Preparation system of ultrathin PET functional master batch

Abstract

The utility model discloses a preparation system of ultrathin PET (Polyethylene Terephthalate) functional master batch, which comprises a stainless steel esterification tank (100) and a stainless steel polycondensation tank (200), and the outlet of the stainless steel esterification tank (100) is connected with the inlet of the stainless steel polycondensation tank (200) through a pipeline; wherein a first vacuum pump (101) is connected above the stainless steel esterification tank (100), and a condenser (102) is arranged in a pipeline, connected with the stainless steel esterification tank (100), of the first vacuum pump (101); a first heat-conducting oil jacket (103) is arranged on the outer side of a tank body of the stainless steel esterification tank (100); a second vacuum pump (201) is connected above the stainless steel polycondensation tank (200); and a second heat-conducting oil jacket (203) is arranged on the outer side of a tank body of the stainless steel polycondensation tank (200). According to the preparation system of the ultrathin PET functional master batch, the blank of lack of a special system for continuously preparing the ultrathin PET functional master batch in the prior art is filled, and the ultrathin PET functional master batch can be continuously produced and prepared in batches and obtained.

Description

TECHNICAL FIELD

[0001] The utility model relates to a kind of preparation systems of ultra-thin PET functional masterbatch. BACKGROUND

[0002] With the progress of science and technology and the continuous upgrading of consumer demand, ultra-thin PET film has been widely used in packaging, electronics, construction and other fields due to its lightweight, high transparency, good mechanical strength and gas barrier properties. For example, in the field of food packaging, ultra-thin PET film can be used to make food packaging bags to reduce material usage and production costs; in the field of electronic products, ultra-thin PET film can be used as a substrate or protective film for flexible displays; in the field of construction, ultra-thin PET film can be used for thermal insulation, sound insulation and decoration. In addition, the lightweight nature of ultra-thin film gives it an advantage in the field of electronic devices, packaging, automobiles, etc., making it easy to transport and apply. Ultra-thin film maintains high transparency and can be applied in fields requiring light transmission properties (such as optical films, display protective films, etc.). Ultra-thin film usually has good flexibility and can be applied in scenarios such as bendable or flexible displays, solar cells, etc.

[0003] However, as the application field continues to expand, the shortcomings of ultra-thin PET film in terms of ultraviolet resistance have gradually become apparent. For example, due to the small thickness of ultra-thin film, the absorption capacity of PET molecular chains themselves to ultraviolet light is limited, which causes the film to age or be damaged when exposed to ultraviolet light and other environmental factors. This not only affects the service life of ultra-thin PET film, but also may cause damage to the products it packages or protects. In addition, during the manufacture of ultra-thin film, especially during the stretching process, the stretching of the film may change the molecular arrangement of the film, leading to uneven distribution of ultraviolet absorbers or reduced light stability. The stretching process may also cause uneven performance in the stretching direction of the film, affecting the uniformity of ultraviolet resistance, especially the distribution of light stabilizers and ultraviolet absorbers in the film.

[0004] Therefore, how to improve the ultraviolet resistance of ultra-thin PET film has become a problem to be solved in the field of high polymer material preparation technology. The present utility model is aimed at this problem and proposes a preparation system for ultra-thin PET functional masterbatch with excellent ultraviolet resistance to fill the gap in the prior art for a dedicated continuous preparation system for ultra-thin PET functional masterbatch. SUMMARY

[0005] The technical problem to be solved by the present utility model is to provide a preparation system for ultra-thin PET functional masterbatch to reduce or avoid the problems mentioned above.

[0006] In order to solve the above technical problems, the utility model provides a kind of preparation system of ultra-thin PET functional masterbatch, for preparing and obtaining ultra-thin PET functional masterbatch, wherein the preparation system includes stainless steel esterification tank and stainless steel polycondensation tank, the outlet of stainless steel esterification tank is connected with the inlet of stainless steel polycondensation tank by pipeline;Wherein, the upper portion of the stainless steel esterification tank is connected with the first vacuum pump, and the pipeline connected with the stainless steel esterification tank is provided with a condenser;The outer side of the tank body of the stainless steel esterification tank is provided with a first heat-conducting oil jacket;The upper portion of the stainless steel polycondensation tank is connected with the second vacuum pump, and the outer side of the tank body of the stainless steel polycondensation tank is provided with a second heat-conducting oil jacket.

[0007] Preferably, the stainless steel esterification tank is provided with a mechanical stirring device.

[0008] Preferably, the outlet of the stainless steel polycondensation tank is connected with the inlet of the double-screw extruder by pipeline.

[0009] Preferably, the outlet of the double-screw extruder is connected with the granulator, and a water cooling system is arranged between the granulator and the double-screw extruder.

[0010] Preferably, the diameter of the particles formed by the granulator is 2-4mm.

[0011] The preparation system of ultra-thin PET functional masterbatch fills the gap of the lack of a special continuous preparation system for ultra-thin PET functional masterbatch in the prior art, and can continuously produce and prepare ultra-thin PET functional masterbatch. In the functional masterbatch prepared by the preparation system, isophorone diester and 2,4-dihydroxybenzoic acid and other UV absorbing groups are introduced, which enhances the absorption capacity of the molecular chain to ultraviolet rays and improves the aging resistance of the film. In addition, the uniform distribution of light stabilizers and ultraviolet absorbers in the molecular structure is improved by using Beta molecular sieve, zinc metaborate and other additives, effectively avoiding the uneven UV absorption performance of the film caused by the change of molecular arrangement during stretching. The synergistic effect of each component in the formula not only improves the ultraviolet resistance, strength and thermal stability of the film, but also ensures the uniformity of the performance of the film, providing an innovative material solution for the preparation of high-performance ultra-thin PET film. Through the preparation method of the utility model, the performance of PET material can be significantly improved, such as mechanical strength, thermal stability, gas barrier property, etc., so as to meet the application requirements of ultra-thin products in packaging, electronics, construction and other fields. BRIEF DESCRIPTION OF DRAWINGS

[0012] The following drawings are only intended to illustrate and explain the present application, and do not limit the scope of the utility model.

[0013] Figure 1The preparation system of the PET functional masterbatch for ultra-thin products is shown in the structural schematic view according to one specific embodiment of the utility model. DETAILED DESCRIPTION

[0014] In order to have a clearer understanding of the technical features, objects and effects of the utility model, the specific embodiments of the utility model are described in detail.

[0015] In view of the problems existing in the ultraviolet resistance function of the ultra-thin PET film, the polyethylene terephthalate (PET) is functionally modified in the utility model to prepare a special functional masterbatch suitable for ultra-thin products. Through the preparation system of the utility model, the ultraviolet resistance performance of the PET material can be significantly improved, and the mechanical strength, thermal stability, gas barrier property and the like of the material are also improved, so as to meet the application requirements of the ultra-thin products in the fields of packaging, electronics, building and the like.

[0016] Specifically, the utility model provides a PET functional masterbatch for ultra-thin products, which can be used as raw material for preparing ultra-thin PET products, for example, as all raw materials for preparing ultra-thin PET products, or as part of the raw materials for preparing ultra-thin PET products, and the required ultra-thin PET products are prepared by combining with other raw materials.

[0017] In one specific embodiment, the PET functional masterbatch for ultra-thin products of the utility model is prepared from the following raw materials by weight: terephthalic acid (PTA): 95-105 parts by weight; ethylene glycol (EG): 65-75 parts by weight; isophorone diester (IPDE): 25-35 parts by weight; 2,4-dihydroxybenzoic acid (2,4-DHBA): 15-25 parts by weight; titanium tetrachloride (TiCl4): 0.05-0.10 parts by weight; antimony acetate (Sb2O3): 0.04-0.08 parts by weight; phosphoric acid (H3PO4): 0.03-0.06 parts by weight; 2,6-di-tert-butyl-p-cresol (BHT): 0.03-0.08 parts by weight; zinc metaborate: 0.01-0.03 parts by weight; diethylene glycol (DEG): 3-7 parts by weight; xylene (Xylene): 2-4 parts by weight; Beta molecular sieve: 8-12 parts by weight.

[0018] PTA as the main diacid component of polyester provides a stable structure for the main chain. EG provides the dihydric alcohol required for the reaction, adjusting the flexibility and viscosity of the polyester molecule. IPDE improves mechanical properties and thermal stability by introducing rigid groups, while helping to improve UV resistance. 2,4-DHBA as a UV absorbing component, participates in copolymerization of the polyester chain through its hydroxyl and carboxyl groups. TiCl4 as a catalyst for the esterification stage, promotes the esterification reaction to proceed quickly. Sb2O3 as a polymerization stage catalyst, used to increase the polymerization rate and molecular weight. H3PO4 is used to stabilize the polyester chain structure and inhibit side reactions. BHT is used to inhibit the oxidative degradation of the material at high temperatures. Zinc metaborate is used to improve the thermal stability of the film in high temperature stretching. DEG as an auxiliary solvent, helps to adjust the viscosity of the reaction, to avoid premature precipitation of the polymer. Xylene is used to improve the miscibility at the beginning of the reaction, and to help the byproduct water evaporate. Beta molecular sieve is a type of nanoscale molecular sieve with a 12-membered ring cross-channel structure, used to ensure efficient dehydration of the esterification reaction, while its unique cage-free three-dimensional pore structure facilitates the diffusion of reactant and product molecules, while having the effect of shape-selective catalysis.

[0019] The raw materials of the present application involve a complex chemical reaction process, mainly including the ester group of IPDE reacting with the carboxyl group of PTA to form a polyester chain. Secondly, the esterification reaction occurs between the carboxyl group of DHBA and the hydroxyl group of EG to form an esterification monomer, providing a precursor for the subsequent polymerization reaction. Thirdly, the ester group of IPDE reacts with the carboxyl group of DHBA to form a copolymer. Finally, all the intermediates mentioned above are mixed together and polymerized with EG to form the high molecular chain of PET.

[0020] Among them, since IPDE has two ester groups, it can undergo esterification reactions with PTA and EG. Moreover, when the ester groups of IPDE undergo esterification reactions with the carboxyl groups in PTA and the hydroxyl groups in EG, long-chain polyesters are formed. The introduction of IPDE can bring rigidity to the molecular chain and a certain ultraviolet absorption capacity. DHBA is an aromatic compound containing phenolic hydroxyl groups. In the reaction, its carboxyl group can undergo esterification reactions with EG and PTA, while its phenolic hydroxyl group can copolymerize with IPDE through esterification reactions. At the same time, the presence of phenolic hydroxyl groups provides a functional group for ultraviolet absorption.

[0021] Further, the ultra-thin PET functional masterbatch of the present application can be prepared by the following method.

[0022] Specifically, the method comprises the following steps: firstly, in a stainless steel esterification tank, terephthalic acid, ethylene glycol, 2,4-dihydroxybenzoic acid, diethylene glycol and dimethylbenzene are weighed and added in sequence, the added materials are stirred uniformly by a mechanical stirring device in the stainless steel esterification tank, and then the temperature is raised to 150 DEG C; then titanium tetrachloride is added as a catalyst, nitrogen is introduced under normal pressure to discharge air from the esterification tank, and the pressure is gradually reduced to 0.5 Mpa, and the esterification reaction is carried out under nitrogen protection for 6-8 hours, and the reaction temperature is controlled to 190-220 DEG C; during the esterification reaction, the by-product water generated in the esterification reaction is evaporated and then condensed and discharged through a condenser connected to the top of the stainless steel esterification tank.

[0023] When the esterification reaction time is left for 30 minutes, Beta molecular sieve is added into the stainless steel esterification tank, and meanwhile, the water discharge amount of the condenser is obviously reduced or even stopped, so that the esterification reaction is judged to be completed; the temperature in the esterification tank is reduced to 220 DEG C; under the nitrogen protection, phosphoric acid is added according to the formula proportion; and the phosphoric acid is uniformly distributed by stirring for 5-10 minutes through the mechanical stirring device in the stainless steel esterification tank.

[0024] The temperature in the esterification tank is gradually raised to 250 DEG C-270 DEG C, the pressure in the tank is adjusted to 500-1000 Pa, antimony acetate is added as a polycondensation catalyst and isophorone diester is added according to the formula proportion under the stirring of the mechanical stirring device, and the pre-polycondensation reaction is continuously carried out in the esterification tank for 3-5 hours under the nitrogen protection and the pressure of 500-1000 Pa.

[0025] When the pre-polycondensation reaction time is up, the pre-polycondensation product is transferred from the stainless steel esterification tank to a stainless steel polycondensation tank, and 2,6-di-tert-butyl-p-cresol and zinc metaborate are added into the stainless steel polycondensation tank; the polycondensation tank is connected to a vacuum pumping system, and the pressure in the polycondensation tank is reduced to 10-50 Pa; then the temperature is gradually raised to 280 DEG C-290 DEG C, and the polycondensation reaction is carried out for 2-3 hours, and the polymer molecular weight reaches 35,000-45,000 g / mol, so that the polycondensation reaction is determined to be completed.

[0026] The polyester melt is introduced into a double-screw extruder from the polycondensation tank, extruded and cooled to form a long strip, the long strip is rapidly cooled through a water cooling system, and the long strip is cut into particles by using a pelletizer to form particles with a diameter of 2-4 mm.

[0027] Corresponding to the preparation method, the utility model further provides a system specially used for preparing the PET functional masterbatch for ultra-thin use, as shown in Figure 1 .

[0028] The preparation system of the PET functional masterbatch for ultra-thin use can be used for preparing the PET functional masterbatch for ultra-thin use, wherein the preparation system comprises a stainless steel esterification tank 100 and a stainless steel polycondensation tank 200, the outlet of the stainless steel esterification tank 100 is connected to the inlet of the stainless steel polycondensation tank 200 through a pipeline, and is used for transferring the pre-polycondensation product from the stainless steel esterification tank 100 to the stainless steel polycondensation tank 200.

[0029] The first vacuum pump 101 is used for controlling the pressure in the tank body by means of air extraction, and the condenser 102 arranged in the pipeline is used for cooling the extracted steam, so as to condense and discharge the by-product water.

[0030] In order to control the reaction temperature in the esterification tank, in one specific embodiment, a first heat-conducting oil jacket 103 is arranged outside the tank body of the stainless steel esterification tank 100.

[0031] Similarly, the second vacuum pump 201 is connected to the upper portion of the stainless steel polycondensation tank 200, and is used for controlling the pressure in the tank body by means of air extraction.

[0032] Further, the mechanical stirring device 104 can also be arranged in the stainless steel esterification tank 100.

[0033] Further, the outlet of the stainless steel polycondensation tank 200 is connected to the inlet of the double-screw extruder 300 through a pipeline, and is used for guiding the polyester melt into the double-screw extruder 300 from the polycondensation tank 200.

[0034] Further, the outlet of the double-screw extruder 300 is connected to the granulator 500, and the water cooling system 400 is arranged between the double-screw extruder 300 and the granulator 500.

[0035] Further, the diameter of the particles formed by the granulator 500 is 2-4 mm.

[0036] The preparation system of the PET functional masterbatch for ultra-thin use fills the blank of the prior art that lacks a special continuous preparation system of the PET functional masterbatch for ultra-thin use, and can continuously and batch-prepared and obtain the PET functional masterbatch for ultra-thin use.

[0037] The performance of the ultra-thin PET film prepared by the PET functional masterbatch for ultra-thin use is described in detail through specific embodiments 1-6.

[0038] For ease of illustration, the raw materials of the PET functional masterbatch for ultra-thin use are represented in alphabetical order.

[0039] A: terephthalic acid (PTA); B: ethylene glycol (EG); C: isophorone diester (IPDE); D: 2,4-dihydroxybenzoic acid (2,4-DHBA); E: titanium tetrachloride (TiCl4); F: antimony acetate (Sb2O3); G: phosphoric acid (H3PO4); H: 2,6-di-tert-butyl-p-cresol (BHT); I: zinc metaborate; J: diethylene glycol (DEG); K: xylene; L: Beta molecular sieve.

[0040] The following table lists the weight parts of each component of the PET functional masterbatch for ultra-thin use of Examples 1-6.

[0041] Embodiments A B C D E F G H I J K L 1 95 65 25 15 0.05 0.04 0.03 0.03 0.01 3 2 8 2 105 75 35 25 0.10 0.08 0.06 0.08 0.03 7 4 12 3 95 70 30 20 0.07 0.06 0.05 0.06 0.02 5 3 10 4 100 75 25 25 0.08 0.08 0.06 0.07 0.03 6 3.5 11 5 100 65 35 20 0.06 0.05 0.04 0.05 0.02 4 3 9 6 100 70 30 15 0.07 0.06 0.05 0.06 0.03 5 3 10

[0042] The following table is the performance parameter of the ultra-thin PET film prepared using the PET functional masterbatch for ultra-thin use of Examples 1-6.

[0043]

[0044]

[0045] The performance parameter analysis is as follows: (1) UV resistance. 2,4-dihydroxybenzoic acid (2,4-DHBA) and isophorone diester (IPDE) provide high-efficiency UV absorption capacity, with absorption peaks covering the UV-A and UV-B ranges. Beta molecular sieve further reduces UV transmittance by adsorbing part of the ultraviolet radiation through pore distribution. (2) Strength performance. The optimization of the PTA and EG ratio provides a balance between the rigidity and flexibility of the main chain. The rigid structure of isophorone diester (IPDE) significantly improves the tensile strength. In the range of 3 μm-8 μm, the strength performance is better. (3) Thermal stability. The synergistic effect of phosphoric acid and BHT inhibits high-temperature degradation, improving the thermal stability of the film. The isophorone group further enhances the mechanical properties at high temperatures. (4) Gas barrier property. The synergistic effect of Beta molecular sieve and zinc metaborate filler reduces the gas transmittance of the film.

[0046] Summary: Examples 1-6 demonstrate the potential for optimizing UV resistance performance through the fine-tuning of raw material ratios and changes in film thickness, while ensuring a balance of strength, thermal stability, and gas barrier properties.

[0047] To make performance comparison, the utility model designs the proportion 1-6, the design idea of proportion is: omit some key components (for example IPDE, 2, 4-DHBA, Beta molecular sieve etc.), test UV absorption or gas barrier parameter;Or replace some components (such as using traditional plasticizing agent to replace IPDE, using conventional antioxidant to replace BHT), test mechanical performance or thermal stability parameter;Or keep basic component (PTA and EG) to ensure copolymerization, test the performance drop of missing functional component.

[0048] The scheme measures used therein are shown in the following table.

[0049]

[0050]

[0051] The following table is the performance parameter of the ultra-thin PET film of the proportion 1-6, and the reason of performance drop is listed in the processing mode of the corresponding proportion.

[0052]

[0053] In the above table, the processing mode of each proportion is as follows: the proportion 1 omits IPDE and 2, 4-DHBA relative to example 1;The proportion 2 uses phthalate to replace IPDE relative to example 2;The proportion 3 omits Beta molecular sieve and Sb2O3 relative to example 3;The proportion 4 replaces BHT with vitamin E relative to example 4;The proportion 5 omits zinc metaborate relative to example 5;The proportion 6 omits H3PO4 relative to example 6. Except for the above differences, the remaining components and weight parts of each proportion and its corresponding example remain unchanged.

[0054] Through performance comparison of the proportion 1-6 and example 1-6, it can be found that the UV transmittance of the film of the proportion is significantly increased (≥8% vs. ≤5% of the example), the main reason is the omission or replacement of IPDE and 2, 4-DHBA, and the omission of Beta molecular sieve. In the example, IPDE provides excellent UV absorption capacity, 2, 4-DHBA enhances UV resistance, and Beta molecular sieve further improves the overall barrier property. In addition, the strength of the proportion is reduced, especially when IPDE is omitted or replaced with flexible plasticizer, the mechanical property is reduced due to insufficient molecular chain rigidity. Moreover, the thermal stability of the proportion is lower than that of the example, mainly due to the omission of phosphoric acid (H3PO4) and antioxidant (BHT) or the use of substitutes. H3PO4 and BHT stabilize the molecular chain in high temperature environment in the example. And the gas barrier property of the proportion is significantly reduced, because Beta molecular sieve and zinc metaborate are omitted. These two components significantly enhance the barrier property by physical filling and interface adsorption in the example.

[0055] By comparing the above comparative examples with the examples, the following conclusions can be drawn: the functional components (such as IPDE, 2, 4-DHBA, Beta molecular sieve, etc.) in the examples have significant contributions to the UV resistance performance, strength, thermal stability and gas barrier property. After the key components are omitted or replaced in the comparative example films, the performance parameters are obviously decreased, which proves the necessity and superiority of the optimized formula and unique design of the example combination.

[0056] In summary, the ultra-thin PET functional masterbatch of the present application significantly overcomes the defects of ultra-thin PET films in the case of limited UV absorption capacity under small thickness by optimizing the molecular structure and functional component combination. By introducing UV absorbing groups such as isophorone diester (IPDE) and 2, 4-dihydroxybenzoic acid (2, 4-DHBA), the molecular chain's ability to absorb UV light is enhanced, and the film's aging resistance is improved. In addition, the use of Beta molecular sieve, zinc metaborate and other additives improves the uniform distribution of light stabilizers and UV absorbers in the molecular structure, effectively avoiding the uneven UV absorption performance of the film due to the change of molecular arrangement during stretching. The synergistic effect of each component in the formula not only improves the film's UV resistance performance, strength and thermal stability, but also ensures the uniformity of the film's performance, providing an innovative material solution for the preparation of high-performance ultra-thin PET films.

[0057] Those skilled in the art should understand that although the present application is described in the form of multiple embodiments, not every embodiment contains only one independent technical solution. The description in the specification is only for clarity, those skilled in the art should understand the specification as a whole and understand the technical solutions involved in each embodiment as a way to combine different embodiments to understand the protection scope of the present application.

[0058] The above is only a specific embodiment of the present application, and is not intended to limit the scope of the present application. Any equivalent changes, modifications and combinations made by those skilled in the art without departing from the concept and principles of the present application shall fall within the scope of protection of the present application.

Claims

1. A system for preparing a functional masterbatch of PET for ultra-thin applications, for preparing a functional masterbatch of PET for ultra-thin applications, characterized by, The preparation system comprises a stainless steel esterification tank (100) and a stainless steel polycondensation tank (200), the outlet of the stainless steel esterification tank (100) is connected to the inlet of the stainless steel polycondensation tank (200) through a pipeline; wherein the upper portion of the stainless steel esterification tank (100) is connected to a first vacuum pump (101), a condenser (102) is arranged in the pipeline connected to the stainless steel esterification tank (100); the outer side of the tank body of the stainless steel esterification tank (100) is provided with a first heat conducting oil jacket (103); the upper portion of the stainless steel polycondensation tank (200) is connected to a second vacuum pump (201), and the outer side of the tank body of the stainless steel polycondensation tank (200) is provided with a second heat conducting oil jacket (203).

2. The preparation system of claim 1, wherein, A mechanical stirring device (104) is arranged in the stainless steel esterification tank (100).

3. The preparation system of claim 1, wherein, The outlet of the stainless steel polycondensation tank (200) is connected to the inlet of a double screw extruder (300) through a pipeline.

4. The preparation system of claim 3, wherein, The outlet of the double screw extruder (300) is connected to a granulator (500), and a water cooling system (400) is arranged between the double screw extruder (300) and the granulator (500).

5. The preparation system of claim 4, wherein, The diameter of the particles formed by the granulator (500) is 2-4 mm.

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