the ability to improve cell density and mechanical properties of the molded body. Compared with Example 1, Comparative Example 1 did not add a compatibilizer, resulting in poor compatibility between the stiffening agent and the PBST resin matrix, affecting the foaming ratio and mechanical properties of the molded body. Compared with Example 1, Comparative Example 2 did not use a stiffening agent, resulting in insufficient melt elasticity and a decrease in cell density. Compared with Example 1, Comparative Example 3 did not use a shrinkage inhibitor, resulting in severe shrinkage of the PBST foam beads, making it impossible to prepare molded bodies through molding, which seriously affects applications. Compared with Example 1, Comparative Example 4 did not use an antioxidant, resulting in degradation during the preparation of the PBST composition, directly causing cell rupture and merging during the foaming process, and a decrease in the mechanical properties of the molded body. Compared with Example 1, Comparative Example 5 did not use a cell nucleating agent, resulting in a decrease in cell density and affecting the mechanical properties of the molded body. Compared to Example 1, Comparative Example 6 used ADR4468 as a chain extender, which had a lower chain extension efficiency than chain extender A, resulting in insufficient melt strength and a decrease in the mechanical properties of the molded body. Compared to Example 1, Comparative Example 7 used ordinary talc as a cell nucleating agent, which had a weaker cell nucleating ability and lower cell density, affecting the mechanical properties of the molded body. Compared to Example 1, Comparative Example 8 used ordinary monoglyceride as a shrinkage inhibitor, which had a poor inhibitory effect and a higher shrinkage rate.

[0181] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

[0182] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. A fatty aromatic copolyester foaming composition, characterized in that, The composition includes aliphatic aromatic copolyester, shrinkage inhibitor, stiffening agent, compatibilizer and additives; Based on 100 parts by weight of aliphatic aromatic copolyester, the shrinkage inhibitor content is 0.2-2 parts by weight, preferably 0.3-1 parts by weight; the stiffening agent content is 0.2-5 parts by weight, preferably 0.5-2 parts by weight; the compatibilizer content is 0.1-2 parts by weight, preferably 0.2-1 parts by weight; and the auxiliary agent content is 0.01-2 parts by weight, preferably 0.15-0.7 parts by weight. The contraction inhibitor is selected from at least one of polysorbate, sucrose ester, sorbitan fatty acid ester, diglyceride palmitate, and isosorbide dinitrate; The additives include chain extenders, antioxidants, and cell nucleating agents.

2. The fatty aromatic copolyester foaming composition according to claim 1, wherein, Based on 100 parts by weight of aliphatic aromatic copolyester, the chain extender content is 0.03 to 1 part by weight, preferably 0.05 to 0.3 parts by weight, the antioxidant content is 0.02 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight, and the cell nucleating agent content is 0.02 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight.

3. The fatty aromatic copolyester foaming composition according to claim 1, wherein, The contraction inhibitor is sorbitan fatty acid ester and / or palmitic acid diglyceride.

4. The fatty aromatic copolyester foaming composition according to claim 1, wherein, The stiffening agent is selected from at least one of polylactic acid, polyglycolic acid, PLGA and polyhydroxy fatty acids.

5. The fatty aromatic copolyester foaming composition according to claim 1, wherein, The compatibilizer is selected from at least one of polytrimethylene carbonate, polyhydroxytrimethylene carbonate, polyvalerone, polyoctyl lactone, polydecyl lactone, and polynonyl lactone, preferably polyhydroxytrimethylene carbonate and / or polydecyl lactone.

6. The fatty aromatic copolyester foaming composition according to claim 1, wherein, The chain extender is a carbonate-type chain extender, preferably selected from at least one of tert-butyl peroxide-2-ethylhexyl carbonate, di(hexadecyl) peroxide, ditetradecyl peroxide, tert-butyl peroxide isopropyl peroxide, diisobutyl peroxide, bis(4-tert-butylcyclohexyl) peroxide, and tert-butyl peroxide isopropyl peroxide, more preferably di(hexadecyl) peroxide and / or ditetradecyl peroxide.

7. The fatty aromatic copolyester foaming composition according to claim 1, wherein, The antioxidant is selected from 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]decane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanuric acid, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and 3,5-bis-(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid branched chain. Or at least one of linear alkyl esters and (3,5-di-tert-butyl-4-hydroxyphenyl)propionate oxaloyl (diimino-2,1-ethylidene ester), preferably 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]decane and / or (3,5-di-tert-butyl-4-hydroxyphenyl)propionate oxaloyl (diimino-2,1-ethylidene ester).

8. The fatty aromatic copolyester foaming composition according to claim 1, wherein, The cell nucleating agent is MXene material with the general formula M. n+1 X n T x M is a transition metal atom, preferably zirconium, chromium, hafnium, molybdenum, titanium, niobium, tantalum, vanadium, scandium, or tungsten, more preferably titanium, vanadium, molybdenum, or niobium; X represents carbon and / or nitrogen; T x It is selected from at least one of -OH, -COOH, -Br, =O, -F and -Cl, preferably -COOH and / or -F; n is 1, 2, 3 or 4; Preferably, the cell nucleating agent is V2CT. x and / or Ti3CNT x .

9. The fatty aromatic copolyester foaming composition according to claim 1, wherein, The fatty aromatic copolyester has a melt index of 0.1–80 g / 10 min, preferably 1–5 g / 10 min, at 190 °C and a load of 2.16 kg, and a weight-average molecular weight of 4–12 × 10⁻⁶. 4 Preferably, it is 4.5 to 10×10 4 The molecular weight distribution is 1-3.5, preferably 2.2-3, and the terminal carboxyl group content is 8-12 mol / t, preferably 8.5-11 mol / t.

10. The fatty aromatic copolyester foaming composition according to claim 9, wherein, The aliphatic aromatic copolyester is obtained by monomers a, b, c and optionally d under the action of a catalyst through a process of diesterization, atmospheric pressure esterification, prepolymerization, final polymerization and liquid phase thickening; preferably, the catalyst includes a first catalyst, a second catalyst and a third catalyst. More preferably, the process of diesterization under normal pressure esterification-pre-polymerization-final-polymerization-liquid phase thickening includes the following steps: (1) In the presence of a first catalyst and / or a second catalyst, monomer a and monomer b are subjected to an esterification reaction in a first esterification reactor, which is a vertical esterification reactor with stirring. When the esterification rate in the first esterification reactor reaches 90-95%, the next reaction step is introduced. (2) The product of the first esterification vessel, the first catalyst and / or the second catalyst, monomer c and optional monomer b and / or optional d are introduced into the second esterification vessel for esterification reaction. The second esterification vessel is a vertical esterification reactor with stirring. When the esterification rate in the second esterification vessel reaches 90-95%, the next reaction step is introduced. (3) In the presence of a third catalyst, the product of the second esterification vessel is introduced into the third esterification vessel for esterification reaction. The third esterification vessel is a vertical esterification reactor with stirring. When the esterification rate in the third esterification vessel reaches more than 98%, the next reaction step is introduced. (4) The product of the third esterification reactor is introduced into the prepolymerization reactor for prepolymerization. The prepolymerization reactor is a vertical stirred tank. When the degree of polymerization reaches 20-30, the product is introduced into the next reaction step. (5) The product of the prepolymerization reactor is introduced into the final polymerization reactor for final polymerization. The final polymerization reactor is a horizontal cage-type film-forming final polymerization reactor. When the degree of polymerization reaches 100-150, the product is introduced into the next reaction step. (6) The product from the final polycondensation reactor is introduced into a thickening reactor for melt thickening, so that the melt index of the reaction product reaches 0.1-20 g / 10 min. The thickening reactor is a biaxial horizontal liquid phase thickening reactor.

11. The fatty aromatic copolyester foaming composition according to claim 10, wherein, The monomer a is selected from aromatic dicarboxylic acids and / or their ester derivatives; the monomer b is selected from C2-C... 10 At least one of aliphatic diols or alicyclic diols; wherein the monomer c is selected from C4-C6. 20 The aliphatic dicarboxylic acid or its ester derivative; wherein the monomer d is selected from at least one of polyols, polycarboxylic acids or anhydrides with a functionality greater than 2; Preferably, the molar ratio of monomers a, b, c and d satisfies the following conditions: (a+c):b is 1:0.8-3; (a+c):d is 100-2000:1; a:c is 60:40-0.1:

100.

12. The fatty aromatic copolyester foaming composition according to claim 10, wherein, The first catalyst is selected from oxides of M and M(OR1). n and M(-OOCR2) n At least one compound, wherein M is titanium, antimony, or zinc, n is the valence state of M, and R1 is C1-C 10 Alkyl group, R2 is C1-C 30 Alkyl groups; The second catalyst is an organotin compound; The third catalyst is at least one of a compound with the chemical formula RE(R3)3, wherein RE is a rare earth metal element, and R3 is selected from halogens, alkoxy groups, aryloxy groups, acetylacetonyl groups, and R4COO. - At least one of the groups, R4 is C1-C 30 Alkyl groups; Preferably, the total amount of catalyst added is in a molar ratio of 1:1000-20000 to monomer (a+c), more preferably 1:4000-12000; More preferably, the molar ratio of the first catalyst: the second catalyst: the third catalyst is 0.1-20:0.1-10:1, preferably 0.1-1.5:0.1-0.5:

1.

13. A type of fatty aromatic copolyester foamed beads, characterized in that, The fatty aromatic copolyester foamed beads are obtained by foaming the fatty aromatic copolyester foaming composition according to any one of claims 1-12.

14. The fatty aromatic copolyester foamed beads according to claim 13, wherein, The density of the foamed beads is 0.03-0.3 g / cm³. 3 The preferred value is 0.05-0.25 g / cm³. 3 The foamed beads have a pore diameter of 10-200 μm, preferably 20-150 μm; a closed-cell rate of 80-98%, preferably 85-95%; and a pore density of 1×10⁻⁶. 9 -1×10 5 cm -3 Preferably 1.1×10 9 -0.98×10 6 cm -3 .

15. A method for preparing fatty aromatic copolyester foamed beads, characterized in that, The method includes: melting and pelletizing the fatty aromatic copolyester foaming composition according to any one of claims 1-12 to obtain fatty aromatic copolyester microparticles, and then foaming the microparticles; Preferably, the foaming is performed by in-vessel immersion foaming.

16. The method according to claim 15, wherein, The pelleting is underwater pelleting or strand pelleting, preferably underwater pelleting; Preferably, the length-to-diameter ratio of the microparticles is 0.5-2, more preferably 0.9-1.1; the average weight of the microparticles is 0.1-20 mg, more preferably 0.2-10 mg, and even more preferably 2-4 mg.

17. The method according to claim 15 or 16, wherein, The in-vessel immersion foaming method includes the following steps: (1) In a reaction vessel, fatty aromatic copolyester microparticles are mixed with a dispersion medium, surfactant, dispersant and dispersion enhancer to obtain a mixture; (2) Feed the foaming agent into the reactor, remove the air from the reactor, and heat the mixture to a temperature 0.1-5℃ lower than the expansion temperature, preferably 0.5-1℃ lower, under stirring conditions; (3) Continue stirring and foaming at foaming temperature and foaming pressure to obtain fatty aromatic copolyester foam beads. (4) While discharging the fatty aromatic copolyester foam beads from the reactor, carbon dioxide gas is fed into the reactor and the pressure inside the reactor is maintained at the foaming pressure.

18. The method according to claim 17, wherein, The stirring speed is 25-300 rpm, preferably 100-200 rpm; Preferably, the foaming temperature is 0.1-10°C lower than the melting temperature of the fatty aromatic copolyester microparticles, and more preferably 5-7°C lower. Preferably, the foaming pressure is 1-10 MPa, more preferably 0.5-4 MPa; Preferably, the foaming time is 0.1-2 hours, more preferably 0.05-0.5 hours.

19. The method according to claim 17 or 18, wherein, The volume ratio of the dispersion medium to the volume of the reactor is (1-4):5, preferably (2.5-3.5):5; Preferably, the dispersion medium is selected from at least one of water, ethylene glycol, glycerol, methanol, and ethanol, and is preferably water; Preferably, relative to 100 parts by weight of fatty aromatic copolyester microparticles, the amount of surfactant is 0.001-1 parts by weight, preferably 0.01-0.5 parts by weight, more preferably 0.1-0.3 parts by weight; the amount of dispersant is 0.01-5 parts by weight, preferably 0.1-3 parts by weight, more preferably 0.5-2 parts by weight; and the amount of dispersion enhancer is 0.0001-1 parts by weight, preferably 0.01-0.1 parts by weight. Preferably, the surfactant is selected from at least one of stearic acid, sodium dodecylbenzenesulfonate, quaternary ammonium compounds, lecithin, amino acids, betaine, fatty acid glycerides, fatty acid sorbitan, and polysorbate, and is preferably sodium dodecylbenzenesulfonate; Preferably, the dispersant is selected from organic dispersants and / or inorganic dispersants, and more preferably inorganic dispersants; More preferably, the inorganic dispersant is selected from at least one of kaolin, mica, pyrope, clay, bauxite, titanium dioxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate, silicon dioxide, zinc borate and iron oxide, preferably montmorillonite; Preferably, the dispersing enhancer is selected from at least one of magnesium nitride, magnesium nitrate, aluminum phosphate, magnesium sulfate, aluminum nitride, aluminum nitrate, aluminum sulfate, ferric chloride, ferric sulfate, and ferric nitrate, and is preferably magnesium sulfate; Preferably, the foaming agent is selected from organic physical foaming agents and / or inorganic physical foaming agents; More preferably, the organic physical foaming agent is selected from at least one of aliphatic hydrocarbons, alicyclic hydrocarbons, and halogenated hydrocarbons; More preferably, the inorganic foaming agent is selected from at least one of air, argon, nitrogen, carbon dioxide, oxygen, and water; More preferably, the foaming agent is carbon dioxide, nitrogen and argon, and the volume ratio of carbon dioxide, nitrogen and argon is 75:20:

5.

20. A fatty aromatic copolyester foamed bead prepared by the preparation method according to any one of claims 15-19.

21. A fatty aromatic copolyester foamed bead molded body, characterized in that, The fatty aromatic copolyester foamed beads are made from fatty aromatic copolyester foamed beads according to any one of claims 13-14 and 20.

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