CN118420571A - Furan-based polyester film composition, nucleating agent and preparation method thereof - Google Patents

Abstract

In order to solve the problem of slow stretching rate and low forming efficiency of furan-based polyester in the process of biaxial stretching, the present invention provides a furan-based polyester film composition with rapid forming and high barrier performance, a nucleating agent and a preparation method. A new nucleating agent N, N'-1,4-benzenedifuranamide was prepared using furoyl chloride of biological origin as a raw material. In terms of mass fractions, 100 parts of furan-based polyester and 0.1-3 parts of nucleating agent were blended to prepare a furan-based polyester film composition with rapid forming and high barrier performance. The present invention uses a new nucleating agent, and the polyester composition film is formed quickly, which effectively improves the barrier performance of the furan-based polyester film and the crystallization efficiency in the biaxial stretching process, and has a good market prospect.

Description

A furan-based polyester film composition, a nucleating agent and a preparation method thereof

Technical Field

The invention belongs to the technical field of biomass furan-based polyesters, and in particular relates to a rapid-forming and high-barrier furan-based polyester film composition, a nucleating agent and a preparation method.

Background technique

With the increasing scarcity of traditional petroleum resources and the serious problem of environmental pollution, the development of biomass-based materials has gradually received widespread attention. Pentahydroxymethylfurfural is a biomass raw material that can be extracted from natural plants. After further preparation, it can be converted into furan dicarboxylic acid (FDCA) monomer. The furan-based polyester prepared from this monomer has developed rapidly in recent years, among which polyethylene furan dicarboxylate (PEF) is a typical example. Compared with the petroleum-based raw material terephthalic acid (PTA), FDCA has the same functional groups and similar aromaticity and reactivity, and can be formed into a series of high-performance polymer materials through polycondensation with diols or diamines. Its derivative products have the advantages of non-toxicity, renewability, and controllable degradation, and the properties such as glass transition temperature, melting point, Young's modulus, and tensile strength are comparable to those of PTA products. Therefore, the polyethylene terephthalate-2,5-furandicarboxylate copolyester (PETF) prepared by introducing FDCA into the PTA system by copolymerization can greatly improve its performance advantages compared with traditional polyethylene terephthalate (PET). However, the slow crystallization rate and long molding cycle of PETF polyester limit the application of PETF in production and life. Developing a new nucleating agent to solve the problem of slow stretching rate and low molding efficiency of furan-based polyester film during biaxial stretching molding is a technical problem that needs to be solved urgently.

Summary of the invention

In order to solve the problem of slow stretching rate and low forming efficiency of furan-based polyester film in the process of biaxial stretching, the present invention provides a nucleating agent for furan-based polyester, a rapid forming and high barrier performance furan-based polyester film composition and a preparation method thereof. The present invention uses a new nucleating agent to promote rapid film forming of the polyester composition, effectively improving the barrier performance of the furan-based polyester film and the efficiency in the biaxial stretching process.

In a first aspect, the present invention provides a type of nucleating agent for furan-based polyesters, wherein the nucleating agent is N,N'-1,4-benzenedifuranamide, and the structural formula is:

In a second aspect, the present invention provides a method for preparing a nucleating agent for improving the rapid prototyping and barrier properties of a furan-based polyester film composition, the specific steps of which are:

S1, add p-phenylenediamine, acid binding agent and solvent into the reactor, control the temperature to -10～5, and stir;

S2, dissolving furoyl chloride in the same solvent and slowly dripping it into the reactor, the dripping time is not less than 20 minutes;

S3, heating to the reflux temperature of the solvent, reacting for not less than 3 hours;

S4. After the reaction is completed, the mixture is cooled to room temperature, filtered, washed and dried to obtain a white powder, which is the nucleating agent N,N'-1,4-benzenedifuranamide.

Furthermore, the molar ratio of p-phenylenediamine to furoyl chloride is 1:2.05-2.2; the molar ratio of furoyl chloride to acid binding agent is 1:1.

Furthermore, the acid binding agent is selected from at least one of triethylamine and pyridine.

Furthermore, the solvent is selected from one of acetonitrile, toluene, chloroform, dioxane, dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone.

Furthermore, in the step S1, the mass ratio of p-phenylenediamine to solvent is 0.02-0.045:1.

Furthermore, the mass ratio of furoyl chloride to solvent in step S2 is 0.06-0.12:1.

Furthermore, in step S1, the mixture is placed in an ice water bath at a temperature of -10 to 5°C and stirred by magnetic force.

Furthermore, the step S4 adopts suction filtration under reduced pressure; washing adopts anhydrous ethanol and distilled water; and the drying method is vacuum drying at 80°C.

The raw material of the nucleating agent prepared by the method is derived from straw biomass, has no odor, good compatibility, is easy to disperse, and does not precipitate.

In a third aspect, the present invention provides a rapid prototyping and high barrier performance furan-based polyester film composition, which comprises, by weight, 100 parts of furan-based polyester and 0.1-3 parts of a nucleating agent;

The nucleating agent is N,N'-1,4-benzenedifuranamide, and the structural formula is:

The furan-based polyester is ethylene furandicarboxylate, propylene furandicarboxylate, butylene furandicarboxylate, pentylene furandicarboxylate, hexanediol furandicarboxylate, octanediol furandicarboxylate, polyethylene terephthalate-2,5-furandicarboxylate copolyester, polypropylene terephthalate-2,5-furandicarboxylate copolyester, polybutylene terephthalate-2,5-furandicarboxylate copolyester, polyhexanediol furandicarboxylate, At least one of poly(2,5-furandicarboxylic acid-ethylene glycol copolyester), poly(adipate-2,5-furandicarboxylic acid-propylene glycol copolyester), poly(adipate-2,5-furandicarboxylic acid-butylene glycol copolyester), poly(2,5-furandicarboxylic acid-cyclohexanedimethanol-ethylene glycol copolyester), poly(2,5-furandicarboxylic acid-cyclohexanedimethanol-propylene glycol copolyester, and poly(2,5-furandicarboxylic acid-cyclohexanedimethanol-butylene glycol copolyester.

Furthermore, the mass ratio of the furan-based polyester to the nucleating agent is preferably 100:0.1-1.

Furthermore, the mass ratio of the furan-based polyester to the nucleating agent is preferably 100:0.3-0.5.

In a fourth aspect, the present invention provides a method for preparing a furan-based polyester film composition with rapid prototyping and high barrier properties, wherein the furan-based polyester and the nucleating agent are pre-mixed in proportion; and then melt blending, cast molding, and biaxial stretching processes are sequentially performed to obtain the furan-based polyester film composition.

Furthermore, the melt blending process is: placing the pre-mixed furan-based polyester and the nucleating agent in a twin-screw extruder for melt blending to obtain a masterbatch; the processing temperature of the twin-screw extruder is 190-250, and the screw speed is 140-160rpm.

Furthermore, the tape-casting process is: placing the masterbatch in a single-screw extrusion tape-casting machine for tape-casting to obtain a sheet; the processing temperature of the single-screw extrusion tape-casting machine is 190-250, and the screw speed is 110-130rpm.

Furthermore, the biaxial stretching process is: placing the sheet in a biaxial stretching machine for biaxial stretching to obtain the furan-based polyester film composition; the processing temperature of the biaxial stretching machine is 100-120, the stretching ratio is 2-5, the stretching speed is 50v/s-400v/s, and the setting temperature is 130-150.

Furthermore, in the tape-casting process, the masterbatch is placed in a single-screw extruder tape-casting machine for tape-casting, thereby obtaining a sheet of the furan-based polyester film composition with a thickness of 500-600 μm.

Furthermore, before biaxial stretching, the tape-cast sheet is cut into sheets not exceeding 20×20 cm. The thickness of the film after biaxial stretching is 25-55 μm.

Furthermore, the processing temperatures of the conveying section, melting section, mixing section, exhaust section, and homogenizing section of the twin-screw extruder are 190, 220, 230, 245, 250, the die temperature is 248, and the screw speed is 150 rpm.

Furthermore, the processing temperatures of the conveying section, melting section, mixing section, exhaust section, and homogenizing section of the single-screw extruder casting machine are 190, 220, 230, 245, and 250, the die temperature is 260, and the screw speed is 120 rpm.

Furthermore, the mass ratio of the furan-based polyester to the nucleating agent is 100:0.1-1.

Furthermore, before pre-mixing, the furan-based polyester and the nucleating agent are first placed in a vacuum oven at 80-100° C. and dried for 12-24 hours.

Furthermore, before preparing the sheet, the masterbatch is dried in an oven at 100-120°C for 12-24 hours.

The invention discloses application of the nucleating agent N,N'-1,4-benzenedifurancarboxamide in polyester, specifically application in improving barrier properties and stretching molding efficiency of furan-based polyester.

Beneficial effects:

Furoyl chloride, one of the raw materials of the nucleating agent selected in the present invention, is derived from straw biomass, is safe and environmentally friendly, and is non-toxic and harmless to the human body and the environment; N,N'-1,4-benzenedifurancarboxamide is used as a nucleating agent, and is melt-blended with a furan-based polyester to obtain a furan-based polyester composition, and a furan-based polyester film composition is prepared by a biaxial stretching process. The preparation steps are simple and economical, and rapid molding is achieved by one-step reaction, so that a furan-based polyester film material with rapid molding and high barrier performance is obtained, which is suitable for industrial production;

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the NMR-H spectrum of the N,N′-1,4-benzenedifuranamide nucleating agent in Example 1.

Detailed ways

In order to more clearly understand the above-mentioned purpose, features and advantages of the present invention, the scheme of the present invention will be further described below. It should be noted that the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein; it is obvious that the embodiments in the specification are only part of the embodiments of the present invention, rather than all of the embodiments.

The preferred embodiments of the present invention will be described in detail below in conjunction with examples. It should be understood that the following examples are provided only for the purpose of illustration and are not intended to limit the scope of the present invention. Those skilled in the art may make various modifications and substitutions to the present invention without departing from the purpose and spirit of the present invention.

Test instrument model: The nuclear magnetic resonance spectrometer used was Vaian DLG400 (Varian, USA), and the gas permeameter used was VAC-V2 (Languang, China).

Example 1 (Preparation of nucleating agent, N,N'-1,4-benzenedifuranamide)

Weigh 1.081g p-phenylenediamine and 2.23g triethylamine in a 100mL two-necked flask with a magnet, add 30mL acetonitrile thereto, and place the flask in a 0.5% ice bath stirring pot. Weigh 2.872g furoyl chloride in a beaker, add 15mL acetonitrile thereto, and after it is fully dissolved, transfer it to a 25mL constant pressure funnel, and transfer the residual liquid in the beaker three times with 5mL acetonitrile. Under a 0.5% environment, slowly drop the furoyl chloride solution in the constant pressure funnel into the flask, and control the total dropwise addition time to about half an hour. After the dropwise addition is completed, heat to 80°C and react for 3 hours. After the reaction is completed, the mixture is cooled to room temperature and filtered. The filter cake is washed twice with deionized water and once with anhydrous ethanol. The mixture is dried under vacuum at 80°C for 12 h to obtain a white powder with a yield of 91.4%. Analysis by hydrogen nuclear magnetic resonance spectroscopy showed that the structure of the obtained product was consistent with that of N, N'-1,4-benzenedifuramide.

Example 2 (Blending)

The nucleating agent and furandicarboxylic acid ethylene glycol prepared in Example 1 were dried in a vacuum oven at 60°C for 12 hours. 5kg of polyethylene furandicarboxylic acid ethylene glycol was mixed with 3g of nucleating agent in a ziplock bag in advance, and then placed in a SHJ20 twin-screw extruder for melt mixing. The five temperature control zone temperatures and the head temperature of the extruder were set to 190, 220, 230, 245, 250, and 248, respectively, and the screw speed was 150rpm. The furandicarboxylic acid ethylene glycol sheet was prepared by a single screw casting machine, and the five temperature control zone temperatures and the head temperature of the single screw casting machine were set to 200, 220, 230, 245, 250, and 260, respectively, and the screw speed was 120rpm.

Example 3 (Blending)

Polyethylene furandicarboxylate was dried at 60°C in a vacuum oven for 12 hours. Then it was placed in a SHJ 20 twin-screw extruder for melt mixing. The five temperature control zone temperatures and the head temperature of the extruder were set to 190, 220, 230, 245, 250, and 248, respectively, and the screw speed was 150 rpm. The single-screw casting machine was used to prepare the ethylene furandicarboxylate sheet, and the five temperature control zone temperatures and the head temperature of the single-screw casting machine were set to 200, 220, 230, 245, 250, and 260, respectively, and the screw speed was 120 rpm.

Example 4 (Blending)

The nucleating agent and furandicarboxylic acid propylene glycol prepared in Example 1 were dried in a vacuum oven at 60°C for 12 hours. 5 kg of poly(propylene glycol furandicarboxylic acid) was mixed with 3 g of nucleating agent in a ziplock bag in advance, and then placed in a SHJ 20 twin-screw extruder for melt mixing. The five temperature control zone temperatures and the head temperature of the extruder were set to 160, 170, 190, 210, 220, and 235, respectively, and the screw speed was 150 rpm. Propylene glycol furandicarboxylic acid sheets were prepared by a single screw casting machine, and the five temperature control zone temperatures and the head temperature of the single screw casting machine were set to 160, 170, 190, 210, 220, and 235, respectively, and the screw speed was 120 rpm.

Example 5 (Blending)

Pure furandicarboxylic acid propylene glycol ester was dried in a vacuum oven at 60°C for 12 hours, and then placed in a SHJ 20 twin-screw extruder for melt mixing. The temperatures of the five temperature control zones of the extruder and the head temperature were set to 160, 170, 190, 210, 220, and 235, respectively, and the screw speed was 150 rpm. The furandicarboxylic acid propylene glycol ester sheet was prepared by a single-screw casting machine, and the temperatures of the five temperature control zones of the single-screw casting machine and the head temperature were set to 160, 170, 190, 210, 220, and 235, respectively, and the screw speed was 120 rpm.

Example 6 (double pull)

The ethylene glycol furandicarboxylate sheet prepared in Example 2 was cut into 13x13 cm pieces and subjected to a biaxial stretching test in a biaxial stretching device at a stretching temperature of 105°C, a stretching rate of 50 v/s, a stretching ratio of 3, and a setting temperature of 150°C.

Example 7 (double pull)

The conditions are consistent with those in Example 6, except that the stretching ratio is changed to 4.

Example 8 (double pull)

The conditions are consistent with those in Example 6, except that the stretching ratio is changed to 5.

Example 9 (double pull)

The conditions were consistent with those in Example 6, except that the stretching rate was changed to 100 v/s.

Example 10 (double pull)

The conditions were consistent with those in Example 6, except that the stretching rate was changed to 200 v/s.

Example 11 (Comparative Example)

The ethylene glycol furandicarboxylate sheet prepared in Example 3 was cut into 13x13 cm pieces and subjected to a biaxial stretching test in a biaxial stretching device at a stretching temperature of 105°C, a stretching rate of 50 v/s, a stretching ratio of 3, and a setting temperature of 150°C.

Example 12 (Comparative Example)

The conditions were consistent with those in Example 11, except that the stretching ratio was changed to 4.

Example 13 (Comparative Example)

The conditions were consistent with those in Example 11, except that the stretching ratio was changed to 5.

Example 14 (Comparative Example)

The conditions were consistent with those in Example 11, except that the stretching rate was changed to 100 v/s.

Example 15 (Comparative Example)

The conditions were consistent with those in Example 11, except that the stretching rate was changed to 200 v/s.

Example 16 (double pull)

The propylene glycol furandicarboxylate sheet prepared in Example 4 was cut into 13x13 cm pieces and subjected to a biaxial stretching test in a biaxial stretching device at a stretching temperature of 85°C, a stretching rate of 50 v/s, a stretching ratio of 3, and a setting temperature of 150°C.

Example 17 (double pull)

The conditions are consistent with those in Example 16, except that the stretching ratio is changed to 4.

Example 18 (double pull)

The conditions were consistent with those in Example 16, except that the stretching ratio was changed to 5.

Example 19 (double pull)

The conditions were consistent with those of Example 16, except that the stretching rate was changed to 100 v/s.

Example 20 (double pull)

The conditions were consistent with those of Example 16, except that the stretching rate was changed to 200 v/s.

Example 21 (Comparative Example)

The propylene glycol furandicarboxylate sheet prepared in Example 5 was cut into 13x13 cm pieces and subjected to a biaxial stretching test in a biaxial stretching device at a stretching temperature of 105°C, a stretching rate of 50 v/s, a stretching ratio of 3, and a setting temperature of 150°C.

Example 22 (Comparative Example)

The conditions are consistent with those in Example 21, except that the stretching ratio is changed to 4.

Example 23 (Comparative Example)

The conditions were consistent with those in Example 21, except that the stretching ratio was changed to 5.

Example 24 (Comparative Example)

The conditions were consistent with those of Example 21, except that the stretching rate was changed to 100 v/s.

Example 25 (Comparative Example)

The conditions were consistent with those in Example 21, except that the stretching rate was changed to 200 v/s.

Example 26 (Blending)

The nucleating agent prepared in Example 1 and poly furandicarboxylic acid-terephthalic acid-ethylene glycol ester (PETF-10) were dried at 60 °C in a vacuum oven for 12 hours. 5 kg PETF-10 and 3 g nucleating agent were mixed in advance in a ziplock bag, and then placed in a SHJ20 twin-screw extruder for melt mixing. The five temperature control zone temperatures and the head temperature of the extruder were set to 190, 220, 230, 245, 250, and 248, respectively, and the screw speed was 150 rpm. The furandicarboxylic acid ethylene glycol ester sheet was prepared through a single screw casting machine, and the five temperature control zone temperatures and the head temperature of the single screw casting machine were set to 200, 220, 230, 245, 250, and 260, respectively, and the screw speed was 120 rpm.

Example 27 (Blending)

Polyfuran dicarboxylic acid-terephthalic acid-ethylene glycol ester (PETF-10) was dried at 60°C for 12 hours in a vacuum drying oven. Then an SHJ20 twin screw extruder was placed and melt mixed. Five temperature control zone temperatures and die temperature of the extruder were set at 190°C, 220°C, 230°C, 245°C, 250°C, and 248°C, and the screw speed was 150rpm. Through a single screw casting machine, ethylene furan dicarboxylic acid sheet was prepared, and five temperature control zone temperatures and die temperature of the single screw casting machine were set at 200°C, 220°C, 230°C, 245°C, 250°C, and 260°C, and the screw speed was 120rpm.

Example 28 (Blending)

The conditions were consistent with those in Example 26, except that the copolyester ratio was changed to PETF20.

Example 29 (Blending)

The conditions were consistent with those in Example 26, except that the copolyester ratio was changed to PETF30.

Example 30 (Blending)

The conditions were consistent with those in Example 26, except that the copolyester ratio was changed to PETF40.

Example 31 (Blending)

The conditions were consistent with those in Example 26, except that the copolyester ratio was changed to PETF50.

Example 32 (double pull)

The PETF10 sheet prepared in Example 26 was cut into 13×13 cm and subjected to a biaxial stretching experiment in a biaxial stretching device with a stretching temperature of 100°C, a stretching rate of 50 v/s, a stretching ratio of 3, and a setting temperature of 140°C.

Example 33 (double pull)

The conditions are consistent with those in Example 32, except that the stretching ratio is changed to 4.

Example 34 (double pull)

The conditions are consistent with those in Example 32, except that the stretching ratio is changed to 5.

Example 35 (double pull)

The conditions were consistent with those of Example 32, except that the stretching rate was changed to 100 v/s.

Example 36 (double pull)

The conditions were consistent with those of Example 32, except that the stretching rate was changed to 200 v/s.

Example 37 (double pull)

The conditions were consistent with those in Example 32, except that the stretching temperature was changed to 110°C.

Example 38 (double pull)

The conditions were the same as those in Example 32, except that the stretching temperature was changed to 120°C.

Example 39 (double pull)

The PETF20 sheet prepared in Example 28 was cut into 13×13 cm and subjected to a biaxial stretching experiment in a biaxial stretching device with a stretching temperature of 100°C, a stretching rate of 50 v/s, a stretching ratio of 3, and a setting temperature of 140°C.

Example 40 (double pull)

The conditions are consistent with those of Example 39, except that the stretching ratio is changed to 4.

Example 41 (double pull)

The conditions are consistent with those of Example 39, except that the stretching ratio is changed to 5.

Example 42 (double pull)

The conditions were consistent with those of Example 39, except that the stretching rate was changed to 100 v/s.

Example 43 (double pull)

The conditions were consistent with those of Example 39, except that the stretching rate was changed to 200 v/s.

Example 44 (double pull)

The conditions were the same as those in Example 39, except that the stretching temperature was changed to 110°C.

Example 45 (double pull)

The conditions were the same as those in Example 39, except that the stretching temperature was changed to 120°C.

Example 46 (double pull)

The PETF30 sheet prepared in Example 29 was cut into 13×13 cm and subjected to a biaxial stretching experiment in a biaxial stretching device with a stretching temperature of 100°C, a stretching rate of 50 v/s, a stretching ratio of 3, and a setting temperature of 140°C.

Example 47 (double pull)

The conditions are consistent with those in Example 46, except that the stretching ratio is changed to 4.

Example 48 (double pull)

The conditions are consistent with those in Example 46, except that the stretching ratio is changed to 5.

Example 49 (double pull)

The conditions were consistent with those of Example 46, except that the stretching rate was changed to 100 v/s.

Example 50 (double pull)

The conditions were consistent with those of Example 46, except that the stretching rate was changed to 200 v/s.

Example 51 (double pull)

The conditions were consistent with those in Example 46, except that the stretching temperature was changed to 110°C.

Example 52 (double pull)

The conditions were the same as those in Example 46, except that the stretching temperature was changed to 120°C.

Example 53 (double pull)

The PETF40 sheet prepared in Example 30 was cut into 13×13 cm and subjected to a biaxial stretching experiment in a biaxial stretching device with a stretching temperature of 100°C, a stretching rate of 50 v/s, a stretching ratio of 3, and a setting temperature of 140°C.

Example 54 (double pull)

The conditions are consistent with those in Example 53, except that the stretching ratio is changed to 4.

Example 55 (double pull)

The conditions are consistent with those in Example 53, except that the stretching ratio is changed to 5.

Example 56 (double pull)

The conditions were consistent with those of Example 53, except that the stretching rate was changed to 100 v/s.

Example 57 (double pull)

The conditions were consistent with those of Example 53, except that the stretching rate was changed to 200 v/s.

Example 58 (double pull)

The conditions were the same as those in Example 53, except that the stretching temperature was changed to 110°C.

Example 59 (double pull)

The conditions were the same as those in Example 53, except that the stretching temperature was changed to 120°C.

Example 60 (double pull)

The PETF50 sheet prepared in Example 31 was cut into 13×13 cm and subjected to a biaxial stretching experiment in a biaxial stretching device with a stretching temperature of 100°C, a stretching rate of 50 v/s, a stretching ratio of 3, and a setting temperature of 140°C.

Example 61 (double pull)

The conditions are consistent with those in Example 60, except that the stretching ratio is changed to 4.

Example 62 (double pull)

The conditions are consistent with those in Example 60, except that the stretching ratio is changed to 5.

Example 63 (double pull)

The conditions were consistent with those of Example 60, except that the stretching rate was changed to 100 v/s.

Example 64 (double pull)

The conditions were consistent with those of Example 60, except that the stretching rate was changed to 200 v/s.

Example 65 (double pull)

The conditions were the same as those in Example 60, except that the stretching temperature was changed to 110°C.

Example 66 (double pull)

The conditions were the same as those in Example 60, except that the stretching temperature was changed to 120°C.

Gas barrier performance test: The prepared furan-based polyester film was cut into circular sheets with a diameter of 5 cm for gas barrier performance test. The test standard was GB/T 1038-2000, the test temperature was 23, and the test humidity was 0% RH. The test results are shown in Figures 1 and 2.

Mechanical properties test: The prepared furan-based polyester film was cut into rectangular sheets of 1 cm × 5 cm for mechanical properties test. The test standard was GB/T 1040.3-2006, and the stretching speed was 100 mm/min. The test results of PEF and PTF biaxially stretched films are shown in Table 1, and the results of PETF biaxially stretched films are shown in Tables 1 and 2.

Table 1 Test results of PEF and PTF biaxially oriented films

Table 2 Test results of PEF and PTF biaxially oriented films

From the barrier properties of the furan-based polyester film, it can be seen that with the gradual increase of the stretching ratio, the barrier properties of the furan-based polyester film with the addition of a nucleator are significantly improved. Secondly, under the premise of stretching to the same stretching ratio, the furan-based polyester film with the addition of a nucleating agent can achieve a lower barrier performance under the premise of a fast stretching rate. The addition of a nucleating agent can produce more nucleation sites during the stretching process, further promote the degree of oriented crystallization of the furan-based polyester film during the stretching process, and further improve the barrier properties of the film. In summary, the addition of a nucleating agent further improves the forming efficiency of the biaxially stretched film, thereby obtaining a high-barrier furan-based polyester film.

Although the above embodiments describe the specific implementation methods of the present invention in conjunction with the accompanying drawings, they are not intended to limit the scope of protection of the present invention. Technical personnel in the relevant field should understand that various modifications or variations that can be made by technical personnel in the field without creative work on the basis of the technical solution of the present invention are still within the scope of protection of the present invention.

Claims (10)

1. The nucleating agent for furan-based polyester is characterized by being N, N' -1, 4-phthalfurancarboxamide, and has a structural formula:

2. a process for the preparation of a class of nucleating agents for furan-based polyesters as claimed in claim 1, comprising the steps of:

t1, adding p-phenylenediamine, an acid binding agent and a solvent into a reactor, controlling the temperature to-10-5, and stirring;

T2, dripping the furoyl chloride solution into the reactor for at least 20min; the solvent of the furoyl chloride solution and the step T1 use the same solvent;

t3, heating to the reflux temperature of the solvent, and reacting for not less than 3 hours;

t4, cooling to room temperature after the reaction is finished, and filtering, washing and drying to obtain white powder, namely the nucleating agent N, N' -1, 4-phthalimide;

the molar ratio of the p-phenylenediamine to the furoyl chloride is 1:2.05 to 2.2; the molar ratio of the furoyl chloride to the acid binding agent is 1:1.

3. The preparation method according to claim 2, wherein the acid-binding agent is at least one selected from triethylamine and pyridine; the solvent is selected from one of acetonitrile, toluene, chloroform, dioxane, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.

4. The preparation method according to claim 2, wherein the mass ratio of p-phenylenediamine to solvent in the step T1 is 0.02-0.045: 1, a step of; the mass ratio of the furoyl chloride to the solvent in the step T2 is 0.06-0.12: 1.

5. The furan-based polyester film composition with rapid forming and high barrier property is characterized by comprising, by mass, 100 parts of furan-based polyester and 0.1-3 parts of nucleating agent;

The nucleating agent is N, N' -1, 4-benzene difuran formamide.

6. The furan-based polyester film composition of claim 5, wherein the furan-based polyester is at least one selected from the group consisting of ethylene furandicarboxylate, propylene furandicarboxylate, butylene furandicarboxylate, pentyfurandicarboxylate, hexylfurandicarboxylate, octylfurandicarboxylate, polyethylene terephthalate-2, 5-furandicarboxylate, polypropylene terephthalate-2, 5-furandicarboxylate, polybutylene terephthalate-2, 5-furandicarboxylate, polyethylene adipate-2, 5-furandicarboxylate, polypropylene adipate-2, 5-furandicarboxylate, polybutylene adipate-2, 5-furandicarboxylate, poly 2, 5-furandimethanol-ethylene cyclohexanedicarboxylate, poly 2, 5-furandimethanol-propylene glycol copolyester, poly 2, 5-furandimethanol-cyclohexanedimethanol-butylene glycol copolyester.

7. A process for preparing the furan-based polyester film composition of any one of claims 5-6, characterized in that the furan-based polyester and the nucleating agent are pre-mixed in proportions; and then sequentially carrying out melt blending, tape casting and two-way stretching processes to obtain the furan-based polyester film composition.

8. The method of claim 7, wherein the melt blending process is: placing the pre-mixed furan-based polyester and nucleating agent in a double-screw extruder for melt blending to obtain a master batch; the processing temperature of the double-screw extruder is 190-250, and the screw rotating speed is 140-160rpm.

9. The method of claim 8, wherein the casting process is: placing the master batch into a single-screw extrusion casting machine for casting forming to obtain a sheet; the processing temperature of the single-screw extrusion casting machine is 190-250, and the screw rotating speed is 110-130rpm.

10. The method according to claim 9, wherein the biaxial stretching process is: placing the sheet in a biaxial stretching machine for biaxial stretching to obtain the furan-based polyester film composition with rapid molding and high barrier property; the processing temperature of the biaxial stretching machine is 100-120, the stretching ratio is 2-5, the stretching speed is 50v/s-400v/s, and the shaping temperature is 130-150.