TW420698B - Method to change synthetic reaction rate of polyethyl terephthalate ester - Google Patents

Abstract

This invention provides a method to change synthetic reaction rate of polyethylene terephthalate (PET) and the catalyst used. This method includes the addition of a pre-treated catalyst composition, into the synthetic reaction of PET. The catalyst composition consists of an antimony-containing substance and a zinc-containing substance. The pre-treatment involves sintering treating the above-mentioned catalyst composition before it is added to the synthetic reaction of PET to change synthetic reaction rate of PET.

Description

Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs ^ 20698 A7 --- ΒΊ V. Description of the Invention (1) Field of the Invention This case relates to a method and catalyst composition for changing the rate of polyethylene terephthalate. β Background of the Invention Polyester fibers have good heat resistance and excellent performance, and are suitable for long fibers and short fibers. Therefore, they are widely used. In the early days, they were mainly used for the production of clothing, and they have gradually expanded to decoration and other industrial applications. The main raw material of the polyester fiber is polyethylene terephthalate (ρ ο 1 y e ΐ h y 1 e n e t e r e p h t h a 1 a t e, p Ε Τ). At present, there are many synthetic methods of PET, and terephthalic acid (TpA) and ethylene glycol (EG) are the main methods for general industrial production. They include two steps, namely, esterification and polycondensation. First, T p a is esterified with EG to produce di-n-ethyl terephthalate (BHET), and then a polycondensation reaction is performed to form PET. In order to increase the polycondensation reaction rate of PET synthesis, so that the reactants reach a high degree of polymerization in a short time, a catalyst is often added to achieve this. The catalysts that are more commonly used today are metal catalysts, including metal compounds such as antimony, zinc, and ‘titanium’ and their derivatives. At present, some patents such as EP0399742A2 and EP 0425215A2 all use S b 2 0 3 as the catalyst to shorten the time of traditional polycondensation reaction. However, a suitable catalyst should have high activity and be unlikely to cause side reactions. ‘And poor color, especially when p E T is used in food packaging’, the toxicity of the catalyst is a factor that cannot be ignored. Therefore, the paper size of the paper is applicable to the Chinese National Standard (CNS) / \ 4 specifications ({Please read the note A on the back before filling this page). Order 420698

V. Description of the invention (2 :) The catalyst meeting the above conditions and accelerating the rate of synthesizing pET is the main purpose of the development of this case. Β The comprehensive description of the invention The main purpose of the present invention is to provide a modified polyethylene terephthalate Method of synthesis rate and catalyst composition. The method includes adding a pretreated catalyst composition to a synthetic reaction of ethylene terephthalate, wherein the catalyst composition includes an antimony-containing substance and a zinc-containing substance. According to the above concept, the polyethylene paraben (ρΕτ) is synthesized by using terephthalic acid and ethylene glycol as reactants, and then synthesized through arsine reaction and polycondensation reaction. Β This pre-treated catalyst combination The catalyst can be added before the esterification reaction or during the polycondensation reaction. The catalyst treatment is to calcinate the catalyst composition, and the preferred range of the forging sound β degree is between 1000 and 500. Between 0.0%. Where ™ The antimony-containing substance is preferably-a compound selected from the group consisting of antimony oxides and antimony phosphonates, such as dioxin. S The zinc-containing substance is preferably-selected From zinc oxides and zinc carbonates, such as acetic acid. The Moore number of this substance and the substance is better 146: 64 »^ The following scheme and details Explanation, worth the understanding. 俾 付-深深. I: I .......-II — ^ 1,

I nn Γί κ n I (Please read the notes on the back of # before writing this page. J Ding,-° Printed by the Consumers' Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs " This paper size applies to China's national standard (〇 奶) 4 Specification (210/297 g) 4206 ^ 8 A7 V. Description of the invention (3) Schematic description ^ The picture shows the zinc antimony of the present invention before the synthesis reaction of synthetic polyethylene terephthalic acid. Co-catalyst, the graph of the relationship between the esterification rate and the time finally obtained. Π The second picture is the different pretreatment of the zinc-antimony co-catalyst of the present invention, which is a second-degree polycondensation of polyethylene terephthalate synthesis. The detailed description of the preferred embodiment printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Film and Economics of the Reaction The present invention discloses a method and catalyst composition for changing the rate of polyethylene terephthalate synthesis ^ The method includes The treated catalyst composition is added to the synthesis reaction of polyethylene terephthalate, wherein the catalyst composition includes an antimony-containing substance and a zinc-containing material. The pretreatment is to forge the catalyst composition. Add to polyethylene terephthalate after firing treatment In the synthesis reaction of acid esters, the synthesis rate of polyethylene terephthalate is changed. A preferred embodiment of this case is used to describe the method and its characteristics in detail. ^ The catalyst composition (also referred to as co- (Catalyst) The preparation method is to prepare an antimony trioxide (Sb203) / zinc acetate (ZηΑ <: 2 · 2Η2〇) co-catalyst with a molar ratio of 1 46:64, and then according to the different pre-treatment calcination temperature Divided into six kinds of co-catalyst system, and heated to 100 ° C, 200 ° C, 300 ° C, 40 (TC and 50 t) at a rate of 1 ° C / mi η, and stayed for four hours Cooling down. It is named 4 according to the different pretreatment and calcination temperatures. This paper size is applicable to China National Standard Soap (CNS) Λ4 gauge (2 丨 〇Χ 297) n-II --11 ^! I-1-1 ^ ^ 1-: .'i .. (# 先 ＭRead the note on the back to fill out this page) ~ ^-Order ------ " ^ Printed by A20698 A7, Consumers Cooperative of Central Standards Bureau, Ministry of Economic Affairs _____B7 V. Description of the Invention (f) ~~~~

SbZn-RT, SbZn-100, SbZn-200, SbZn-300,

SbZii-40 0 and SbZn-5 0 0, RT represents room temperature, and numbers represent the calcination temperature. The catalyst is added by adding the catalyst immediately before the vinegarization reaction. The amount of the catalyst is 0.11632 g (0.008745 < g Sb203 + 0.02887 g ZnAc2.2H2). The time required for the esterification rate of each co-catalyst system to reach 90% and the final esterification rate after the end of the vinegarization reaction (410 minutes) were used as the pre-treatment zinc catalyst co-catalyst to catalyze the esterification reaction. Judgment criteria for activity. 'From the first figure, it can be seen that with the exception of SbZn-500, the other g-catalyst systems obtained after the S-chemical reaction can achieve a g conversion rate of more than g $%, and the esterification rate reached 90%. The time required for the SbZn-3 0 0 co-catalyst system is as short as 326 minutes. The order of catalytic activity of each catalyst system for esterification:

SbZn-300 > SbZn-400 > SbZn-200 > SbZn-RT >

SbZn-100 > SbZn-500, and the order of the acetic acid conversion rate of each catalyst system after the S reaction is

SbZn-400 (98.58%) > SbZn-3〇〇 (97.87%) > SbZn-200 (96.23%) > SbZn- 100 (95.79%) > SbZn-RT (95.45%) > SbZn- 500 (90.39%) From the above results, it can be seen that the antimony co-catalyst system after high temperature heat treatment has indeed a good catalytic activity for the quenching reaction. 5 The paper scale is applicable to the Chinese National Standard (CNS) Λ4 {210X297 ^ 77 (Please read the precautions on the back before filling this page)

42 0698 Central Standard of the Ministry of Economic Affairs MS: Printed by Industrial and Consumer Cooperatives Λ7 B7 V. Description of the invention (f) In addition, please refer to the second picture. Effect of Polycondensation on Phthalic Acid Synthesis. From the results in the second figure, it can be seen that the viscosity of the catalyst systems other than SbZn-5 0 0 is significantly higher than that of catalyst systems containing only antimony. Therefore, the catalytic activity of the calcined co-catalyst system will not be attenuated by the temperature treatment process. The second figure also shows that when the co-catalyst system of SbZn-300 reaches three hours of polymerization, although its viscosity value reaches 0.75 dl / g, which is only slightly higher than the co-catalyst system of other groups, At two hours, the viscosity value has reached 0.73 dl / g, which is significantly higher than other co-catalyst systems. After calcination at 300 ° C, new activation centers or zinc-antimony are formed between the co-catalysts. Bimetallic compounds further increase the rate of polymerization, so the zinc-antimony co-catalyst after calcination does indeed have a good effect on the catalytic activity of the polymerization reaction. In this case, the effect of the antimony-zinc co-catalyst on the synthesis reaction of pET after different heat treatment temperatures is mainly based on the inherent viscosity as a method to evaluate the activity of the catalyst system. Table 1 shows the solid viscosity values obtained by adding each catalyst system before the esterification reaction of pET synthesis. 1- n IT ---- I --- ΛI I L --- n T _I —_____ into L____ a Js-, '':., * (Please read the precautions on the back before filling itT page) Sheet Zhang Chiqian _ (210χ297λ > ^ ------ 420698 Α7 Β7 V. Description of the invention (Dagger) Table 1 Intrinsic viscosity of the catalyst added before the esterification reaction (dl / g) Sb2〇3 0.52 SbZn-RT 0 73 SbZn-100 0. 74 SbZn-200 0. 74 SbZn-300 0.75 SbZn-400 0.71 SbZn-500 0. 52 1 1 — —One. — Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. When the calcination temperature is lower than 500 ° C, the catalytic activity of the zinc-antimony co-catalyst system is higher than that of the catalyst system containing only Sb203. The zinc-antimony co-catalyst has the best effect. In addition, the zinc-antimony co-catalyst was added before the esterification reaction, and the esterification and polymerization rates were found to be faster than those of pure Sb203. Of course, the above is better. Various conditions such as the amount of the catalyst composition used in the examples, the calcination treatment temperature, and the reaction time are only for the convenience of further detailed description of this case, and should not be used to limit the scope of the patent application for this claim. In addition, the timing of the addition of the catalyst grade can be added before the esterification reaction or during the polycondensation reaction. In summary, the change in the polyethylene terephthalate synthesis rate provided by this case The method is to first treat the catalyst composition by calcination, and its catalytic activity will not be attenuated by the high temperature treatment process. The catalytic activity of the oblique polymerization reaction has a good effect, which can increase the polyethylene return field 7 n-I Γ —Ϋ-* ί I 1 / ^^^ ^^^ 1 II (Please read the notes on the back before filling this page) Ί !! Ί;

This paper size is applicable to China National Standard #CNS (210X297) H 420698 A7 ________B7________ 5. Description of the invention (" I) The synthesis rate of benzalkorate shortens the reaction time, so it can be applied to industrial production. Yes Therefore, this case may be modified by people who are familiar with this technology, but they are not as good as those who want to protect the scope of patent application. (# 先 间 # Note on the back of this page, please fill out this page) Employees of the Central Ministry of Standards and Technology of the Ministry of Industry and Commerce Cooperative Cooperative Print 8 This paper size applies to the Chinese National Standard {CNS) Λ4 ^ 格 （210X297,0 ^ 7

Claims (1)

420698 Application for Patent Scope September 1988 Application for Patent Scope Correction Page Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs · 1 · A method for synthesizing polyethylene terephthalate (PET), which includes warming the The burning catalyst composition is added to the synthesis reaction of polyethylene terephthalate, wherein the catalyst composition includes a recording material and a zinc-containing material, and the calcination temperature range is 100%. . 〇 ^^ 11 ^ less than 50000 2. The method as described in the application for patent i., Wherein the synthesis of polyethylene terephthalate (PET) is based on terephthalic acid and Ethylene glycol is a reactant, which is synthesized via an acetation reaction and a polycondensation reaction. 3. The method as described in item 2 of the scope of patent application, wherein the high-temperature calcined catalyst composition is added before the esterification reaction. 4. The method according to item 2 of the scope of patent application, wherein the high-temperature calcined catalyst composition is added during the polycondensation reaction. ^. The method as described in claim 1 of the patent claim, wherein the antimony-containing substance is a compound selected from the group consisting of oxides of antimony and acetates of antimony. 6. The method according to item i of the patent application scope, wherein the antimony-containing substance is antimony trioxide. The method described in item 1 of the patent claim, wherein the zinc-containing substance: a compound selected from the group consisting of zinc oxide, acetate and zinc carbonate. j & π 8 ′ 2 The method described in item 1 of the patent scope, wherein the zinc-containing substance is zinc acetate. Please read the notes of the memorandum before-f This page © This paper size is 210X297 mm)