WO2008113230A1 - Procédé de préparation de catalyseur liquide contenant du titane pour le polyester ou le copolyester - Google Patents

Procédé de préparation de catalyseur liquide contenant du titane pour le polyester ou le copolyester Download PDF

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Publication number
WO2008113230A1
WO2008113230A1 PCT/CN2007/002917 CN2007002917W WO2008113230A1 WO 2008113230 A1 WO2008113230 A1 WO 2008113230A1 CN 2007002917 W CN2007002917 W CN 2007002917W WO 2008113230 A1 WO2008113230 A1 WO 2008113230A1
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WO
WIPO (PCT)
Prior art keywords
polyester
acid
butyl titanate
mol
reaction
Prior art date
Application number
PCT/CN2007/002917
Other languages
English (en)
Chinese (zh)
Inventor
Fantao Kong
Xinsheng Ma
Qiufang Wu
Fuqing Li
Jinghui Yang
Gang Chen
Rui Ma
Qihua Dong
Original Assignee
Shanghai Huaming Hi-Tech (Group) Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Huaming Hi-Tech (Group) Co., Ltd. filed Critical Shanghai Huaming Hi-Tech (Group) Co., Ltd.
Priority to JP2009553884A priority Critical patent/JP5366838B2/ja
Publication of WO2008113230A1 publication Critical patent/WO2008113230A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

Definitions

  • the present invention relates to a process for the preparation of polyesters and copolyesters, and more particularly to titanium-based catalysts used in the polycondensation process. Background technique
  • polyester and copolyester have a wide range of applications in light industry, machinery, electronics, packaging and other fields.
  • the polyester and copolyester according to the present invention are polymer compounds having the following structural fragments (for example, polyester):
  • n is the degree of polymerization, usually n > 50, and its molecular weight is greater than 10,000.
  • the copolyester is a component added to the polyester polymerization process for improving the properties of the polyester, such as isophthalic acid and its derivatives, polyethylene glycol, polytetramethylene glycol, and the like.
  • the catalysts currently used in the preparation of polyesters mainly include lanthanide, lanthanide and titanium catalysts.
  • Lanthanide catalysts have moderate activity, few side reactions, mature technology, good product hue and low production cost. They are widely used polyester polycondensation catalysts, but the use of ruthenium catalysts will cause environmental pollution and human body to some extent. Health hazard;
  • Titanium catalysts are the most active polyester polycondensation catalysts, but their selectivity is not as good as that of lanthanide catalysts. The hue of products is usually not satisfactory. .
  • the selectivity of the titanium-based catalyst is not good because most of the titanium-based catalysts have poor solubility in the reaction system as compared with the ruthenium-based catalyst, and are used as heterogeneous 7 002 917 used in the chemical. Therefore, by technical means, the solubility of the titanium-based catalyst in the polyester synthesis system is improved, and the heterogeneous catalysis of the titanium-based catalyst is converted into homogeneous catalysis, which is to improve the selectivity of the titanium-based catalyst and improve the polymerization using the titanium-based catalyst. An important method of ester product quality.
  • the method disclosed in CN1583823A is to dissolve the existing powdery titanium-based polyester catalyst in ethylene glycol by heating, and then add it to the reaction system to achieve the purpose of homogeneous catalysis, but this method is actually used. Time is still not convenient enough. Moreover, since the solubility of the catalyst in ethylene glycol is not very large, its application in actual production is also limited to some extent.
  • the patent CN1644601A discloses a preparation method of a liquid titanium homogeneous catalyst. The liquid titanium catalyst obtained by the method has good solubility in ethylene glycol, catalytic activity and selectivity. Higher characteristics, with better application prospects. However, the patent CN1644601A uses isopropyl titanate as a starting material.
  • the technical problem to be solved by the present invention is to disclose a preparation method of a liquid titanium-based catalyst for preparing a polyester and a copolyester to overcome the above-mentioned drawbacks of the prior art.
  • the preparation method of the liquid titanium catalyst for preparing polyester and copolyester according to the present invention is characterized in that it comprises the following steps:
  • the n-butyl titanate, ethylene glycol, ethyl orthosilicate and a metal promoter are reacted in a solvent for 0.5 to 2.5 hours, the reaction temperature is 80 to 180 ° C, and the reaction temperature is preferably 85 to 160 ° C.
  • the reaction temperature is 80 to 180 ° C, and the reaction temperature is preferably 85 to 160 ° C.
  • the method for separating and removing small molecules in the reaction system is a conventional method such as a conventional distillation method
  • the inventors have surprisingly found that the choice of metal promoters and complexing agents and their ratios have a greater impact on the present invention and will directly affect the activity and selectivity of the catalyst. To this end, the inventors have undergone extensive testing and have chosen the following -
  • the metal promoter is selected from one or more of the acetate or nitrate of the metal elements of Groups IA, IIA, IIIA, IIB, IIIB, VIIB, VIIIB, preferably cobalt acetate, zinc acetate, acetic acid. Magnesium, aluminum nitrate, calcium acetate or manganese acetate.
  • the complexing agent is a phosphate ester and an ⁇ -hydroxycarboxylic acid
  • the phosphate ester is preferably trimethyl phosphate, trimethyl phosphite, triethyl phosphate and triethyl phosphite, and the hydroxycarboxylic acid refers to hydrated citric acid, tartaric acid, L-lactic acid and salicylic acid;
  • the ⁇ -hydroxycarboxylic acid is preferably L-lactic acid and hydrated citric acid;
  • the solvent is one or a mixture of two of ethanol and/or butanol.
  • the molar ratio of n-butyl titanate to ethylene glycol is 1:16 ⁇ 1:30, preferably 1:20 ⁇ 1:30 ;
  • the molar ratio of n-butyl titanate to phosphate is 1:0.5 ⁇ 1:2, preferably 1:0.5 ⁇ 1:1.5; the molar ratio of n-butyl titanate to hydroxycarboxylic acid is 1:0.5 ⁇ 1: 2, preferably 1 : 0.5 ⁇ 1 : 1.5; the molar ratio of n-butyl titanate to ethyl orthosilicate is 20:1 ⁇ 1:1, preferably 7:1 ⁇ 5:2 ;
  • the molar ratio of the butyl ester to the total amount of the metal element is 20:1 to 3:1, preferably 17
  • the molar ratio of n-butyl titanate to solvent is 1:10 to 1:30, preferably 1:15 to 1:25.
  • the catalyst prepared by the above method can be used for preparing polyester and copolyester.
  • polyester and copolyester are prepared by using terephthalic acid and ethylene glycol as raw materials
  • the catalyst can be directly added to the reaction system or After being diluted in ethylene glycol and added to the reaction system, it may be added to the reaction system between the esterification reactions or may be added to the reaction system after the end of the esterification reaction or before the start of the pre-polycondensation reaction.
  • the catalyst is added in an amount of 1 X 10" 6 ⁇ 8 X 10" 6 o by weight of the titanium atom to the purified terephthalic acid.
  • the catalyst is added in an amount of preferably 1 X 10" 6 ⁇ 4X 10" 6 c by weight of the titanium atom to the purified terephthalic acid.
  • the present invention adopts n-butyl titanate having a small steric hindrance in the complexation reaction as a starting material and preferably other raw materials, compared with the prior art, the complexation reaction speed can be ensured to be faster and the reaction is more thorough. Not only does it have a large solubility in ethylene glycol, but it also significantly improves the compatibility with polyester.
  • the catalyst of the present invention has high catalytic activity for polyester polycondensation reaction, and the amount of addition is small, and the obtained polyester product has advantages of good hue (low yellow phase value and high brightness value) and good spinnability, and another aspect of the present invention
  • One advantage is that the prepared catalyst is not hydrolyzed, and it is not necessary to add a heat stabilizer when used, and the toxic and harmful solvent is not used in the preparation method, the obtained catalyst can be mutually miscible with ethylene glycol, and can be stably stored for a long period of time, and has good Industrial application prospects and value.
  • the invention is described in more detail by means of the following examples.
  • the analysis of the quality of the polyester was carried out in accordance with the GB/T 14190-1993 fiber grade polyester chip analysis method.
  • the intrinsic viscosity of the slice was measured in a phenol-tetrachloroethane mixture (mass ratio of 1:1) at 25 °C.
  • the hue of the polyester was evaluated using the L, a, b color system. In this system, L is the lightness factor, and 1) is the color measurement Number.
  • b represents the balance of yellow and blue, which is very important for the color of the polyester. The lower the b value, the better the hue of the polyester, especially for the fiber-forming polyester chips. For polyester products that are not critical to color requirements, higher b values are acceptable.
  • Example 4 To a 250 ml flask equipped with a stirring paddle and a condensing device, 106 g of ethylene glycol (1.71 mol) was added, 3.29 g of zinc acetate (0.015 mol) was dissolved therein, and then 22.80 g of n-butyl titanate (0.067 mol) was added to the solution. 3, 3.12 g of tetraethyl orthosilicate (0.015 mol) and 46 g of ethanol (1 mol) were reacted at 100 ° C for 1 h.
  • Example 8 The same procedure as in Example 8 was carried out except that 0.1794 g (Ti content: 4 ppm) of the liquid catalyst prepared in Example 2 was added, and after a final polycondensation reaction time of 100 minutes, an intrinsic viscosity of 0.67 and a melting point of 256 ° C were obtained.
  • Example 8 In the same manner as in Example 8, except that 0.1581 g (Ti content: 4 ppm) of the liquid catalyst prepared in Example 3 was added, after 95 minutes of final polycondensation reaction time, an intrinsic viscosity of 0.67 and a melting point of 257 ° C were obtained.
  • Example 8 In the same manner as in Example 8, except that 0.1794 g (Ti content: 4 ppm) of the liquid catalyst prepared in Example 4 was added, after an initial polycondensation reaction time of 105 minutes, an intrinsic viscosity of 0.67 and a melting point of 258 ° C were obtained. A polymer having an L value of 71 and a b value of 2.0.
  • Example 13 In the same manner as in Example 8, except that 0.1786 g (Ti content: 4 ppm) of the liquid catalyst prepared in Example 5 was added, after a final polycondensation reaction time of 108 minutes, an intrinsic viscosity of 0.67 and a melting point of 258 ° C were obtained. A polymer having an L value of 77 and a b value of 4.0.
  • Example 8 In the same manner as in Example 8, except that 0.1754 g (Ti content: 4 ppm) of the liquid catalyst prepared in Example 6 was added, after 94 minutes of final polycondensation reaction time, an intrinsic viscosity of 0.66 and a melting point of 256 ° C were obtained. A polymer having an L value of 71 and a b value of 1.9.
  • Example 8 The same procedure as in Example 8 was carried out except that 0.1770 g (Ti content: 4 ppm) of the liquid catalyst prepared in Example 7 was added, and after a final polycondensation reaction time of 102 minutes, an intrinsic viscosity of 0.68 and a melting point of 260 ° C were obtained.
  • Example 8 In the same manner as in Example 8, except that 0.35 g of Sb 2 O 3 catalyst was added, 40 ppm of trimethyl phosphate was added as a heat stabilizer after the end of the esterification reaction, and after a final polycondensation reaction time of 125 minutes, A polymer having an intrinsic viscosity of 0.67, a melting point of 258 ° C, an L value of 66, and a b value of 3.1.

Abstract

L'invention concerne un procédé de préparation de catalyseur liquide contenant du titane pour le polyester ou le copolyester, qui consiste à faire réagir tétra n-butyl titanate, éthylène glycol, tétraéthyl orthosilicate et un cocatalyseur métallique dans un solvant, à évacuer la petite molécule dans le système de réaction, et ensuite à introduire l'agent complexant et à faire réagir pour obtenir le catalyseur liquide contenant du titane.
PCT/CN2007/002917 2007-03-20 2007-10-10 Procédé de préparation de catalyseur liquide contenant du titane pour le polyester ou le copolyester WO2008113230A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2009553884A JP5366838B2 (ja) 2007-03-20 2007-10-10 ポリエステル又はコポリエステルに用いられるチタン含有液状触媒の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200710038230.7 2007-03-20
CN 200710038230 CN101270185B (zh) 2007-03-20 2007-03-20 用于制备聚酯与共聚酯的液态钛系催化剂的制备方法

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WO2008113230A1 true WO2008113230A1 (fr) 2008-09-25

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JP (1) JP5366838B2 (fr)
CN (1) CN101270185B (fr)
WO (1) WO2008113230A1 (fr)

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CN114989405A (zh) * 2022-07-11 2022-09-02 青岛大学 一种dmt法合成聚酯的钛系催化剂及其制备方法和应用

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CN101724140B (zh) * 2009-12-04 2012-09-05 清华大学 一种用于可生物降解聚酯催化剂的制备方法
CN102391490B (zh) * 2011-09-29 2014-04-16 南昌航空大学 一种负载型钛系聚酯催化剂的制备方法及其应用
CN103333328A (zh) * 2013-06-05 2013-10-02 新疆蓝山屯河化工股份有限公司 生物降解聚酯复合催化剂及其制备方法和使用方法
CN103435794B (zh) * 2013-07-26 2015-08-12 旭阳化学技术研究院有限公司 一种缩聚催化剂的制备方法、由其制备的催化剂以及以该催化剂制备pbs及其共聚物的方法
CN106084189A (zh) * 2015-04-28 2016-11-09 安庆和兴化工有限责任公司 液态钛系催化剂及使用其制造聚酯聚合物的制备方法
CN106589340A (zh) * 2015-10-19 2017-04-26 中国石油化工股份有限公司 低乙醛聚酯制品的生产方法
CN108034046B (zh) * 2017-11-23 2024-04-16 中科启程新材料科技(海南)有限公司 一种高效聚酯复合催化剂及其制备方法和应用
CN109232865B (zh) * 2018-08-08 2020-12-15 济南朝晖科技有限公司 一种含钛组合物及其制备方法和应用
CN109265668A (zh) * 2018-09-05 2019-01-25 浙江恒澜科技有限公司 一种用于聚酯合成的硅钛复合均相催化剂的制备方法及其应用
CN109337058B (zh) * 2018-09-11 2021-04-06 浙江恒逸石化有限公司 一种环保型聚酯用钛系复合催化剂的制备方法及应用
CN110117356A (zh) * 2019-05-21 2019-08-13 中国石油化工股份有限公司 一种低羧基含量聚酯用组合物及组合物溶液的制备方法及应用
CN110643026B (zh) * 2019-10-22 2022-02-18 华润化学材料科技股份有限公司 一种用于聚酯的钛系催化剂及制备方法
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CN113881027A (zh) * 2020-07-01 2022-01-04 中国石油化工股份有限公司 一种钛系聚酯催化剂及其制备方法和应用
CN113881027B (zh) * 2020-07-01 2023-06-06 中国石油化工股份有限公司 一种钛系聚酯催化剂及其制备方法和应用
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JP5366838B2 (ja) 2013-12-11
JP2010521565A (ja) 2010-06-24
CN101270185A (zh) 2008-09-24
CN101270185B (zh) 2010-11-10

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