Metal complex composite PET (Polyethylene Terephthalate)-based static dissipative polyester as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of polymer modification, and discloses a metal complex composite PET-based static dissipative polyester and a preparation method and application thereof.The preparation method comprises the following steps that terephthalic acid, 2, 5-furandicarboxylic acid and ethylene glycol are added into a reaction kettle and subjected to an esterification reaction in an inert atmosphere; adding polyethylene glycol, a metal organic complex and graphene, dispersing into the mixture, and carrying out condensation polymerization reaction; and after the reaction is finished, cooling to obtain the metal complex composite PET-based static dissipative polyester. The polyester master batch prepared by the invention has stable static dissipation performance, the surface resistance of the polyester master batch can be reduced to 107-108 omega.m, effective dissipation of static charges can be realized, and harm caused by static accumulation is avoided. The master batch can be directly prepared into a product, the requirements of the fields of electronic packaging, medical equipment and the like can be met without subsequent addition of an electrostatic agent or surface modification treatment, and meanwhile, the master batch has excellent thermal stability and transparency and has a relatively great application prospect.

Description

Technical Field

[0001] This invention belongs to the field of polymer material modification technology, specifically relating to a metal complex composite PET-based electrostatic dissipative polyester, its preparation method, and its application. Background Technology

[0002] Polyethylene terephthalate (PET) is widely used in packaging, electronics, medical and health, construction, and automotive industries due to its excellent properties. Packaging is the largest non-fiber application market for polyester and also the fastest-growing sector for PET. With the development of the high-end electronics industry, the demand for antistatic packaging materials is increasing year by year. However, ordinary PET packaging materials are prone to generating and accumulating static electricity due to contact or friction during use, posing serious safety hazards to production and practical applications. Therefore, research on antistatic PET packaging materials has also grown rapidly. However, most technologies involve surface coatings, adding antistatic agents, blending intrinsically conductive polymers, or surface-modified in-situ polymerizing conductive polymers.

[0003] Existing technologies for surface conductive coatings are problematic due to two main issues: firstly, the process is complex, requiring pre-molding followed by further coating; secondly, the coating is easily scratched and peeled off during use, resulting in a loss of electrostatic dissipation properties. Adding antistatic agents can easily atomize the PET substrate, severely reducing transparency, and secondly, these agents can migrate to the surface, gradually losing their electrostatic dissipation properties. Blending intrinsically conductive polymers is costly, and surface-modified polymerizing conductive polymers is complex, requiring swelling of the PET surface after molding, followed by in-situ polymerization of the conductive polymer, and then washing away the solvent and unreacted components. In summary, current technical solutions are either inconvenient to use, requiring pre-molding and subsequent processing, or complex and costly. Therefore, providing an electrostatic dissipative polyester with a simple preparation process, good electrostatic dissipation properties, and good transparency has broad application prospects. Summary of the Invention

[0004] In order to overcome the shortcomings and deficiencies of the prior art, the primary objective of this invention is to provide a method for preparing a metal complex composite PET-based electrostatic dissipative polyester.

[0005] This invention first introduces furanyl dicarboxylic acid (FDCA) and PEG during the polymerization stage of PET to obtain a PET-PEF-PEG copolyester. The numerous ether bonds in the polyester significantly increase its polarity, giving it good hygroscopicity. The polyester surface can adsorb water from the air to form a water molecule layer. During resin preparation, metal-organic complexes, such as metal-organic framework (MOF) materials, are introduced and dispersed within the polyester. When water molecules adsorb onto the resin surface to form a water molecule film, the numerous metal particles and anions contained in the metal complex are ionized and dispersed within it, resulting in a well-conductive water molecule layer. The addition of graphene further enhances conductivity, thereby significantly reducing the surface resistivity of the resin to 10 Ω·cm. 7 -10 8 Ω·m.

[0006] Another object of the present invention is to provide a metal complex composite PET-based electrostatic dissipative polyester.

[0007] Another object of the present invention is to provide the application of metal complex composite PET-based electrostatic dissipative polyester.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] A method for preparing a metal complex composite PET-based electrostatic dissipative polyester includes the following steps:

[0010] Terephthalic acid, 2,5-furandicarboxylic acid and ethylene glycol were added to a reaction vessel and esterified under an inert atmosphere. Then, polyethylene glycol, organometallic complex and graphene were added and dispersed therein for polycondensation. After the reaction was completed, the mixture was cooled to obtain a metal complex composite PET-based electrostatic dissipative polyester.

[0011] Preferably, the esterification reaction is carried out at a temperature of 190℃±50℃, a pressure of 360±40KPa, and a time of 1~5h.

[0012] Preferably, the total molar ratio of terephthalic acid and 2,5-furandicarboxylic acid to ethylene glycol is 1:1.2 to 1.6, more preferably 1:1.4;

[0013] The molar ratio of terephthalic acid and 2,5-furandicarboxylic acid is 2 to 6:1, preferably 2.8:1;

[0014] The polyethylene glycol has a molecular weight of 2000-10000, preferably PEG6000, and is added in an amount of 10-20 wt.% of the mass of phthalic acid.

[0015] Preferably, the organometallic complex is selected from MIL-53(Fe)(C8H4O5Fe) and MOF-5(C 24 H4O 13At least one of Zn4 or ZIF-67 (C4H6N2.Co).

[0016] Preferably, the mass ratio of the organometallic complex to terephthalic acid is 1 to 3:200.

[0017] Preferably, the polycondensation reaction is carried out at a temperature of 260℃±50℃, a vacuum degree of <100Pa, and a reaction time of 1 to 5 hours.

[0018] Preferably, the mass ratio of graphene to terephthalic acid is 0.01 to 0.1:600.

[0019] A metal complex composite PET-based electrostatic dissipative polyester was prepared by the above method.

[0020] Preferably, the surface resistivity of the metal complex composite PET-based electrostatic dissipative polyester is 1.0 × 10⁻⁶. 7 ~3.0×10 8 The transparency of a 75mm thin film is 60%–92% (Ω·m), and the decomposition temperature is >420℃.

[0021] The above-mentioned complexes are used in the application of PET-based electrostatic dissipative polyesters in packaging materials and medical devices.

[0022] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0023] (1) The polyester masterbatch prepared by this invention has stable electrostatic dissipation properties, and its surface resistance can be reduced to 10. 7 ~10 8 Ω·m enables the effective dissipation of static charge, avoiding the hazards caused by static electricity accumulation.

[0024] (2) The polyester masterbatch prepared by the present invention can be directly made into products without the need for subsequent addition of electrostatic agents or surface modification treatment of the products, which can meet the requirements of electronic packaging, medical devices and other fields and has great application prospects.

[0025] (3) The polyester masterbatch prepared by the present invention has excellent thermal stability and a decomposition temperature of >420℃, which can meet the requirements of high temperature processing technology and ensure the performance stability of the product during long-term use. It also has excellent transparency, with a transparency of 60% to 92% for 75mm thin sheets, which solves the technical problem of reduced transparency when adding antistatic agents in the prior art. Attached Figure Description

[0026] Figure 1 The infrared spectra of the PET-based polyester masterbatches obtained in Example 1 and Comparative Example 1 are shown. Detailed Implementation

[0027] The present invention will be further described in detail below with reference to specific embodiments, but the implementation of the present invention is not limited thereto. For process parameters not specifically noted, conventional techniques can be referred to.

[0028] 2,5-Furfurandicarboxylic acid (FDCA) was purchased from Guangzhou Seye Biotechnology Co., Ltd.

[0029] Diethanol (EG) was purchased from Guangzhou Seye Biotechnology Co., Ltd.

[0030] Graphene was purchased from: Chengdu Organic Chemistry Co., Ltd., Chinese Academy of Sciences;

[0031] The polyethylene glycol (PEG) was PEG6000, purchased from Guangzhou Seye Biotechnology Co., Ltd.

[0032] MIL-53(Fe), with the molecular formula C8H4O5Fe, was purchased from Hangzhou Xinqiao Biotechnology Co., Ltd.

[0033] MOF-5, with the molecular formula C5 24 H4O 13 Zn4, purchased from: Beijing Beike New Materials Technology Co., Ltd.;

[0034] Surface resistance test method: Measured using a surface resistivity meter, model: MODEL 800.

[0035] Example 1

[0036] 600g PTA (3.6mol), 200g FDCA (1.3mol), and 418g EG (6.7mol), with a total molar ratio of PTA and FDCA to EG of 1:1.4, were added to a reactor for esterification. The reactor was purged with nitrogen for protection, and the temperature was controlled at 190℃ and the reaction was carried out at 360±40KPa for 3 hours. Then, 120g PEG6000 (20% of the PTA mass) was added to the reactor, along with 3g C8H4O5Fe and 0.05g graphene, and a polycondensation reaction was carried out. The reactor was maintained under a vacuum of less than 100Pa, and the reaction temperature was controlled at 260℃ for 3 hours. After the reaction, the reactor was cooled and the product was discharged to obtain PET-based polyester masterbatch. C8H4O5Fe and graphene were physically mixed and uniformly dispersed in the polyester, forming a metal complex composite PET-based electrostatic dissipative polyester.

[0037] In this embodiment, a transparent, grayish-white polyester masterbatch was prepared with a surface resistivity of 2.6 × 10⁻⁶. 8 The Ω·m, Tg is 77.65℃, melting point is 243.68℃, decomposition temperature is 423.73℃, and the transparency of a 75mm thin film is 90.23%.

[0038] Figure 1 This is the infrared spectrum of the metal complex composite PET-based electrostatic dissipative polyester from Example 1. Compared with blank PET resin, this infrared spectrum clearly shows the strong asymmetric stretching vibration ν of the coordinating oxalate groups. as (C=O)=1590cm -1 The most crucial characteristic is the ν(Fe-O) peak at 587 cm⁻¹. -1 The presence of Fe-O coordination bonds was confirmed, indicating that the metal complex was successfully incorporated into the PET-based resin.

[0039] Example 2

[0040] 600g PTA, 200g FDCA, and 418g EG (with a total molar ratio of PTA and FDCA to EG of 1:1.4) were added to a reactor for esterification. The reactor was purged with nitrogen for protection, and the temperature was controlled at 190℃. The reaction was carried out at 360±40KPa for 3 hours. Then, 120g PEG6000 (20% of the PTA mass) was added to the reactor, along with 6g C8H4O5Fe and 0.05g graphene, which were dispersed within the mixture. A polycondensation reaction was carried out under a vacuum of less than 100Pa, with the reaction temperature controlled at 260℃ for 3 hours. After the reaction, the reactor was cooled and the product was discharged to obtain PET-based polyester masterbatch. C8H4O5Fe and graphene were physically mixed and uniformly dispersed in the polyester, forming a metal complex composite PET-based electrostatic dissipative polyester.

[0041] In this embodiment, a transparent, grayish polyester masterbatch was prepared with a surface resistivity of 4.1 × 10⁻⁶. 7 The Ω·m, Tg is 78.26℃, melting point is 245.77℃, decomposition temperature is 422.23℃, and the transparency of a 75mm thin film is 86.06%.

[0042] Example 3

[0043] 600g PTA, 200g FDCA, and 418g EG (with a total molar ratio of PTA and FDCA to EG of 1:1.4) were added to a reactor for esterification. The reactor was purged with nitrogen for protection, and the temperature was controlled at 190℃. The reaction was carried out at 360±40KPa for 3 hours. Then, 120g PEG6000 (20% of the PTA mass) was added to the reactor, along with 9g C8H4O5Fe and 0.05g graphene, which were dispersed within the mixture. A polycondensation reaction was then carried out under a vacuum of less than 100Pa at 260℃ for 3 hours. After the reaction, the reactor was cooled, and the resulting material was discharged to obtain PET-based polyester masterbatch. C8H4O5Fe and graphene were physically and uniformly dispersed in the polyester, forming a metal complex composite PET-based electrostatic dissipative polyester.

[0044] In this embodiment, a transparent, grayish-white polyester masterbatch was prepared with a surface resistivity of 1.3 × 10⁻⁶. 7 The Ω·m, Tg is 78.98℃, melting point is 246.35℃, decomposition temperature is 421.76℃, and the transparency of a 75mm thin film is 67.12%.

[0045] Example 4

[0046] 600g PTA, 200g FDCA, and 418g EG were added to a reactor with a total molar ratio of PTA and FDCA to EG of 1:1.4 for esterification. The reactor was purged with nitrogen for protection, and the temperature was controlled at 190℃ and reacted at 360±40KPa for 3 hours. Then, 120g PEG6000 (20% of the PTA mass) was added to the reactor, followed by 6g C. 24 H4O 13 Zn4 and 0.05g of graphene were dispersed in the reactor for a polycondensation reaction. The reactor was kept under a vacuum of less than 100Pa, and the reaction temperature was controlled at 260℃ for 3 hours. After the reaction was completed, the reactor was cooled and the product was discharged to obtain PET-based polyester masterbatch. C 24 H4O 13 Zn4 and graphene are physically mixed and uniformly dispersed in polyester, which is a metal complex composite PET-based electrostatic dissipative polyester.

[0047] In this embodiment, a transparent, grayish-white polyester masterbatch was prepared with a surface resistivity of 1.2 × 10⁻⁶. 7 The Ω·m, Tg is 79.17℃, melting point is 246.81℃, decomposition temperature is 423.35℃, and the transparency of a 75mm thin film is 85.82%.

[0048] Comparative Example 1

[0049] 600g PTA, 200g FDCA, and 418g EG (with a total molar ratio of PTA and FDCA to EG of 1:1.4) were added to a reactor for esterification. The reactor was purged with nitrogen for protection, and the temperature was controlled at 190℃ and reacted at 360±40 kPa for 3 hours. Then, 120g PEG6000 (20% of the PTA mass) was added to the reactor for polycondensation. The reactor was maintained under a vacuum of less than 100 Pa, and the reaction temperature was controlled at 260℃ for 3 hours. After the reaction was completed, the reactor was cooled and the product was discharged to obtain PET-based polyester masterbatch.

[0050] This comparative example yielded a transparent, grayish-white polyester masterbatch with a surface resistivity of 2.3 × 10⁻⁶. 10The Ω·m, Tg is 77.22℃, melting point is 244.89℃, decomposition temperature is 421.13℃, and the transparency of a 75mm thin film is 85.78%.

[0051] Comparative Example 2

[0052] 600g PTA, 200g FDCA, and 418g EG (with a total molar ratio of PTA and FDCA to EG of 1:1.4) were added to a reactor for esterification. The reactor was purged with nitrogen for protection, and the temperature was controlled at 190℃. The reaction was carried out at 360±40 kPa for 3 hours. Then, 120g PEG6000 (20% of the PTA mass), 15g C8H4O5Fe, and 0.05g graphene were added to the reactor for polycondensation. The reactor was maintained under a vacuum below 100 Pa, and the reaction temperature was controlled at 260℃ for 3 hours. After the reaction was completed, the reactor was cooled and the product was discharged to obtain PET-based polyester masterbatch.

[0053] In this comparative example, a transparent to slightly dark polyester masterbatch was prepared, with a surface resistivity of 2.1 × 10⁻⁶. 6 The Ω·m, Tg is 79.35℃, melting point is 247.45℃, decomposition temperature is 420.14℃, and the transparency of a 75mm thin film is 45.49%.

[0054] Comparative Example 3

[0055] 600g PTA, 200g FDCA, and 418g EG (with a total molar ratio of PTA and FDCA to EG of 1:1.4) were added to a reactor for esterification. The reactor was purged with nitrogen for protection, and the temperature was controlled at 190℃. The reaction was carried out at 360±40 kPa for 3 hours. Then, 120g PEG6000 (20% of the PTA mass), 6g C8H4O5Fe, and 0.5g graphene were added to the reactor for polycondensation. The reactor was maintained under a vacuum of less than 100 Pa, and the reaction temperature was controlled at 260℃ for 3 hours. After the reaction was completed, the reactor was cooled and the product was discharged to obtain PET-based polyester masterbatch.

[0056] The comparative example yielded a dark-colored polyester masterbatch with a surface resistivity of 1.2 × 10⁻⁶. 7 The Ω·m, Tg is 78.86℃, melting point is 244.97℃, decomposition temperature is 423.54℃, and the transparency of a 75mm thin film is 35.73%.

[0057] Comparative Example 4

[0058] 600g PTA (3.6mol), 200g FDCA (1.3mol), and 418g EG (6.7mol), with a total molar ratio of PTA and FDCA to EG of 1:1.4, were added to a reactor for esterification. The reactor was purged with nitrogen for protection, and the temperature was controlled at 190℃ and 360±40KPa for 3 hours. Then, 120g PEG6000 (20% of the PTA mass) and 3g C8H4O5Fe were added to the reactor for polycondensation. The reactor was kept under a vacuum of less than 100Pa, and the reaction temperature was controlled at 260℃ for 3 hours. After the reaction, the reactor was cooled and the product was discharged to obtain PET-based polyester masterbatch. C8H4O5Fe was physically dispersed in the polyester, forming a metal complex composite PET-based electrostatic dissipative polyester.

[0059] In this comparative example, a transparent, grayish-white polyester masterbatch was prepared, with a surface resistivity of 5.2 × 10⁻⁶. 9 Ω·m, T g Its temperature is 77.87℃, melting point is 243.46℃, decomposition temperature is 423.54℃, and the transparency of a 75mm thin film is 92.93%.

[0060] Comparative Example 5

[0061] 600g PTA (3.6mol), 200g FDCA (1.3mol), and 418g EG (6.7mol), with a total molar ratio of PTA and FDCA to EG of 1:1.4, were added to a reactor for esterification. The reactor was purged with nitrogen for protection, and the temperature was controlled at 190℃ and 360±40KPa for 3 hours. Then, 120g PEG6000 (20% of the PTA mass) and 0.05g graphene were added to the reactor for polycondensation. The reactor was kept under a vacuum below 100Pa, and the reaction temperature was controlled at 260℃ for 3 hours. After the reaction, the reactor was cooled and the product was discharged to obtain PET-based polyester masterbatch. The graphene was physically and uniformly dispersed in the polyester, forming a composite PET-based electrostatic dissipative polyester.

[0062] In this comparative example, a transparent, grayish-white polyester masterbatch was prepared, with a surface resistivity of 8.7 × 10⁻⁶. 9 The Ω·m, Tg is 77.61℃, melting point is 243.54℃, decomposition temperature is 423.68℃, and the transparency of a 75mm thin film is 90.03%.

[0063] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A process for the preparation of a metal complex compounded PET based electrostatic dissipative polyester characterized in that, It comprises the following steps: terephthalic acid, 2,5-furan dicarboxylic acid and ethylene glycol are added into a reaction kettle to carry out esterification under inert atmosphere; polyethylene glycol, metal organic complex and graphene are dispersed therein to carry out polycondensation reaction; after the reaction is completed, cooling is carried out to obtain metal complex composite PET-based static dissipative polyester.

2. The process for the preparation of metal complex compounded PET based electrostatic dissipative polyester as claimed in claim 1 wherein, The temperature of the esterification reaction is 190℃±50℃, the pressure is 360±40KPa, and the time is 1-5h.

3. The process for the preparation of metal complex compounded PET based electrostatic dissipative polyester as claimed in claim 1 wherein, The total mole amount of terephthalic acid and 2,5-furan dicarboxylic acid is 1:1.2-1.6 to the mole amount of ethylene glycol. The mole amount of terephthalic acid is 2-6 to the mole amount of 2,5-furan dicarboxylic acid. The molecular weight of the polyethylene glycol is 2000-10000, and the addition amount is 10-20wt.% of the mass of the terephthalic acid.

4. The process for the preparation of metal complex compounded PET based electrostatic dissipative polyester as claimed in claim 1 wherein, The metal organic complex is at least one selected from MIL-53(Fe), MOF-5 or ZIF-67.

5. The process for the preparation of metal complex compounded PET based electrostatic dissipative polyester as claimed in claim 1 wherein, The mass ratio of the metal organic complex to terephthalic acid is 1-3:

200.

6. The process for the preparation of metal complex compounded PET based electrostatic dissipative polyester as claimed in claim 1 wherein, The temperature of the polycondensation reaction is 260℃±50℃, the vacuum degree is <100Pa, and the reaction time is 1-5h.

7. The process for preparing a metal complex compounded PET based electrostatic dissipative polyester as claimed in claim 1, wherein, The mass ratio of the graphene to terephthalic acid is 0.01-0.1:

600.

8. A metal complex compounded PET based electrostatic dissipative polyester characterized in that, It is prepared by the method in any one of claims 1-7.

9. The metal complex compounded PET based electrostatic dissipative polyester of claim 8, wherein, The surface resistance of the metal complex composite PET-based static dissipative polyester is 1.0 x 10 7 ~ 3.0 x 10 8 Ω·m.

10. Application of the complex composite PET-based static dissipative polyester in claim 8 or 9 in the field of packaging materials and medical devices.

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