CN115637026A

CN115637026A - Degradable copolyester composition, antistatic biodegradable film material, antistatic biodegradable film and application

Info

Publication number: CN115637026A
Application number: CN202110814267.4A
Authority: CN
Inventors: 郭鹏; 吕明福; 祝桂香; 徐耀辉; 宋志海; 郑萃; 张韬毅; 高达利; 王湘; 张龙贵; 张宗胤
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2021-07-19
Filing date: 2021-07-19
Publication date: 2023-01-24

Abstract

The invention belongs to the field of macromolecules, and relates to a degradable copolyester composition, an antistatic biodegradable film material, an antistatic biodegradable film and application. The degradable copolyester composition comprises the following components in parts by weight: 100 parts of degradable copolyester; 0.05-5 parts of antistatic agent; the antistatic agent is edge-modified graphene, and the edge-modified graphene has the following characteristics: the average sheet diameter is 2-30 mu m; the average aspect ratio is 600-10000: 1; the conductivity is 200-800S/m; in the edge modified graphene, the oxygen content is 3-30 at% in terms of oxygen element; the hydrogen content is 1 to 10at% in terms of hydrogen element. The degradable copolyester composition can be used as a film material to prepare a degradable copolyester blown film, and the film has the characteristics of good mechanical property, easiness in opening, good antistatic property and biodegradability.

Description

Degradable copolyester composition, antistatic biodegradable film material, antistatic biodegradable film and application

Technical Field

The invention belongs to the field of macromolecules, and particularly relates to a degradable copolyester composition, application of the degradable copolyester composition, an anti-static biodegradable film material containing the degradable copolyester composition and a preparation method thereof, an anti-static biodegradable film prepared from the anti-static biodegradable film material, and application of the degradable copolyester composition, the anti-static biodegradable film material or the anti-static biodegradable film in preparation of an electronic packaging bag film.

Background

1950, 83 million tons of plastics have been produced all over the world, 63 million tons of plastics have become waste plastics. Of these, only 9% is recovered, 12% is incinerated, and the remaining 79% (nearly 50 hundred million tons) is buried or scattered in the environment. According to research, the plastic microparticles enter an ecological cycle system. About 4 million tons of plastics are produced every year all over the world, and 120 million tons of waste plastics are produced by 2050 years, which requires more than 100 years of degradation. In the world environment day of 6/5/2018, the environmental planning agency of the United nations sets the theme as 'Plastic warfare fast decision' (Beat Plastic Pollution), and calls for a fair concerted effort to resist the Pollution of disposable Plastic products. The european union has acted that, according to the current trend, disposable plastic products, which account for 40% of plastic products, will be banned from use step by step. Conventionally, the base resin of the film material is generally a general-purpose resin such as PP, PE, PS, and the like. However, the film prepared by the polymer material cannot be automatically degraded after the use period is finished, and is easy to pollute soil, rivers and oceans. In recent years, attention has been paid to degradable films in the industry and academia. Poly (butylene succinate-butylene terephthalate) ester (PBST) is a biodegradable high molecular compound that can be biodegraded in a composting manner in the natural environment. The molecular weight of poly (butylene succinate-butylene terephthalate) ester is regulated, so that the poly (butylene succinate-butylene terephthalate) ester can be prevented from being degraded in the using process, has certain melt strength, can meet the requirement of film inflation in the blown film production process without film bubble breakage, is stable in film bubble, and can be widely used for film products such as packaging bags, mulching films, greenhouse films and the like produced by a blowing process.

Electrostatic interference is a specific object or charge that naturally represents a static or moving state of a specific object in life, and when such specific charge naturally accumulates in the interior or on the surface of a specific object, so-called semiconductor static electricity is naturally formed. In general, the resulting semiconductor electronic interference, integration breakdown, contaminated semiconductor integrated circuits, and other semiconductor electronic components that have been damaged are all likely to be considered to be operational and environmental hazards due to semiconductor electrostatic interference. Among them are increasing the discharge distance by using some plastic parts in the semiconductor-packaged electronic product, electrostatic shielding of the chassis by using plastic in the semiconductor-packaged electronic product, and insulation protection by using the chassis. In the modern packaging of some semiconductor electronic products, a plurality of the traditional antistatic treatment methods which are available before are proved by the state not to be practical in application, but for the current electronic products, the damage caused by static electricity not only affects the efficiency or reduces the product quality like on a production line, and many modern electronic components often have the thickness of an oxide layer below 100A and the endurable voltage less than 24V, and under the condition, if the packaging material of the electronic product components can not meet the requirement of antistatic, the electronic components can be directly failed. At present, non-degradable PET and PP packages are mostly used for anti-static electronic accessories and products used at the present stage, and after the electronic products are taken out, the waste packages are disposed at will, so that soil and water pollution is easily caused.

Therefore, it is necessary to develop an antistatic and degradable material and a film product.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a degradable copolyester composition, wherein the degradable copolyester composition takes controllable biodegradable copolyester as base resin, edge modified graphene is taken as an antistatic agent and an opening agent, the degradable copolyester composition can be taken as a film material to prepare a degradable copolyester blown film, and the film has the characteristics of good mechanical property, easiness in opening, good antistatic property and biodegradability.

The first aspect of the invention provides a degradable copolyester composition, which comprises the following components in parts by weight:

100 parts of degradable copolyester;

0.01 to 10 parts of antistatic agent, preferably 0.05 to 5 parts, more preferably 0.1 to 1 part;

the antistatic agent is edge modified graphene, and the edge modified graphene has the following characteristics:

the average sheet diameter is 2 to 30 μm, preferably 5 to 15 μm; and/or

The average aspect ratio is 600-10000: 1, preferably from 1200 to 4500:1, more preferably 1500 to 3800:1; and/or

The conductivity is 200 to 800S/m, preferably 300 to 600S/m; and/or

In the edge-modified graphene, the oxygen content in terms of oxygen element is 3 to 30at%, preferably 5 to 18at%; the hydrogen content is 1 to 10at%, preferably 3 to 8at%, in terms of hydrogen element.

The second aspect of the present invention provides the use of the above-mentioned degradable copolyester composition as an antistatic biodegradable material.

The third aspect of the invention provides an antistatic biodegradable film material, which comprises the degradable copolyester composition and a film assistant, wherein the content of the film assistant is 1-50 parts by weight based on 100 parts by weight of the degradable copolyester composition.

The fourth aspect of the present invention provides a method for preparing the above-mentioned antistatic biodegradable film material, comprising the following steps:

mixing degradable copolyester, antistatic agent, film additive and optional compatilizer, and then extruding and granulating to prepare the antistatic biodegradable film material; alternatively, the first and second electrodes may be,

mixing and granulating the degradable copolyester and an optional antioxidant to obtain a base resin, mixing the base resin with an antistatic agent and at least one of an optional slipping agent, a nucleating agent, a compatilizer and a degradable resin, and then extruding and granulating to obtain the anti-static biodegradable film material.

The fifth aspect of the present invention provides an antistatic biodegradable film, which is made of the above antistatic biodegradable film material.

The sixth aspect of the present invention provides the use of the above degradable copolyester composition, antistatic biodegradable film material, or antistatic biodegradable film in the preparation of electronic packaging bag films.

Compared with the prior art, the invention has the following beneficial effects:

1) The degradable copolyester composition provided by the invention has good mechanical properties, so that the degradable copolyester composition is suitable for excellent materials in the fields of electronic packaging, electronic protective films and the like. The preparation method of the degradable copolyester composition provided by the invention is simple and effective and is easy to operate.

2) The anti-static biodegradable film has a controllable degradation structure, can be degraded by garbage compost, does not cause secondary pollution, meets the requirement of circular economy, and has the characteristics of good mechanical property, easy opening and good antistatic property, and the preparation process is simple and convenient.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The invention provides a degradable copolyester composition, which comprises the following components in parts by weight:

100 parts of degradable copolyester;

the average sheet diameter is 2 to 30 μm, preferably 5 to 15 μm; and/or

The average aspect ratio is 600-10000: 1, preferably 1200 to 4500:1, more preferably 1500 to 3800:1; and/or

The conductivity is 200 to 800S/m, preferably 300 to 600S/m; and/or

In the edge-modified graphene, the oxygen content in terms of oxygen element is 3 to 30at%, preferably 5 to 18at%; the hydrogen content is 1 to 10at%, preferably 3 to 8at%, based on the hydrogen element.

According to a preferred embodiment of the present invention, the degradable copolyester is a fatty aromatic copolyester; the aliphatic aromatic copolyester contains a structural unit derived from a monomer b, a structural unit derived from a monomer c, a structural unit derived from a monomer d and optionally a structural unit derived from a monomer a; the monomer a is aromatic dibasic acid and/or ester derivative thereof, the monomer b is at least one of aliphatic dibasic acid and alicyclic dibasic alcohol, the monomer c is aliphatic dibasic acid and/or ester derivative thereof, and the monomer d is at least one of polyfunctional polyhydric alcohol, polybasic carboxylic acid and anhydride;

the melt index of the degradable copolyester at 190 ℃ under the load of 2.16kg is 0.1-10 g/10min, preferably 0.5-8 g/10min, and more preferably 1-6 g/10min; the number average molecular weight is 4-8 ten thousand, preferably 4-6 ten thousand; the molecular weight distribution is 1.5 to 4, preferably 2 to 3.

According to the degradable copolyester composition of the invention, preferably, the monomer a is C ₈ -C ₁₆ More preferably terephthalic acid and/or dimethyl terephthalate, and/or ester derivatives thereof.

According to the degradable copolyester composition of the present invention, preferably, the monomer b is C ₂ -C ₁₀ Aliphatic diols and C ₃ -C ₁₀ More preferably 1, 3-propanediol and/or 1, 4-butanediol.

According to the degradable copolyester composition of the invention, preferably, the monomer C is C ₄ -C ₂₀ Further preferably C ₄ -C ₈ More preferably selected from succinic acid, dimethyl succinate, adipic acid or dimethyl adipate.

According to the degradable copolyester composition of the present invention, preferably, the monomer d is at least one of polyol with functionality more than 2, polycarboxylic acid with functionality more than 2 or anhydride with functionality more than 2, more preferably at least one of pyromellitic dianhydride, glycerol and pentaerythritol.

The content of each monomer can be used in conventional amounts as long as the aliphatic aromatic copolyester of the corresponding melt index is obtained, preferably, the molar content a of the structural unit derived from the monomer a, the molar content B of the structural unit derived from the monomer B, the molar content C of the structural unit derived from the monomer C and the molar content D of the structural unit derived from the monomer D satisfy:

the molar ratio of (A + C): B is 1: 0.5-5, preferably 1: 0.7-3; and/or the presence of a gas in the gas,

the molar ratio of (A + C): D is (100-2000): 1, preferably (300-1500): 1; and/or the presence of a gas in the gas,

the molar ratio of A to C is 0: 100-60: 40. Wherein A + C refers to the total molar content of the monomer a and the monomer C.

In order to obtain an aliphatic aromatic copolyester with more excellent performance, it is preferable that the molar content a of the structural unit derived from the monomer a, the molar content B of the structural unit derived from the monomer B, the molar content C of the structural unit derived from the monomer C, and the molar content D of the structural unit derived from the monomer D satisfy:

the molar ratio of (A + C) to B is 1: 0.8-3; and/or the presence of a gas in the atmosphere,

the molar ratio of (A + C): D is (100-2000): 1; and/or the presence of a gas in the gas,

the molar ratio of A to C is 30: 100-60: 40.

The edge-modified graphene has the advantages that the sheet diameter is in a micron scale, the adjustable aspect ratio and the content of carbon and oxygen elements are realized, the conductivity is higher, the edge-modified graphene can be obviously different from the existing nano-grade graphene (such as US 20130018204), and the problem that the nano-grade graphene is easy to gather can be solved.

In the present invention, the "aspect ratio" refers to the ratio of the long side (sheet diameter) to the thickness of graphene.

According to the present invention, preferably, the edge-modified graphene is prepared by grinding graphite by a grinding disc under supercritical carbon dioxide.

Under the condition of supercritical carbon dioxide, the properties of the carbon dioxide are greatly changed, the density is close to that of liquid, the viscosity is close to that of gas, and the diffusion coefficient is 100 times that of the liquid. The inventor of the invention discovers that in the state, carbon dioxide is inserted into the graphite sheet layer, so that pi-pi interaction between the graphite sheet layers is reduced, and graphite is stripped into graphene after the carbon dioxide is sheared by a grinding disc; meanwhile, graphite or graphene is also crushed by the aid of the shearing action of the grinding disc, and a newly generated high-activity edge reacts with carbon dioxide, so that carboxyl is modified on the edge of the graphene. Compared with the common ball milling method, the method can prepare the graphene with carboxylated edges without milling the graphite to be extremely fine, and the common ball milling method needs to mill the graphite to be in a nanometer level, otherwise the graphene cannot be prepared.

In the present invention, the terms "edge-modified graphene", "carboxylated graphene", "edge-carboxylated graphene" and "edge-carboxylated modified graphene" refer to the same.

The edge modified graphene provided by the invention is prepared by a method comprising the following steps: grinding graphite powder in a high-pressure grinding disc kettle in the presence of supercritical carbon dioxide.

According to a specific embodiment of the present invention, the edge-modified graphene is prepared by a method comprising the following steps:

step S1, adding purified or unpurified graphite powder into a high-pressure grinding disc kettle;

s2, introducing carbon dioxide into the high-pressure grinding disc kettle, and enabling the carbon dioxide to be in a supercritical state to form a material containing graphite powder and supercritical carbon dioxide;

and S3, grinding the material containing the graphite powder and the supercritical carbon dioxide.

According to some embodiments of the invention, the graphite powder is selected from the group consisting of flake graphite powder and expanded graphite powder, preferably the graphite powder has a particle size of 10 to 80 mesh, preferably 20 to 60 mesh.

According to some embodiments of the invention, prior to milling, the graphite powder is preferably subjected to a purification treatment, for example by ultrasonic cleaning and/or chemical treatment, to remove impurities, such as hetero-phase substances and impurity elements.

According to some embodiments of the invention, in step S2, the carbon dioxide is brought into a supercritical state by bringing the temperature in the tank to over 32.26 ℃ and the pressure to over 72.9 atm.

According to some embodiments of the invention, in step S3, after grinding is completed, the pressure in the high-pressure grinding disc kettle is rapidly decreased; preferably, the pressure in the high-pressure millstone kettle is reduced to below 1atm within 5-20 seconds.

According to some embodiments of the invention, the temperature in the high-pressure millstone kettle is between 35 and 200 ℃, preferably between 35 and 100 ℃, more preferably between 35 and 70 ℃.

According to some embodiments of the invention, the pressure in the high-pressure millstone kettle is 75 to 165atm, preferably 75 to 150atm, more preferably 75 to 125atm.

According to some embodiments of the invention, the stirring speed in the high-pressure millstone kettle is 500 to 10000r/min, preferably 500 to 5000r/min.

According to some embodiments of the invention, the time of milling is 6 to 48 hours.

Through the setting of the specific grinding conditions, the prepared edge modified graphene can meet the structural and performance characteristics.

In the invention, the graphite and the supercritical carbon dioxide can be fully mixed by adopting a high-pressure millstone kettle, and the graphite is ground and peeled.

According to the preferred embodiment of the invention, the high-pressure grinding disc kettle is a self-circulation grinding disc device used in a high-pressure environment.

According to the invention, the degradable copolyester can be obtained by reacting a mixture containing a monomer b, a monomer c, a monomer d and an optional monomer a; preferably, the degradable copolyester is prepared by reacting a mixture containing a monomer b, a monomer c, a monomer d and an optional monomer a under the action of a catalyst to obtain long-chain branched aliphatic aromatic copolyester, and then performing extrusion reaction with an organic peroxide.

Specifically, the degradable copolyester is prepared by a method comprising the following steps:

(1) Preparation of long-chain branched aliphatic aromatic copolyester: under the action of a catalyst, mixing a monomer b, a monomer c, a monomer d and an optional monomer a for esterification reaction, or mixing the monomer b or the esterification product of the monomer a and the monomer b and the esterification product of the monomer c and the monomer d for copolycondensation reaction to obtain the long-chain branched aliphatic aromatic copolyester;

(2) And (2) carrying out extrusion reaction on the long-chain branched aliphatic aromatic copolyester prepared in the step (1) and organic peroxide to obtain the degradable copolyester.

According to the present invention, the catalyst contains at least one of a first catalyst, a second catalyst and a third catalyst;

the first catalyst is selected from the oxides of M, M (OR) ₁ ) n and M (OOCR) ₂ ) M, where M is titanium, antimony or zinc, n and M are each independently of the other the valence of M, R ₁ Is C ₁ -C ₁₀ Alkyl of R ₂ Is C ₁ -C ₂₀ Alkyl groups of (a); preferably, the first catalyst is selected from at least one of titanium alkoxide, antimony acetate, zinc oxide, antimony oxide, titanium oxide, titanate, and titanium alkoxide; more preferably, the first catalyst is selected from at least one of tetrabutyl titanate, titanium isopropoxide, titanium dioxide, antimony trioxide, antimony acetate and zinc acetate;

and/or the presence of a gas in the gas,

the second catalyst is RE (R) ₃ ) ₃ At least one of compounds of (1) and hydrates thereof, wherein RE is a rare earth metal element and/or a titanium-based metal element, R ₃ Selected from the group consisting of halogen, alkoxy, aryloxy, acetylacetonate and R ₄ At least one of COO-groups, R ₄ Is C ₁ -C ₃₀ Alkyl groups of (a); preferably, RE is selected from at least one of lanthanum, cerium, praseodymium, neodymium, terbium, ytterbium, dysprosium, samarium, scandium, titanium, zirconium, and hafnium; the halogen is chlorine and/or bromine, and the alkoxy is C ₃ ～C ₆ An aryloxy group which is an aryloxy group comprising at least one benzene ring and/or naphthalene ring, R ₄ Is C ₁ ～C ₂₀ Alkyl groups of (a);

more preferably, RE is at least one selected from lanthanum, cerium, praseodymium, neodymium and scandium, the halogen is chlorine and/or bromine, the alkyl group in the alkoxy group is at least one of isopropyl group, n-butyl group and isoamyl group, the aryl group in the aryloxy group is at least one of 2, 6-di-tert-butyl-4-methylphenyl group and 4-butylphenyl group, R is ₄ Is C ₃ -C ₁₈ At least one of alkyl groups of (a);

further preferably, the second catalyst is at least one of lanthanum acetylacetonate, neodymium isopropoxide, lanthanum isopropoxide, scandium isopropoxide, lanthanum stearate, neodymium stearate, lanthanum chloride, lanthanum tris (2, 6-di-tert-butyl-4-methylphenoxy) and hydrates thereof;

and/or the presence of a gas in the atmosphere,

the third catalyst is at least one organic tin compound; preferably, the third catalyst is selected from at least one of dibutyl tin oxide, methylphenyl tin oxide, tetraethyl tin, hexaethyl tin oxide, hexacyclohexyl tin oxide, didodecyl tin oxide, triethyl hydroxyl tin, triphenyl hydroxyl tin, triisobutyl tin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyl tin trichloride, tributyl tin chloride, dibutyl tin sulfide, butyl hydroxyl tin oxide, methyl stannic acid, ethyl stannic acid, and butyl stannic acid; more preferably, the third catalyst may be selected from a mixture of at least two of dibutyl tin oxide, tetraethyl tin, triphenyl hydroxyl tin, dibutyl tin diacetate, diphenyl tin dilaurate, monobutyl tin trichloride, tributyl tin chloride, dibutyl tin sulfide, butyl hydroxyl tin oxide, methyl stannoic acid, ethyl stannoic acid, and butyl stannoic acid; further preferably, the content of each component in the third catalyst is 10 to 90 mol%, preferably 30 to 70 mol%, based on the total molar amount of the third catalyst being 100 mol%.

The catalyst of the present invention can be used in conventional amount in the art, preferably, the molar ratio of the total amount of the catalyst to the total amount of the monomers (a + c) is 1: 1000-20000; preferably 1: (1000 to 10000); and/or the presence of a gas in the atmosphere,

the molar ratio of the first catalyst to the second catalyst to the third catalyst is (0.1-20): 0.1-10): 1, preferably (0.1-10): 1.

According to the invention, the organic peroxide may be selected from organic peroxides having a half-life of 0.2 to 10min, preferably a half-life of 0.2 to 2min, within the processing temperature range.

Preferably, the organic peroxide is selected from at least one of alkyl peroxides, acyl peroxides, and peroxyesters.

More preferably, the organic peroxide is selected from at least one of 2, 5-bis (t-amylperoxy) -2, 5-dimethylhexane, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane, 3, 6-bis (t-butylperoxy) -3, 6-dimethyloctane, 2, 7-bis (t-butylperoxy) -2, 7-dimethyloctane, 8, 11-bis (t-butylperoxy) -8, 11-dimethyloctadecane or a mixture thereof, bis (alkylperoxy) benzene, bis (alkylperoxy) alkyne and dibenzoyl peroxide; wherein the bis (alkylperoxy) benzene is preferably selected from the group consisting of α, α '- (t-amylperoxy-isopropyl) benzene, α' -bis (t-butylperoxy-isopropyl) benzene, or mixtures thereof; the bis (alkylperoxy) alkyne is selected from at least one of 2, 7-dimethyl-2, 7-di (t-butylperoxy) -octadiyne-3, 5,2, 7-dimethyl-2, 7-di (peroxyethyl carbonate) -octadiyne-3, 5,3, 6-dimethyl-3, 6-di (t-butylperoxy) octyne-4, 2, 5-dimethyl-2, 5-di (peroxy-n-propyl-carbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (peroxy-isobutyl carbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (peroxyethyl monocarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di ((α -cumylperoxy) hexyne-3, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3.

The organic peroxide used in the present invention may be used in a conventional amount, for example, the amount of the organic peroxide is 0.01 to 5wt%, preferably 0.01 to 1wt% of the amount of the long-chain branched aliphatic aromatic copolyester.

In the present invention, the conditions of the esterification reaction and the polycondensation reaction can be conventionally selected according to the prior art. In the step 1), the temperature of the esterification reaction can be 150-220 ℃; the conditions of the polycondensation reaction may include: the temperature is 250-270 deg.C, and the time is 2-3 hours.

The melt index of the long-chain branched aliphatic aromatic copolyester prepared in the step 1) at 190 ℃ under the load of 2.16kg can be 5-100 g/10min.

In the step 2), the extrusion temperature can be 150-200 ℃, and preferably 160-180 ℃;

the melt index of the copolyester prepared in the step 2) is 0.1-10 g/10min at 190 ℃ under the load of 2.16kg.

In order to increase the interfacial compatibility of graphene and degradable polyester, the degradable copolyester composition of the invention preferably comprises a compatibilizer, which can be at least one of maleic anhydride grafted PBST (MAH-PBST), glycidyl methacrylate grafted PBST (GMA-PBST), maleic anhydride grafted PBAT (MAH-PBAT) and glycidyl methacrylate grafted PBAT (GMA-PBAT), and the grafting ratio is more than 1wt%. The content of the compatibilizer is preferably 1 to 10 parts by weight, more preferably 3 to 7 parts by weight, based on 100 parts by weight of the total amount of the degradable copolyester and the antistatic agent.

The degradable copolyester composition can be prepared by mixing the components.

The degradable copolyester composition can be used as an antistatic biodegradable material. The long-chain branched aliphatic aromatic copolymer is adopted as a main material, and is extruded, chain extended and tackified, the length of the branched chain is further increased, the melt strength of the long-chain branched aliphatic aromatic copolymer is increased while the melt index is reduced, and meanwhile, a high-strength film product is prepared by matching with a corresponding processing aid, and the film can be completely degraded into micromolecular products such as carbon dioxide, water and the like under natural or composting conditions.

Specifically, the invention provides an antistatic biodegradable film material, which comprises the degradable copolyester composition and a film assistant, wherein the content of the film assistant is 1-50 parts by weight, preferably 2-22 parts by weight, based on 100 parts by weight of the degradable copolyester composition. The film auxiliary agent can be various auxiliary agents which are conventional in the field of films, and specifically, the film auxiliary agent can be at least one of a slipping agent, a nucleating agent, an antioxidant and a degradable resin.

According to the invention, the antistatic biodegradable film material may comprise a slip agent; wherein, the content of the slipping agent can be 0.05 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the degradable copolyester composition.

The slipping agent can be selected from stearate and/or organic carboxylic acid amide, wherein the stearate can be selected from calcium stearate and the like, and the organic carboxylic acid amide can be selected from at least one of erucamide, oleamide, stearic acid stearamide and N, N '-ethylene bisstearamide, and preferably the N, N' -ethylene bisstearamide.

According to the present invention, the antistatic biodegradable film material may comprise a nucleating agent; wherein, the content of the nucleating agent can be 0.1 to 20 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the degradable copolyester composition.

The nucleating agent can be selected from at least one of hyperbranched polyamide, low-density polyethylene, ethylene-methacrylic acid ionomer and ethylene-butyl acrylate-glycidyl methacrylate terpolymer; preferably an ethylene-methacrylic acid ionomer and/or an ethylene-butyl acrylate-glycidyl methacrylate terpolymer.

According to the invention, the antistatic biodegradable film material can comprise an antioxidant; wherein, the content of the antioxidant is 0.05 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the degradable copolyester composition.

The antioxidant may be any antioxidant conventionally used in the art. For example, the antioxidant can be a hindered phenol antioxidant and a phosphite ester antioxidant which are mixed according to the mass ratio of 1; wherein the hindered phenol antioxidant can be selected from at least one of antioxidant 1010 (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, CAS No. 6683-19-8), antioxidant 3114 (1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, CAS No. 27676-62-6) and antioxidant 330 (1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-tert-butyl-4-hydroxybenzyl) benzene), CAS No. 1709-70-2); the phosphite antioxidant may be selected from the group consisting of antioxidant 168 (tris [ 2.4-di-tert-butylphenyl ] phosphite; CAS: 31570-04-4), antioxidant 618 (distearyl pentaerythritol diphosphite; CAS: 3806-34-6) and antioxidant 2,2' -ethylenebis (4, 6-di-tert-butylphenyl) fluorophosphite; CAS: 118337-09-0).

According to the present invention, the antistatic biodegradable film material may further comprise a degradable resin conventionally used in the art; wherein, the content of the degradable resin can be 2 to 20 parts by weight, preferably 4 to 12 parts by weight, based on 100 parts by weight of the degradable copolyester composition.

The degradable resin can be at least one selected from polycaprolactone, polybutylene succinate adipate, polyglycolic acid, polylactic acid, polyhydroxyalkanoate (PHA) and polymethyl ethylene carbonate (PPC).

The invention also provides a preparation method of the antistatic biodegradable film material, which comprises the following steps:

mixing degradable copolyester, antistatic agent, film additive and optional compatilizer, and then extruding and granulating to prepare the antistatic biodegradable film material; specifically, mixing degradable copolyester, an antistatic agent, at least one of a slipping agent, a nucleating agent, an antioxidant and degradable resin and an optional compatilizer, and then extruding and granulating to prepare the antistatic biodegradable film material; alternatively, the first and second liquid crystal display panels may be,

mixing and granulating the degradable copolyester and an optional antioxidant to obtain a base resin, mixing the base resin with the antistatic agent and at least one of an optional slipping agent, a nucleating agent, a compatilizer and the degradable resin, and then extruding and granulating to obtain the anti-static biodegradable film material.

In the extrusion granulation step, the processing temperature can be 150-200 ℃, preferably 160-190 ℃, and the screw rotation speed can be 250-350 rpm.

The invention also provides an anti-static biodegradable film which is prepared from the anti-static biodegradable film material.

According to the invention, the thickness of the film can be adjusted according to requirements and specific processes. Preferably, the film may have a thickness of 5 to 100 μm, preferably 10 to 20 μm.

Preferably, the film has the following properties: the light transmittance of the film is more than 87%; the haze of the film is 15% or less;the falling mark impact failure mass of the film is more than 20 g; the tensile breaking stress of the film is greater than 18MPa, preferably greater than 25MPa, more preferably from 25 to 100MPa; the film has a longitudinal tensile strength of 18MPa or more, preferably a longitudinal tensile strength of 24MPa or more; a transverse tensile strength of 16MPa or more, preferably 20MPa or more; the film has a longitudinal elongation at break of 250% or more, preferably 300% or more; a transverse elongation at break of 300% or more, preferably 350% or more; the MD direction right-angle tearing load of the film is more than 2.2N, and the TD direction right-angle tearing load of the film is more than 2.5N; the opening force of the film is greater than 0.01N/cm ³ (ii) a The film has a water permeability of less than 370 g.m at 38 ℃, 90% RH ^-2 ·d ^-1 (ii) a The surface resistivity of the film is less than 2 x 10 ¹⁰ Ω。

The film meets the environmental protection requirement, is controllably degradable, is easy to open, has low production cost and is suitable for large-scale production.

According to a preferred embodiment of the present invention, the antistatic biodegradable film is a blown film, and is prepared by blowing the antistatic biodegradable film material into a film.

Preferably, the temperature of the blown film can be 150 to 210 ℃, preferably 160 to 200 ℃.

In the blown film process, the blow-up ratio may be 1.5 to 3, preferably 2 to 2.5.

According to the method, the components of the antistatic biodegradable film material can be mixed by a double-screw extruder, extruded and granulated, and then blown into a film by a film blowing machine.

Preferably, the extrusion temperature is 150 to 200 ℃, more preferably 170 to 190 ℃; the screw rotation speed is 250-350 rpm.

The extrusion temperature refers to the extrusion temperature set by the extrusion equipment, such as an extruder. The temperature of the blown film refers to the film opening temperature of a film blowing device such as a film blowing machine.

According to the invention, the film blowing machine can be a downward blowing water-cooled type, a flat blowing water-cooled type or a traditional upward blowing water-cooled type degradable copolyester film blowing machine set.

The film prepared by the antistatic controllable biodegradable film material is a degradable copolyester blown film, has the advantages of controllable biodegradation, good antistatic property, easy opening and the like, and can be applied to occasions with higher requirements on biodegradability, antistatic property and opening of plastic products, such as electronic packaging films and the like.

The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.

In the following examples and comparative examples, the relevant data were obtained according to the following test methods:

the average sheet diameter and aspect ratio of graphene were determined by Scanning Electron Microscopy (SEM).

The oxygen content and hydrogen content of the graphene were characterized by X-ray photoelectron spectroscopy (XPS).

The conductivity of the graphene was determined as described in DB 13/T2768.3-2018 using a powder resistivity conductivity tester.

The melt index was determined according to the method specified in GB/T3682-2000, with a test temperature of 190 ℃ and a load of 2.16kg.

Gel Permeation Chromatography (GPC) determined the molecular weight and molecular weight distribution of the polymer, using Tetrahydrofuran (THF) as solvent, on a Waters-208 (with a Waters 2410RI detector, 1.5ml/min flow rate, 30 ℃) instrument, molecular weight calibrated to styrene standards.

The light transmittance and haze were measured by the GB/T2410 method.

The falling mark impact failure quality is determined by the GB/T9639 method.

Tensile breaking stress, tensile strength and elongation at break were measured by the GB/T1040 method.

Right angle tear load was measured by the QB/T1130 method.

The opening force was measured by the method of GB/T16276.

The water permeability is determined by the GB/T1037 method.

The surface resistivity was measured by the GB/T1410 method.

Preparation example 1

The preparation example is used for illustrating the preparation of the edge-modified graphene.

G101

Ultrasonically cleaning 100g 32-mesh crystalline flake graphite powder (washing with water for 1 time and washing with ethanol for 2 times) to remove impurity phase substances and impurity elements, placing the crystalline flake graphite in a high-pressure grinding disc kettle, sealing the high-pressure grinding disc kettle, heating the high-pressure grinding disc kettle to 40 ℃, and pumping CO into the high-pressure grinding disc kettle ₂ And (3) raising the pressure in the high-pressure grinding disc kettle to 85atm, setting the rotating speed to 500r/min, grinding and stripping graphite by utilizing the shearing force generated by the grinding disc, reducing the pressure to 1atm within 10s after stirring for 24h, and sampling from the high-pressure grinding disc kettle to obtain the edge modified graphene G101.

When the prepared edge-modified graphene G101 is analyzed by a Scanning Electron Microscope (SEM), the average sheet diameter of the graphene is 12.6 μm, the average thickness is 3.4nm, and the average aspect ratio is 3706:1, X-ray photoelectron spectroscopy (XPS), an oxygen content of 5.60at%, a hydrogen content of 3.22at%, and an electrical conductivity of 506S/m.

G102

Ultrasonic cleaning 40g 32 mesh expanded graphite powder (water washing for 1 time, ethanol washing for 2 times) to remove impurity phase substances and impurity elements, placing the expanded graphite powder in a high-pressure grinding disc kettle, sealing the high-pressure grinding disc kettle, heating the high-pressure grinding disc kettle to 40 deg.C, pumping CO into the high-pressure grinding disc kettle ₂ And (3) increasing the pressure in the high-pressure grinding disc kettle to 85atm, setting the rotating speed to 500r/min, grinding and stripping graphite by utilizing the shearing force generated by the grinding disc, reducing the pressure to 1atm within 10s after stirring for 48h, and sampling from the high-pressure grinding disc kettle to obtain the edge modified graphene G102.

When the prepared edge-modified graphene G102 is analyzed by a Scanning Electron Microscope (SEM), the average sheet diameter of the graphene is 9.6 μm, the average thickness is 3.2nm, and the average aspect ratio is 3000:1,X-ray photoelectron spectroscopy (XPS) was conducted, and the oxygen content was 7.83at%, the hydrogen content was 3.23at%, and the electrical conductivity was 425S/m.

G103

100g 32 meshUltrasonically cleaning flake graphite powder (washing with water for 1 time and washing with ethanol for 2 times) to remove impurity phase substances and impurity elements, placing the flake graphite in a high-pressure grinding disc kettle, sealing the high-pressure grinding disc kettle, heating the high-pressure grinding disc kettle to 70 ℃, and pumping CO into the high-pressure grinding disc kettle ₂ And (3) raising the pressure in the high-pressure grinding disc kettle to 125atm, setting the rotating speed to 1000r/min, grinding and stripping the graphite by utilizing the shearing force generated by the grinding disc, reducing the pressure to 1atm within 10s after stirring for 24h, and sampling from the high-pressure grinding disc kettle to obtain the edge modified graphene G103.

When the prepared edge-modified graphene is analyzed by a Scanning Electron Microscope (SEM), the average sheet diameter of the graphene is 6.2 microns, the average thickness of the graphene is 2.9nm, and the average aspect ratio of the graphene is 2138:1, X-ray photoelectron spectroscopy (XPS), an oxygen content of 13.40at%, a hydrogen content of 7.3at%, and a conductivity of 339S/m.

G104

Ultrasonically cleaning 100g 32-mesh crystalline flake graphite powder (water washing for 1 time and ethanol washing for 2 times) to remove impurity phase substances and impurity elements, placing the crystalline flake graphite in a high-pressure grinding disc kettle, sealing the high-pressure grinding disc kettle, heating the high-pressure grinding disc kettle to 70 ℃, and pumping CO into the high-pressure grinding disc kettle ₂ And (3) increasing the pressure in the high-pressure grinding disc kettle to 125atm, setting the rotating speed to 1000r/min, grinding and stripping graphite by utilizing the shearing force generated by the grinding disc, reducing the pressure to 1atm within 10s after stirring for 72h, and sampling from the high-pressure grinding disc kettle to obtain the edge modified graphene G104.

When the prepared edge-modified graphene is analyzed by a Scanning Electron Microscope (SEM), the average sheet diameter of the graphene is 4.3 μm, the average thickness is 3.18nm, and the average aspect ratio is 1352:1, X-ray photoelectron spectroscopy (XPS), an oxygen content of 19.40at%, a hydrogen content of 9.63at%, and an electrical conductivity of 286S/cm.

G105

Ultrasonically cleaning 100g 32-mesh crystalline flake graphite powder (washing with water for 1 time and washing with ethanol for 2 times) to remove impurity phase substances and impurity elements, placing the crystalline flake graphite in a high-pressure grinding disc kettle, sealing the high-pressure grinding disc kettle, heating the high-pressure grinding disc kettle to 40 ℃, and pumping CO into the high-pressure grinding disc kettle ₂ The pressure in the high-pressure grinding disc kettle is raised to 125atm, the rotating speed is 1000r/min, the graphite is ground and peeled off by utilizing the shearing force generated by a grinding disc, the pressure is reduced to 1atm within 10s after stirring for 16h, and the edge modified graphene G105 is obtained by sampling from a high-pressure grinding disc kettle.

When the prepared edge-modified graphene is analyzed by a Scanning Electron Microscope (SEM), the average sheet diameter of the graphene is 14.9 microns, the average thickness of the graphene is 3.8nm, and the average aspect ratio of the graphene is 3921:1,X-ray photoelectron spectroscopy (XPS) was conducted, and the oxygen content was 4.32at%, the hydrogen content was 2.35at%, and the conductivity was 536S/m.

Preparation example 2

Preparation example 2 is to illustrate the preparation process of the degradable copolyester.

PBST101

1) Under the action of a catalyst, 423.8g (2.55 mol) of monomer a terephthalic acid (PTA), 650g (7.21 mol) of monomer b1, 4-Butanediol (BDO), 330g (2.79 mol) of monomer c Succinic Acid (SA) and 1g (0.01 mol) of monomer d glycerol are mixed and subjected to esterification reaction to prepare long-chain branched aliphatic aromatic copolyester, wherein the temperature of the esterification reaction is 226 ℃, and the melt index of the long-chain branched aliphatic aromatic copolyester under the load of 2.16kg at 190 ℃ is 23g/10min; the catalyst contained 0.245g of tetrabutyl titanate (available from Beijing Chemicals), 0.31g of lanthanum stearate, 0.1g of dibutyltin oxide (available from Beijing chemical company III), 0.14g of triphenylhydroxytin (available from Beijing Chemicals);

2) 500g of the long-chain branched aliphatic aromatic copolyester prepared in the step 1) and 2.5g of 3, 6-bis (t-butylperoxy) -3, 6-dimethyloctane are subjected to extrusion reaction at 170 ℃ in an extruder to prepare the copolyester, and the prepared copolyester has a melt index of 1.9g/10min, a number average molecular weight of 4.6 ten thousand and a molecular weight distribution of 2.1 at 190 ℃ under a load of 2.16kg.

PBST102

1) Preparation of long-chain branched aliphatic aromatic copolyester: under the action of a catalyst, 423.8g (2.55 mol) of a monomer a terephthalic acid, 570.8g (7.5 mol) of a monomer b1, 3-propanediol, 438.4g (3 mol) of a monomer c dimethyl succinate and 1g (0.0046 mol) of a monomer d pyromellitic dianhydride are mixed for esterification reaction to prepare long-chain branched aliphatic aromatic copolyester, wherein the temperature of the esterification reaction is 235 ℃, and the melt index of the long-chain branched aliphatic aromatic copolyester under the load of 190 ℃ and 2.16kg is 15g/10min; the catalyst contained 0.245g of tetrabutyltitanate (available from Beijing Chemicals), 0.31g of lanthanum stearate, 0.1g of dibutyltin oxide (available from Beijing chemical three factories), 0.14g of triphenylhydroxytin (available from Beijing Chemicals);

2) 500g of the long-chain branched aliphatic aromatic copolyester prepared in the step 1) and 2.5g of 3, 6-bis (t-butylperoxy) -3, 6-dimethyloctane are subjected to extrusion reaction at 170 ℃ in an extruder to prepare the copolyester, and the prepared copolyester has a melt index of 2.0g/10min, a number average molecular weight of 5.2 ten thousand and a molecular weight distribution of 2.4 at 190 ℃ under a load of 2.16kg.

PBAT101

1) Preparation of long-chain branched aliphatic aromatic copolyester: under the action of a catalyst, mixing 679.6g (3.5 mol) of dimethyl terephthalate monomer a, 570.8g (7.5 mol) of 1, 3-propanediol monomer b, 657.6g (4.5 mol) of adipic acid monomer c and 0.7g (0.005 mol) of pentaerythritol monomer d for esterification reaction to prepare long-chain branched aliphatic aromatic copolyester, wherein the temperature of the esterification reaction is 232 ℃, and the melt index of the long-chain branched aliphatic aromatic copolyester under the load of 2.16kg at 190 ℃ is 40g/10min; the catalyst contained 0.245g of tetrabutyltitanate (available from Beijing Chemicals), 0.31g of lanthanum stearate, 0.1g of dibutyltin oxide (available from Beijing chemical three factories), 0.14g of triphenylhydroxytin (available from Beijing Chemicals);

2) 500g of the long-chain branched aliphatic aromatic copolyester prepared in the step 1) and 2.5g of 3, 6-bis (t-butylperoxy) -3, 6-dimethyloctane are subjected to extrusion reaction at 170 ℃ in an extruder to prepare the copolyester, and the prepared copolyester has a melt index of 2.6g/10min, a number average molecular weight of 4.8 ten thousand and a molecular weight distribution of 2.3 at 190 ℃ under a load of 2.16kg.

PBST103

1) Preparation of long-chain branched aliphatic aromatic copolyester: under the action of a catalyst, 423.8g (2.55 mol) of a monomer a terephthalic acid (PTA), 650g (7.21 mol) of a monomer b1, 4-Butanediol (BDO), 330g (2.79 mol) of a monomer c Succinic Acid (SA) and 1g (0.01 mol) of a monomer d glycerol are mixed for esterification, the temperature of the esterification is 229 ℃, and the melt index of the prepared long-chain branched aliphatic aromatic copolyester under the load of 2.16kg at 190 ℃ is 40g/10min; the catalyst contained 0.174g of tetrabutyl titanate (available from Beijing Chemicals), 0.071g of dibutyltin oxide (available from Beijing chemical three Mills), 0.099g of triphenylhydroxytin (available from Beijing Chemicals), and 0.22g of lanthanum stearate;

2) 500g of the long-chain branched aliphatic aromatic copolyester prepared in the step 1) and 5g of 2, 7-bis (tert-butylperoxy) -2, 7-dimethyloctane are subjected to extrusion reaction at 180 ℃ in an extruder to prepare the copolyester, and the prepared copolyester has the melt index of 2.3g/10min, the number average molecular weight of 4.5 ten thousand and the molecular weight distribution of 2.1 at 190 ℃ under the load of 2.16kg.

PBST104

1) Preparation of long-chain branched aliphatic aromatic copolyester: under the action of a catalyst, 423.8g (2.55 mol) of a monomer a terephthalic acid, 570.8g (7.5 mol) of a monomer b1, 3-propanediol, 438.4g (3 mol) of a monomer c dimethyl succinate and 1g (0.0046 mol) of a monomer d pyromellitic dianhydride are mixed for esterification reaction to prepare long-chain branched aliphatic aromatic copolyester, wherein the temperature of the esterification reaction is 234 ℃, and the melt index of the long-chain branched aliphatic aromatic copolyester under the load of 190 ℃ and 2.16kg is 15g/10min; the catalyst contained 0.245g of tetrabutyltitanate (available from Beijing Chemicals), 0.31g of lanthanum stearate, 0.1g of dibutyltin oxide (available from Beijing chemical three factories), 0.14g of triphenylhydroxytin (available from Beijing Chemicals);

2) 500g of the long-chain branched aliphatic aromatic copolyester prepared in the step 1) and 0.5g of dibenzoyl peroxide are subjected to extrusion reaction at 160 ℃ in an extruder to prepare the copolyester, and the prepared copolyester has the melt index of 1.5g/10min, the number average molecular weight of 5.0 ten thousand and the molecular weight distribution of 2.5 at 190 ℃ under the load of 2.16kg.

PBST105

1) Preparation of long-chain branched aliphatic aromatic copolyester: under the action of a catalyst, 423.8g (2.55 mol) of a monomer a terephthalic acid (PTA), 650g (7.21 mol) of a monomer b1, 4-Butanediol (BDO), 330g (2.79 mol) of a monomer c Succinic Acid (SA) and 1g (0.01 mol) of a monomer d glycerol are mixed and subjected to esterification reaction to prepare long-chain branched aliphatic aromatic copolyester, wherein the temperature of the esterification reaction is 233 ℃, and the melt index of the long-chain branched aliphatic aromatic copolyester under the load of 190 ℃ and 2.16kg is 25g/10min; the catalyst contained 0.245g of tetrabutyl titanate (available from Beijing Chemicals), 0.31g of lanthanum stearate, 0.1g of dibutyltin oxide (available from Beijing chemical company III), 0.14g of triphenylhydroxytin (available from Beijing Chemicals);

2) 500g of the long-chain branched aliphatic aromatic copolyester prepared in the step 1) and 2.5g of dibenzoyl peroxide are subjected to extrusion reaction at 170 ℃ in an extruder to prepare the copolyester, and the prepared copolyester has the melt index of 1.8g/10min, the number average molecular weight of 5.2 ten thousand and the molecular weight distribution of 2.6 at 190 ℃ under the load of 2.16kg.

PBS101

1) Preparation of long-chain branched aliphatic copolyesters: under the action of a catalyst, 550g (7.21 mol) of monomer b1, 4-Butanediol (BDO), 360g (2.79 mol) of monomer c Succinic Acid (SA) and 1.2g (0.01 mol) of monomer d glycerol are mixed for esterification reaction to prepare long-chain branched aliphatic aromatic copolyester, wherein the temperature of the esterification reaction is 230 ℃, and the melt index of the long-chain branched aliphatic aromatic copolyester under the load of 2.16kg and 190 ℃ is 15g/10min; the catalyst contained 0.245g of tetrabutyl titanate (available from Beijing Chemicals), 0.31g of lanthanum stearate, 0.1g of dibutyltin oxide (available from Beijing chemical company III), 0.14g of triphenylhydroxytin (available from Beijing Chemicals);

2) 500g of the long-chain branched aliphatic aromatic copolyester prepared in the step 1) and 3.1g of 2, 5-di-tert-butylperoxy-2, 5-dimethylhexane are subjected to extrusion reaction at 170 ℃ in an extruder to prepare the copolyester, and the prepared copolyester has the melt index of 1.8g/10min, the number average molecular weight of 4.6 ten thousand and the molecular weight distribution of 2.1 at 190 ℃ under the load of 2.16kg.

Examples 1 to 13

The examples serve to illustrate the antistatic biodegradable film of the present invention and the preparation method thereof:

the copolyester of the corresponding component in preparation example 2 is mixed with antioxidant 1010, antioxidant 168, edge modified graphene in preparation example 1, an antistatic agent, a slipping agent and a nucleating agent, and the mixture is added into a double-screw extruder to be subjected to melt extrusion granulation at 170 ℃ to prepare the film blowing material. And (3) blowing the film blowing material on a film blowing machine to obtain a film with the thickness of 10 +/-0.5 mu m at a certain die temperature and blowing ratio.

The types and proportions of the corresponding copolyester, slipping agent, nucleating agent, antistatic agent and compatilizer; the temperature of the film blowing die and the blow-up ratio are shown in Table 1. The type and the amount of the antioxidant are fixed as 1010:168=1, 100 parts of copolyester, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168.

The obtained film was subjected to a performance test, and the results of the optical properties and thermal properties thereof are shown in table 2, and the antistatic properties, opening properties, mechanical properties, barrier properties and other properties thereof are shown in table 3.

Comparative examples 1 to 4

Comparative examples 1-3 use other long-lasting antistatic agents such as carbon black, chemically exfoliated graphene (available from NanoScien technologies, inc., nanjing GmbH, oxygen content 32 at%), graphene mentioned in US20130018204 instead of edge-modified graphene obtained by the millstone method. Comparative example 4 silica was used instead of edge-modified graphene. The specific amounts added are shown in Table 1.

The obtained film was subjected to a performance test, and the optical and thermal performance test results thereof are shown in table 2, and the antistatic properties, the opening properties, the mechanical properties, the barrier properties and other properties thereof are shown in table 3.

As can be seen from the data in tables 2 and 3, the films prepared by blowing the degradable copolyester composition of the present invention have excellent opening performance, antistatic performance and better mechanical properties.

Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

Claims

1. The degradable copolyester composition is characterized by comprising the following components in parts by weight:

100 parts of degradable copolyester;

the average sheet diameter is 2 to 30 μm, preferably 5 to 15 μm; and/or

The conductivity is 200 to 800S/m, preferably 300 to 600S/m; and/or

2. The degradable copolyester composition according to claim 1, wherein the degradable copolyester is a fatty aromatic copolyester; the aliphatic aromatic copolyester contains a structural unit derived from a monomer b, a structural unit derived from a monomer c, a structural unit derived from a monomer d and an optional structural unit derived from a monomer a; the monomer a is aromatic dibasic acid and/or ester derivative thereof, the monomer b is at least one of aliphatic dibasic alcohol and alicyclic dibasic alcohol, the monomer c is aliphatic dibasic acid and/or ester derivative thereof, and the monomer d is at least one of polyfunctional polyalcohol, polycarboxylic acid and anhydride;

the melt index of the degradable copolyester at 190 ℃ under the load of 2.16kg is 0.1-10 g/10min, preferably 0.5-8 g/10min, and more preferably 1-6 g/10min; the number average molecular weight is 4-8 ten thousand, preferably 4-6 ten thousand; the molecular weight distribution is from 1.5 to 4, preferably from 2 to 3.

3. The degradable copolyester composition according to claim 2, wherein,

the monomer a is C ₈ -C ₂₀ Preferably terephthalic acid and/or dimethyl terephthalate;

the monomer b is C ₂ -C ₁₀ Aliphatic diols and C ₃ -C ₁₀ Preferably 1, 3-propanediol and/or 1, 4-butanediol;

the monomer C is C ₄ -C ₂₀ Preferably C and/or an ester derivative thereof ₄ -C ₈ More preferably selected from succinic acid, dimethyl succinate, adipic acid or dimethyl adipate;

the monomer d is at least one of polyalcohol with the functionality of more than 2, polycarboxylic acid with the functionality of more than 2 and anhydride with the functionality of more than 2, and is preferably at least one of pyromellitic dianhydride, glycerol and pentaerythritol.

4. The degradable copolyester composition according to claim 2, wherein the molar content of the structural unit derived from monomer a, the molar content of the structural unit derived from monomer B, the molar content of the structural unit derived from monomer C, and the molar content of the structural unit derived from monomer D, A, B, satisfy:

the molar ratio of (A + C): D is (100-2000): 1, preferably (300-1500): 1; and/or the presence of a gas in the atmosphere,

the molar ratio of A to C is 0: 100-60: 40, preferably 30: 100-60: 40.

5. The degradable copolyester composition according to claim 1, wherein the edge modified graphene is prepared by grinding graphite by a grinding disc under supercritical carbon dioxide; preferably, the edge-modified graphene is prepared by a method comprising the following steps: grinding graphite powder in a high-pressure grinding disc kettle in the presence of supercritical carbon dioxide;

the graphite powder is preferably selected from crystalline flake graphite powder and/or expanded graphite powder, and more preferably, the particle size of the graphite powder is 10-80 meshes, and is preferably 20-60 meshes.

6. The degradable copolyester composition according to claim 5, wherein the edge modified graphene is prepared by a method comprising the steps of:

s3, grinding a material containing graphite powder and supercritical carbon dioxide;

preferably, in step S2, the carbon dioxide is brought into a supercritical state by bringing the temperature in the tank to over 32.26 ℃ and the pressure to over 72.9 atm;

preferably, in step S3, after the grinding is completed, the pressure in the high-pressure grinding disc kettle is rapidly decreased; preferably, the pressure in the high-pressure grinding disc kettle is reduced to below 1atm within 5-20 seconds;

preferably, the temperature in the high-pressure grinding disc kettle is 35-200 ℃, preferably 35-100 ℃, and more preferably 35-70 ℃; a pressure of 75 to 165atm, preferably 75 to 150atm, more preferably 75 to 125atm; the stirring speed is 500-10000 r/min, preferably 500-5000 r/min; the grinding time is 6 to 48 hours.

7. The degradable copolyester composition according to claim 2, wherein the degradable copolyester is obtained by reacting a mixture comprising monomer b, monomer c, monomer d and optionally monomer a; preferably, the degradable copolyester is prepared by reacting a mixture containing a monomer b, a monomer c, a monomer d and an optional monomer a under the action of a catalyst to obtain long-chain branched aliphatic aromatic copolyester, and then performing extrusion reaction with an organic peroxide.

8. The degradable copolyester composition according to claim 7, wherein the degradable copolyester is prepared by a process comprising the steps of:

(1) Preparation of long-chain branched aliphatic aromatic copolyester: under the action of a catalyst, mixing a monomer b, a monomer c, a monomer d and an optional monomer a for esterification reaction, or mixing the monomer b or the monomer b with an esterification product of the monomer a and an esterification product of the monomer c with the monomer d for copolycondensation reaction to obtain the long-chain branched aliphatic aromatic copolyester;

9. The degradable copolyester composition according to claim 7 or 8, wherein the catalyst contains at least one of a first catalyst, a second catalyst and a third catalyst;

the first catalyst is selected from the oxides of M, M (OR) ₁ ) n and M (OOCR) ₂ ) M is at least one of titanium, antimony or zinc, n and M are each independently the valence of M, R ₁ Is C ₁ -C ₁₀ Alkyl of R ₂ Is C ₁ -C ₂₀ Alkyl groups of (a); preferably, the first catalyst is selected from at least one of titanium alkoxide, antimony acetate, zinc oxide, antimony oxide, titanium oxide, titanate, and titanium alkoxide; more preferably, the first catalyst is selected from at least one of tetrabutyl titanate, titanium isopropoxide, titanium dioxide, antimony trioxide, antimony acetate and zinc acetate;

and/or the presence of a gas in the atmosphere,

the second catalyst is RE (R) ₃ ) ₃ Wherein RE is a rare earth metal element and/or a titanium-based metal element, R is at least one of a compound of (1) and a hydrate thereof ₃ Selected from the group consisting of halogen, alkoxy, aryloxy, acetylacetonate and R ₄ At least one of COO-groups, R ₄ Is C ₁ -C ₃₀ Alkyl groups of (a); preferably, RE is selected from at least one of lanthanum, cerium, praseodymium, neodymium, terbium, ytterbium, dysprosium, samarium, scandium, titanium, zirconium, and hafnium; the halogen is chlorine and/or bromine, and the alkoxy is C ₃ ～C ₆ An aryloxy group being an aryloxy group comprising at least one benzene ring and/or naphthalene ring, R ₄ Is C ₁ ～C ₂₀ Alkyl groups of (a);

more preferably, RE is selected from at least one of lanthanum, cerium, praseodymium, neodymium and scandium, the halogen is chlorine and/or bromine, the alkyl group in the alkoxy group is at least one of isopropyl, n-butyl and isoamyl, the aryl group in the aryloxy group is at least one of 2, 6-di-tert-butyl-4-methylphenyl and 4-butylphenyl, R is ₄ Is C ₃ -C ₁₈ At least one of alkyl groups of (a);

and/or the presence of a gas in the gas,

the third catalyst is at least one organotin compound; preferably, the third catalyst is selected from at least one of dibutyl tin oxide, methylphenyl tin oxide, tetraethyl tin, hexaethyl tin oxide, hexacyclohexyl ditin oxide, didodecyl tin oxide, triethyl hydroxyl tin, triphenyl hydroxyl tin, triisobutyl tin acetate, dibutyltin diacetate, diphenyl tin dilaurate, monobutyl tin trichloride, tributyl tin chloride, dibutyl tin sulfide, butyl hydroxyl tin oxide, methyl stannic acid, ethyl stannic acid, and butyl stannic acid; more preferably, the third catalyst is selected from the group consisting of mixtures of at least two of dibutyl tin oxide, tetraethyl tin, triphenyl hydroxyl tin, dibutyl tin diacetate, diphenyl tin dilaurate, monobutyl tin trichloride, tributyl tin chloride, dibutyl tin sulfide, butyl hydroxyl tin oxide, methyl stannoic acid, ethyl stannoic acid, and butyl stannoic acid; further preferably, the content of each component in the third catalyst is 10 to 90 mol%, preferably 30 to 70 mol%, based on the total molar amount of the third catalyst being 100 mol%.

10. The degradable copolyester composition according to claim 7 or 8, wherein the molar ratio of the total amount of the catalyst to the total amount of the monomer (a + c) is 1: 1000-20000; preferably 1: (1000-10000); and/or the presence of a gas in the atmosphere,

11. The degradable copolyester composition according to claim 7 or 8, wherein,

the organic peroxide is selected from organic peroxides with half-life period of 0.2-10 min, preferably 0.2-2 min within the processing temperature range;

preferably, the organic peroxide is selected from at least one of alkyl peroxides, acyl peroxides, and peroxyesters;

more preferably, the organic peroxide is selected from at least one of 2, 5-bis (t-amylperoxy) -2, 5-dimethylhexane, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane, 3, 6-bis (t-butylperoxy) -3, 6-dimethyloctane, 2, 7-bis (t-butylperoxy) -2, 7-dimethyloctane, 8, 11-bis (t-butylperoxy) -8, 11-dimethyloctadecane or a mixture thereof, bis (alkylperoxy) benzene, bis (alkylperoxy) alkyne and dibenzoyl peroxide; wherein the bis (alkylperoxy) benzene is preferably selected from the group consisting of α, α '- (t-amylperoxy-isopropyl) benzene, α' -bis (t-butylperoxy-isopropyl) benzene, or mixtures thereof; the bis (alkylperoxy) alkyne is selected from at least one of 2, 7-dimethyl-2, 7-di (t-butylperoxy) -octadiyne-3, 5,2, 7-dimethyl-2, 7-di (peroxyethyl carbonate) -octadiyne-3, 5,3, 6-dimethyl-3, 6-di (t-butylperoxy) octyne-4, 2, 5-dimethyl-2, 5-di (peroxy-n-propyl-carbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (peroxy-isobutyl carbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (peroxyethyl monocarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di ((α -cumylperoxy) hexyne-3, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3;

the dosage of the organic peroxide is 0.01-5 wt%, preferably 0.01-1 wt% of the dosage of the long-chain branched aliphatic aromatic copolyester.

12. The degradable copolyester composition according to claim 8, wherein,

in the step 1), the temperature of the esterification reaction is 150-220 ℃; the conditions of the polycondensation reaction include: the temperature is 250-270 ℃, and the time is 2-3 hours;

the melt index of the long-chain branched aliphatic aromatic copolyester prepared in the step 1) is 5-100 g/10min at 190 ℃ under the load of 2.16 kg;

in step 2), the extrusion temperature is 150-200 ℃, preferably 160-180 ℃.

13. The degradable copolyester composition according to claim 1, wherein the degradable copolyester composition further comprises a compatibilizer, the content of which is 1 to 10 parts by weight, preferably 3 to 7 parts by weight, based on 100 parts by weight of the total amount of the degradable copolyester and the antistatic agent;

the compatilizer is preferably at least one of maleic anhydride grafted PBST, glycidyl methacrylate grafted PBST, maleic anhydride grafted PBAT and glycidyl methacrylate grafted PBAT, and the grafting rate is more than 1wt%.

14. Use of the degradable copolyester composition of any one of claims 1 to 13 as an antistatic biodegradable material.

15. An antistatic biodegradable film material, comprising the degradable copolyester composition of any one of claims 1 to 13, and a film aid in an amount of 1 to 50 parts by weight, preferably 2 to 22 parts by weight, based on 100 parts by weight of the degradable copolyester composition; the film auxiliary agent is preferably at least one of a slipping agent, a nucleating agent, an antioxidant and a degradable resin.

16. The antistatic biodegradable film material according to claim 15, wherein the slip agent is contained in an amount of 0.05 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the degradable copolyester composition;

the slipping agent is selected from stearate and/or organic carboxylic acid amide, wherein the stearate is preferably self-calcium stearate, and the organic carboxylic acid amide is preferably selected from at least one of erucamide, oleamide, stearic acid stearamide and N, N '-ethylene bisstearamide, and is more preferably N, N' -ethylene bisstearamide.

17. The antistatic biodegradable film material according to claim 15, wherein the nucleating agent is contained in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the degradable copolyester composition;

the nucleating agent is selected from at least one of hyperbranched polyamide, low-density polyethylene, ethylene-methacrylic acid ionomer and ethylene-butyl acrylate-glycidyl methacrylate terpolymer; preferably an ethylene-methacrylic acid ionomer and/or an ethylene-butyl acrylate-glycidyl methacrylate terpolymer.

18. The antistatic biodegradable film material according to claim 15, wherein the antioxidant is contained in an amount of 0.05 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the degradable copolyester composition;

the antioxidant is a hindered phenol antioxidant and a phosphite antioxidant which are mixed according to the mass ratio of 1; wherein the hindered phenol antioxidant is preferably at least one selected from the group consisting of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-tert-butyl-4-hydroxybenzyl) benzene; the phosphite antioxidant is preferably at least one selected from the group consisting of tris [2, 4-di-tert-butylphenyl ] phosphite, pentaerythrityl distearyl diphosphite and 2,2' -ethylidene bis (4, 6-di-tert-butylphenyl) fluorophosphite.

19. The antistatic biodegradable film material according to claim 15, wherein the degradable resin is contained in an amount of 1 to 20 parts by weight, preferably 2 to 12 parts by weight, based on 100 parts by weight of the degradable copolyester composition;

the degradable resin is at least one of polycaprolactone, polybutylene succinate adipate, polyglycolic acid, polylactic acid, polyhydroxyalkanoate and polymethyl ethylene carbonate.

20. A method for preparing the antistatic biodegradable film material according to any one of claims 15-19, comprising the steps of:

21. An antistatic biodegradable film made of the antistatic biodegradable film material as set forth in any one of claims 15 to 19.

22. An antistatic biodegradable film according to claim 21, wherein the thickness of said film is 5-100 μm, preferably 10-20 μm;

the light transmittance of the film is more than 87%;

the haze of the film is 15% or less;

the falling mark impact failure mass of the film is more than 20 g;

the tensile breaking stress of the film is greater than 18MPa, preferably greater than 25MPa, more preferably between 25 and 100MPa;

the film has a longitudinal tensile strength of 18MPa or more, preferably 24MPa or more; a transverse tensile strength of 16MPa or more, preferably 20MPa or more;

the film has a longitudinal elongation at break of 250% or more, preferably 300% or more; a transverse elongation at break of 300% or more, preferably 350% or more;

the MD direction right-angle tearing load of the film is more than 2.2N, and the TD direction right-angle tearing load of the film is more than 2.5N;

the opening force of the film is more than 0.01N/cm ³ ；

The film has a water permeability of less than 370g m at 38 ℃, 90% RH ^-2 ·d ^-1 ；

The surface resistivity of the film is less than 2 x 10 ¹⁰ Ω。

23. The antistatic biodegradable film of claim 21 wherein the antistatic biodegradable film is made from the antistatic biodegradable film material by blow molding;

preferably, the temperature of the blown film forming is 150-210 ℃, preferably 160-200 ℃;

preferably, in the blown film process, the blow-up ratio is 1.5 to 3, preferably 2 to 2.5.

24. Use of the degradable copolyester composition of any one of claims 1 to 13, the antistatic biodegradable film material of any one of claims 15 to 19, or the antistatic biodegradable film of any one of claims 21 to 23 in the preparation of electronic packaging bag films.