TW200918575A - Polyester copolymer that is oxygen absorptive and air-resistant and method for preparing the same - Google Patents

Abstract

The invention provides a polyester copolymer that is oxygen absorptive and air-resistant, prepared by copolymerizing (a) a modified prepolymer represented by formula (1) with (b) a polyester or a polyester prepolymer formed from dicarboxylic acid and glycol. Formula (1) Where R.sub.2 represents an alkyl chain of 1 to 24 carbon atoms and pbd represents polybutadiene.

Description

200918575 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to polyester copolymers, and more particularly to polyester copolymers having oxygen and gas barrier properties. [Prior Art] Recently, as people's lives have become more and more busy, and there has been no food and drink, and thanks to advances in food preservation and packaging technology, the food industry has been flourishing: people's diverse fast foods and beverages. In order to make the consumer portable and extend the shelf life of food or beverages, glass or metal 2 was used as a packaging container for food or beverage in the early stage. In recent years, plastic materials have gradually replaced the advantages of light weight and rapid production. Glass or metal is the mainstream of packaging containers. Therefore: some foods or beverages are prone to lose their original flavor due to oxidation, and their packaging materials require higher gas barrier properties to reduce the entry into the container. For example, 'in order to maintain the quality and taste of beer, beer, two containers Must have good gas barrier properties, heat resistance, long-term pressure resistance, pure taste retention and transparency, etc., especially in order to prevent oxygen from entering the gas and carbon dioxide escape gas barrier, but - The plastic material has poor gas barrier properties, and the packaging container of the human material has a large market demand. Therefore, it is used for: the gas barrier property of the wide-pack packaging container, so that it can be widely used for beer. The packaging of aerated beverages is the goal of researchers in this field. The method of improving the gas barrier properties of plastic materials is mainly to modify the commonly used 200918575 polyethylene terephthalate (PET) in beverage packaging, including surface coating method, composite layer method and bonding method. The surface coating method is to form a gas barrier layer by coating a high-barrier coating on the inner and outer surfaces of the PET bottle to prevent gas from entering and exiting. For example, US Pat. No. 6,827,972 and US Pat. No. 6,919,114 disclose the introduction of acetylene gas into a PET bottle. A method of forming a highly hydrogenated amorphous carbon as a gas barrier layer on the inside of a bottle by microwave plasma chemical vapor deposition and a product thereof. However, although the surface coating can achieve the function of blocking gas, the coating may have uneven thickness due to creep or frequent friction, and the barrier property may be degraded. In particular, the inner coating of the bottle also has a problem of food safety. The composite layer method is to use PET and a high barrier resin such as ethylene-vinyl alcohol copolyester (EVOH), m-xylylenediamine nylon (MXD6), p-ethylene naphthalate (PEN), etc., or the like. The oxygen-absorbing resin forms a multilayer composite layer which is mostly three or five layers. However, the multilayer composite PET bottle has many disadvantages such as high cost of manufacturing equipment required, layer separation may occur during the forming process, and difficulty in recycling, etc., so that its practicality is greatly reduced. The blending method is to directly mix high-barrier resin such as PEN or MXD6 in PET to improve the gas barrier property of PET. However, because PET is mixed with PEN or MXD6, it is also difficult to recycle. In addition to the method of increasing the gas barrier properties, some provide an active oxygen absorbing effect by adding an oxygen scavenger to the polyester, for example, in the case of U.S. Patent No. 6,083,585 and US Pat. No. 6,863,988. The absorption efficiency of the polyolefin oligomer is copolymerized with PET or PEN to form a copolymer of poly(S) and poly(200918575) olefin polymer, which can reduce the oxygen content in the packaging container. Keep the fresh taste of the contents of the package. However, this method also has its disadvantages, because the polyolefin-based oligomer is easily subjected to thermal degradation by adding a high-temperature polyester reaction system, and is affected by water produced by esterification in an acidic (for example, terephthalic acid) environment. The hydrolysis reaction is caused to cause a large decrease in the oxygen absorbing function of the polyolefin-based oligomer. There are still some shortcomings in the above-mentioned ways of increasing the gas barrier properties of plastic packaging containers, so that the packaging containers for beer and other aerated beverages are still mainly made of glass or aluminum. Therefore, there is still much room for improvement in how to improve the gas barrier properties and oxygen absorption of plastic materials. SUMMARY OF THE INVENTION The inventors of the present invention are eager to utilize the method of co-polymerization in view of the fact that the above-mentioned surface coating method is complicated and may affect food safety, and that the composite layer method and the mixed-mix method are difficult to recycle, and do not meet environmental protection requirements and the like. A polyester copolymer that combines oxygen and gas barrier properties is formed to simplify the process and make recycling easier. Therefore, the inventors have sought a modified material capable of both oxygen absorption and oxygen barrier functions and copolymerization with polyester. Since the molecular structure of PET is parallel to the benzene ring and the ethylene glycol ester, the gas molecules are easy to pass through the gap between the linear molecular chains, and polyethylene isophthalate (PEI) ) is a meta-molecular structure that forms a molecular chain like a valve structure that blocks gas molecules from traversing, so the gas barrier of PEI is much higher than that of PET (Kotek et al, Journal of Polymer Science: Part B: Polymer Physics , 42, 4247-4254, 2004), so the inventors pushed 200918575 to measure the combination of materials with meta-molecular structure and low-molecular-weight polyolefin polymers with oxygen-absorbing function, which should form both gas barrier and suction. Oxygen modified material. After extensive research and experimentation, it was found that polybutadiene (pBD, p〇Iybutadiene) with a molecular weight of about 1,000 to 5,000 was first reacted with Dimethyisophthalate having a meta molecular structure to form polybutadiene. - an m-phenylene diester intermediate, which is then subjected to an ester-reversion reaction with a diol such as ethylene glycol to obtain a modified prepolymer as shown in the formula:

Wherein R 2 is an alkyl chain having a carbon number of 1 to 24, and pbd is a polybutadiene, and the modified prepolymer of the formula 1 is superior in heat resistance to the polyolefin-based polymer, and during the reaction. The by-product is A_, which does not cause the hydrolysis reaction of polybutadiene, and can effectively solve the disadvantage that the oxygen absorption ability of the above-mentioned poly-smoke-type condensate in the high-temperature polymerization reaction system is greatly reduced. The modified prepolymer represented by Formula 1 can be subjected to a polycondensation reaction with a polyester prepolymer to form a polyester copolymer, or a reaction type extruder can be used to condense the modified prepolymer with poly-starting The poly-polymer is formed by the exchange reaction or other auxiliary agent, and the polyester copolymer is subjected to solid-state polycondensation reaction to increase the molecular weight. Thus, the enthalpy of both oxygen absorption and gas barrier can be formed. The polyester copolymer prepared by the octa octamer in this manner has good formability and can be applied to a food packaging container which requires high gas barrier properties and a packaging material for medical use. In particular, when the (4) copolymer obtained by the copolymerization of the modified prepolymer represented by Formula 1 is used to produce a beer/酉 bottle, the manufacturing cost is higher than that of the conventional PEN. 200918575 is cheaper and has the advantage of competing with glass or metal bottles at market price. Therefore, it is an object of the present invention to provide a poly-copolymer having oxygen absorption and gas barrier properties. Another object of the present invention is to provide a process for preparing a poly(S) copolymer having oxygen absorption and gas barrier properties. The polyester copolymer having oxygen absorbing and gas barrier properties of the present invention is composed of a) a modified prepolymer represented by Formula 1 and b) a polyester or polyester formed from a dicarboxylic acid and a diol. Polymer copolymerization: Ο Ο Ο Ο

In the polyester copolymer having oxygen absorption and gas barrier properties of the present invention, the higher the proportion of the modified prepolymer represented by Formula 1, the better the effect of oxygen absorption and gas barrier, but the higher the manufacturing cost, so The molar ratio of the modified prepolymer of a) to the polyester or polyester prepolymer of b) is suitably from 1:1 to 50. The dicarboxylic acid component of the polyester or polyester prepolymer of (b) is terephthalic acid 'isophthalic acid, naphthalene dicarboxylic acids, and P-hydroxybenzoic acid, hydroxynaphthoic acids, cyclohexane dicarboxylic acids, succinic acid, glutaric acid, adipic acid Adipic acid ), sebacic acid, 1,12-dodecane dioic acid or itaconic acid are preferred, and in 200918575, especially benzoic acid Formic acid, naphthalenedicarboxylic acid and isophthalic acid are suitable; in addition, the 'diol component is ethylene glycol, 1,3-propane diol, nathnhalylene glycol. 1,2-propane diol, 1,2-cyclohexane dimethanol, 1, 3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, diethylene glycol ), hydroquinone, 1,3-butane diol, 1,5-pentane diol, 1,6-hexanediol ( A glycol such as a 6-hexane diol, a triethylene glycol or a resorcinol is suitable, and ethylene glycol is particularly suitable. More specifically, the polyester copolymer of the present invention may, for example, be a polyester copolymer represented by Formula 2 or Formula 3: H(CH2)2〇-f.00.

ο _IL (Formula 3)

·〇—(CH2)2—

Wherein m: n = 1 to 50: 1 molar ratio, R 2 represents a alkyl group having a carbon number of 1 to 24, and pbd represents a polybutylene dilute. A method for preparing the polyester copolymer of the present invention, for example, first reacting a low molecular weight polybutadiene with a compound having a meta structure, such as m-xylylene dichloride, to form a formula 4 or formula 5 Intermediates: 10 200918575

In Formula 4, R1 represents an alkyl chain having a carbon number of 1 to 24, and pbd is a polybutadiene, Ο Ο 0 0 X-JVV pbdwx^O - χ --- (Formula 5) uu In Formula 5, X represents Halogen C Br group or hydroxyl group. The reaction procedure is shown in Reaction Scheme 1, and the reaction process is, for example, shown in Reaction Scheme 1, HOo^^pbd ^wv-oh +

+ Zn(OAc)2

- Reaction Scheme 1 The catalyst used in this example is acetic acid; then, a glycol compound such as ethylene glycol is added, and a transesterification is carried out with the formed intermediate to obtain a formula as shown in Formula 1. Modified prepolymer: 〇〇〇〇H0R20—pbd%^〇—U^^rvxU—ORsOH ---(Formula 1) uu In Formula 1, R2 represents an alkyl chain having a carbon number of 1 to 24, and pbd represents a poly Butadiene. The reaction procedure is shown in Reaction Scheme 2, 11 200918575

The reaction process also uses zinc acetate as a catalyst. It can be seen from the above-described reaction procedure for forming the modified prepolymer represented by Formula 1, that the by-product formed is an alcohol compound, does not cause hydrolysis reaction of polybutadiene, and the process temperature required for the transesterification reaction is lower than that. The process temperature of the polycondensation reaction can simultaneously reduce the probability of thermal degradation of the polybutadiene, and the modified prepolymer produced is an esterified product, and the heat resistance is better than that of the polybutadiene oligomer. When the modified prepolymer is further copolymerized with the polyester, the polybutadiene can be more fully utilized for its oxygen absorbing function. The modified prepolymer represented by Formula 1 can be subjected to a polycondensation reaction with a polyester prepolymer to form a polyester copolymer of the present invention, or a modified prepolymer and a polyester by a reactive extruder. Melting together, the polyester copolymer of the present invention is formed by a transesterification reaction or other auxiliary agent. For example, the modified prepolymer represented by Formula 1 and the Bien-hydroxy-ethylene iso/tere-phthalate (BHEIT, Bis-hydroxy-ethylene iso/tere-phthalate) The case where a melt phase polycondensation reaction is carried out to form a polyester copolymer can be expressed by the following reaction formula 3 12 200918575

- Reaction Formula 3 Further, the polyester copolymer obtained by the above melt-polycondensation reaction can be subjected to solid state polymerization to obtain a polyester copolymer having a higher molecular weight, which is suitable for forming a bottle and a film. . The polyester copolymer of the invention forms a copolymer with the polyester by the modified prepolymer, has the functions of oxygen absorption and gas barrier, and has good processability, and can be widely applied to foods with high gas barrier demand and Packaging materials for medical supplies. Further, the production of the polyester copolymer can utilize the existing production equipment and processing equipment for manufacturing polyester, which makes the process simpler and saves the expenditure of the process equipment. [Embodiment] Hereinafter, the contents of the present invention will be described in more detail by way of examples. &lt;Example 1 &gt; Synthetic modified prepolymer: 38.8 g (0.2 mole) of m-benzoic acid ester and 2,100 g/mol of HTPB, Hydroxy terminated polybutadiene 21 Og (0·1 mole ) and 0.12g of zinc acetate were poured into a 500 ml glass reactor and stirred at a constant temperature, and gradually heated to 235 ° C in 5 hours while allowing the methanol formed in the reaction to pass through the reactor. The distillation tube is distilled off and collected. Immediately after cooling to 150 ° C, add 9.3 g of ethylene glycol and continue to stir and stir, and gradually increase the temperature to 235 ° C within 5 hours, the reaction is full 13 200918575 Cheng Tong with a small amount of nitrogen until the total weight of the methanol reaches 12 8g When the above reaction is stopped, the product, i.e., the modified prepolymer, is discharged, cooled, and sealed for storage.成 成 酉 hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy (autoclave), in an environment where the pressure does not exceed 4 kg/cm2, the temperature is continuously increased (mixer speed is 60 rpm), and the temperature is gradually increased to 250 C in 5 hours while allowing the water generated by the reaction to pass through the fine tube. The museum collects. When the effluent weight of the museum reaches lG6g or more, the reaction is stopped, and the product, that is, the polyacetate prepolymer BHET, is discharged, cooled, pulverized, and ground into a white powder for use. Synthetic polyglycol copolymer Take the above-mentioned BHET 585g, modified prepolymer 15g, and add antimony trioxide (SbA3) 0_18g as a catalyst and antioxidant methyl trimethyl phosphate (tdmethyl phosphate) 0.045g, the volume is 丨 liter The stainless steel reactor is continuously heated and stirred (mixer speed is 6 rpm), and gradually heated to 28 〇t in about 5 hours, while vacuuming to ι torr in i hours, at the end of the reaction, when the mixer is stirred When the power was gradually increased from 7 〇w to 105 W, the reaction was stopped, and the product, that is, the polyester copolymer represented by Formula 2, was discharged, and after cooling, it was pelletized to prepare an ester granule. The modified prepolymer in the obtained polyester copolymer accounted for about 2.5% by weight. Dissolving 1 g of the aforementioned ester granules in 1 gram of phenol/tetra-ethane ethane (Phen〇l/terachl〇r〇ethane) i: ! (weight ratio) mixed solvent, and Ubdenide viscosity agent (Ubelode) -viscosimeter) The intrinsic viscosity (IV, intrinsic viscosity) of the 14 200918575 polyester copolymer measured at 30 ° C was 0.688 dL / g. &lt;Example 2&gt; The preparation procedure of Example 2 was the same as that of Example 1, except that the BHET used in the synthesis of the polyester copolymer of Example 2 was 570 g of the modified prepolymer was 30 g, wherein the modified prepolymer was The material accounts for about 5 wt ° / 〇, and the intrinsic viscosity of the obtained product is 0.672 dL / g. &lt;Comparative Example 1 &gt; Synthetic PET Polyester 519 g (3.12 mole) of terephthalic acid and 204 g (3.28 mole) of ethylene glycol were poured into a stainless steel reaction vessel having a volume of 1 liter, at a pressure not In an environment of more than 4 kg/cm2, the temperature is continuously stirred (mixer rotation speed is 60 rpm), and the temperature is gradually increased to 250 in 5 hours. (: At the same time, the water generated in the reaction is collected through the management of the tube. When the water weight of the water is 106g or more, 0.18 g of catalyst antimony trioxide and 0.045 g of trimethyl phosphate are added, and about 3 hours. The temperature is gradually increased to 280 ° C, and the vacuum is evacuated to about 1 torr in 1 hour. At the end of the reaction, when the stirring power of the mixer is gradually increased from 70 W to 105 W, the reaction is stopped, and the product is discharged, and then granulated after cooling. It is a PET ester granule. The intrinsic viscosity (IV) of the PET ester granule was tested to be 0.688 dL/g. <Comparative Example 2 &gt; Commercially available vinegar granules_Comparative example of the masterbatch of the getter ester button PET pellet (manufactured by Far Eastern Textile Co., Ltd., model CB608) 970g and oxyacetin masterbatch (masterbatch, 15 200918575 COLORMATRIX company sold under the trade name Amosorb) 30g, plastic spectrometer (made by Toyo Seiki Co., Ltd., LABO PLASTICMILL) After extruding the ester strip by a biaxial extruder of 50C150), the sample was sealed and sealed, wherein the mother particles of the oxygen absorbing ester particles accounted for about 3 wt%. <Comparative Example 3 &gt; The preparation method of Comparative Example 3 was the same as that of Comparative Example 2. But the PET ester granule is 950g, the mother of the oxygen absorbing ester granule It is 50g, in which the mother particles of the oxygen absorbing ester particles account for about 5 wt%. The oxygen absorption rate test is tested according to the test standard of oxidative stability (ASTM D6186) and oxidative induction time-ASTM D3895. The ester granule samples of Examples 1, 2 and Comparative Examples 1, 2, and 3 were each about 40 ± 2 mg, respectively, using a thermogravimetric analyzer (TGA, manufactured by ΤΑ Instruments, Model TGA 2950). In an oxygen atmosphere, the temperature is raised from 50 ° C to 300 ° C at a heating rate of 2 ° C / min, wherein the temperature is constant at 150 ° C for 30 minutes, and at 250 ° C for 10 minutes, and the oxygen is calculated from the measured curve. Absorption rate. The test results are shown in Table 1. Table 1 Thermogravimetric change (mg) Oxygen absorption rate (〇2 mg/mg) Example 1 +9.8956 10.14 Example 2 +28.8900 14.90 Comparative Example 1 -1.1237 _ Comparative Example 2 + 5.6044 9.33 Comparative Example 3 + 14.0488 14.04 16 200918575 The results of Table 1 show that Comparative Example 1 (general PET polyester) does not have oxygen absorption capacity, whereas the present invention utilizes a modified prepolymer to form a polyester copolymer ( Embodiments 1, 2) can be large The width increases the oxygen absorption effect. Further, the modified prepolymer contained in the polyester copolymer of Example 1 was about 2.5 wt%, and the oxygen absorbing granules contained in the pet ester granule of Comparative Example 2 were about 4 wt% compared with the commercially available oxygen absorbing granules. 3 wt%, the oxygen absorption rate from Example 1 was higher than that of Comparative Example 2, and Example 1 had a better oxygen absorption effect than Comparative Example 2. Further, when the modified prepolymer contained in the polyester copolymer of Example 2 was about $wt/〇, and the oxygen absorbing ester particles contained in the PET ester particles of Comparative Example 3 were also about 5 wt%, Example 2 also had an oxygen absorbing effect better than that of Comparative Example 3. Since the vinegar granule of the poly-g-copolymer of the present invention can be directly processed and formed, the handle is more than the master batch of the commercially available oxygen-absorbing ester granule, and it needs to be subjected to a mixing processing procedure at the time of use, and therefore, the polyester of the present invention Compared with the commercially available oxygen absorbing granules, the copolymer has a better oxygen absorbing effect in addition to the cost of regranulation during downstream processing. &lt;Example 3 &gt; Gold-forming polyester copolymer Pour 24.6 kg of terephthalic acid, 126 kg of m-dicarboxylic acid and 12.1 kg of ethylene glycol into a reactor of 1 liter liter stainless steel, and continue to heat and stir. And gradually raise the temperature to 25 Torr in 5 hours, the pressure is controlled within 3 kg/cm2, and the water produced by the reaction is distilled off through the distillation tube. When the distillate weighs more than 5.6 kg, the reactants are transferred to the recombination reaction tank, and 9.0 g of Sb2〇3 catalyst, 27 g of H3p〇4 (concentration 17 200918575 5.6%), and 0.9 kg of upgrading are added. The prepolymer was gradually heated to 280 ° C while vacuuming the vacuum pump to about ltorr in 1 hour. At the end of the reaction, when the current of the mixer shows that the original 2.3A gradually rises to 2.5A, the reaction is stopped, and the product is discharged, cooled, and pelletized to form a polyester copolymer ester granule. The intrinsic viscosity (IV) was tested to be 0.62 dL/g. Solid state polymerization 15 kg of the polyester copolymer ester granules obtained above were poured into a 30 liter solid state polymerization reactor, and solid state polymerization was carried out at 220 ° C for 8 hours, and the degree of vacuum during the reaction was controlled within 1. Torr torr. The intrinsic viscosity of the ester particles after solid state polymerization was increased to 0.78 dL/g. The dough was formed by the above-mentioned solid-state polymerization of the ester particles, and a bottle having a capacity of 350 cc was obtained through an injection and blow molding process. Oxygen, oxygen transmission rate; test the bottle prepared above, using analytical instrument [ModekOXTRAN MOCON 2/21], relative humidity (RH) 55% ~ 65%, temperature 23 ° C ± 2 The oxygen permeability was measured in an inflated atmosphere of ° C, an environmental condition containing 21% of oxygen, and a mixed gas containing 98% of nitrogen and 2% of hydrogen. As shown in Fig. 1, in order to continuously measure the oxygen permeability measurement value for 65 days, the oxygen permeability measured at the 65th day was 3.09x10 cc/day-atm ο &lt;Comparative Example 4 &gt; PET PET pellets were prepared in the same capacity and bottle shape as in Example 3, and the oxygen permeability of the PET bottle was measured by the test method of the same conditions as described above. 18 200918575, the oxygen permeability measured on the 65th day. (4), which is the test result of the 5.7xl〇'2 cc/day-atm milk gas permeability, ..., the bottle made by the polyester of the present invention can be compared with the PET and the two inventions. 1 has better gas barrier effect. It has a good oxygen absorption effect and has a high-interval content of foods with high oxygen barrier function, Μ ^ has been widely used in gas barriers, such as beer, and packaging materials for medical supplies. Therefore, it is possible to achieve the object of the present invention. The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto. BRIEF DESCRIPTION OF THE DRAWINGS The simple equivalent changes and modifications made by the present invention are still within the scope of the present invention. [Simplified Schematic] FIG. 1 is a graph of oxygen permeability versus tracking days, illustrating that the present invention has oxygen absorption and The oxygen barrier of the bottle holder prepared in Example 3 of the gas barrier polyester copolymer measured within 65 days of the tracking test. [Main component symbol description] 19

Claims (1)

200918575 X. Patent Application Range·· 1. A polyester copolymer with oxygen absorption and gas barrier properties, which is composed of a) modified prepolymer represented by formula 1 and b) dicarboxylic acid and diol The formed polyester or polyester prepolymer is copolymerized: hor2o 〇 〇 pbdvwO- Or2oh (wherein h represents an alkyl chain having a carbon number of 2424, and pbd represents a polybutadiene. 2. A polyacetic acid copolymer having oxygen and gas barrier properties according to the scope of claim ii. 'The illusion and b' of the Mobi ratio is 1: 丨 ~ don't. 3. The invention relates to a polyester copolymer having oxygen absorption and gas barrier properties as described in the above item 1, wherein the dicarboxylic acid is selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and p-hydroxy group. a group consisting of benzoic acid, hydroxynaphthoic acid, cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecamic acid, itaconic acid; Ethylene glycol, H alcohol, butanol, 1,2-propanediol, Li cyclohexanedimethanol, hydrazine, cyclohexanedimethanol, U4-cyclohexanedimethanol, diethylene glycol, p-benzoic acid, di- A group of yeast, i, 5-pentanediol, hydrazine-hexanediol, triethylene glycol, and isophthalene. 4. According to the third aspect of the patent, the oxygen-absorbing and gas-blocking poly U-products are selected, wherein the diacid is selected from the group consisting of terephthalic acid, naphthalene dicarboxylic acid and meta-dicarboxylic acid. The diol is ethylene glycol. 5. According to the scope of the patent application No. 4 β, the polysulfonated copolymer having the gas content of the material is represented by the formula 2 or the formula 3: 20 200918575 H(CH2)2CH^—1^3-(C*&quot ;*2)2. ----(式2) O^^pbdwvsQ. 〇R2〇*)n-H H(CH2)20 o 11 ----(Formula 3) -o-(CH2): O^WpbdvW'Q. OR2〇 烷基 1~24 alkyl wherein 'm : n=l~50 : 1 molar ratio, r2 represents a carbon number chain, and pbd represents polybutane. 6. A method for preparing a polyester copolymer having oxygen absorption and gas barrier properties by first forming an intermediate between polybutadiene and a compound having a meta structure, and then making the intermediate and a glycol compound The transesterification reaction is carried out to form a modified % prepolymer. The modified prepolymer is reacted with a polyester or polyester prepolymer formed from a di-acid and a glycol to form a polyester copolymer. 7_ A method for preparing a polyacetic acid copolymer having oxygen absorption and gas barrier properties according to the scope of claim 6 wherein the modified prepolymer is subjected to a transesterification reaction with the polymerization system to form a polyester copolymerization Things. 8. The method for preparing a polystyrene copolymer having oxygen absorption and gas barrier properties according to claim 6, wherein the modified prepolymer and the polyester prepolymer are subjected to a polycondensation reaction to form Polyester copolymer. A method for producing a polyester copolymer having oxygen absorbing and gas barrier properties according to any one of claims 6 to 8, wherein the molecular formula of the intermediate is as shown in Formula 4 or Formula 5: Ο 0 ρ5ά,'-Γί/ν'0 (Formula 4) 21 200918575 In Equation 4, Ri represents a burnt-base chain with a carbon number of 1 to 24, and Pbd represents a polybutane In the formula 5, 'X' represents a halogen c-br group or a hydroxyl group. 10. A method for preparing a polyester copolymer having oxygen absorption and gas barrier properties according to the scope of claim 9 of the patent application, wherein the modified prepolymer has a molecular formula as shown in Figure 1: ~, - The method of using a six' negative and rolled and hindered polyester copolymer, wherein the glycol compound is ethylene glycol. 13::: A method for preparing a polystyrene copolymer having oxygen absorption and gas barrier properties according to claim 11, wherein the glycol compound is money 14:: please refer to item 6 of the scope of interest Preparing a method for absorbing oxygen-aerobic X-rays from a total amount of enthalpy, wherein the modified prepolymer and the vinegar prepolymer have a molar ratio of 41: .. A method for preparing an oxygen-absorbing and gas-barrier S曰 co-offer is prepared by reacting a phthalic acid 22 200918575 acid with ethylene glycol. A method for producing a polyester copolymer having oxygen absorbing and gas barrier properties according to the scope of claim 6 wherein the polybutene has a molecular weight of from 1,000 to 5,000. twenty three