WO2018113496A1 - 一种pbs树脂组合物及其制备方法 - Google Patents

一种pbs树脂组合物及其制备方法 Download PDF

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WO2018113496A1
WO2018113496A1 PCT/CN2017/113750 CN2017113750W WO2018113496A1 WO 2018113496 A1 WO2018113496 A1 WO 2018113496A1 CN 2017113750 W CN2017113750 W CN 2017113750W WO 2018113496 A1 WO2018113496 A1 WO 2018113496A1
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resin composition
pbs resin
phosphorus
titanium
pbs
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PCT/CN2017/113750
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English (en)
French (fr)
Inventor
王伟伟
袁志敏
蔡彤旻
黄险波
曾祥斌
苑仁旭
郭志龙
唐美军
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金发科技股份有限公司
珠海万通化工有限公司
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Application filed by 金发科技股份有限公司, 珠海万通化工有限公司 filed Critical 金发科技股份有限公司
Priority to EP17884479.1A priority Critical patent/EP3560995A4/en
Priority to KR1020197000698A priority patent/KR20190016096A/ko
Priority to US16/317,648 priority patent/US10815332B2/en
Priority to JP2019502633A priority patent/JP6905300B2/ja
Publication of WO2018113496A1 publication Critical patent/WO2018113496A1/zh

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    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention belongs to the field of polymer material modification, and in particular relates to a PBS resin composition having good hydrolysis performance.
  • PBS (polybutylene succinate) resin is a biodegradable resin that can be completely degraded into water and carbon dioxide, thereby reducing the production of plastic waste. It is used in supermarket shopping bags, household garbage bags, agricultural mulch films, packaging films, etc. Has a wide application prospects. Although the PBS resin sold in the market meets the requirements of environmental protection and biodegradability, the speed of hydrolysis is too fast, so that the PBS resin cannot be stored for a long time, and it often begins to decompose before being fully used, thereby seriously affecting the PBS in each. Applications within the field. Therefore, how to provide a PBS resin with better hydrolysis performance has become an urgent problem to be solved in today's society.
  • Another object of the present invention is to provide a method for producing the above PBS resin composition.
  • a PBS resin composition comprising the following components:
  • the weight ratio of the titanium element to the phosphorus element ranges from 0.6 to 10:1, the titanium element is derived from the titanium-containing compound, and the phosphorus element is derived from the phosphorus-containing compound.
  • the weight ratio of the titanium element to the phosphorus element in the PBS resin composition is preferably in the range of 0.7 to 4:1, more preferably 1.25 to 1.5:1.
  • the weight content of the titanium element in the PBS resin composition is preferably from 20 to 200 ppm, and the weight content of the phosphorus element is from 15 to 70 ppm.
  • Titanium has a catalytic effect on the reaction.
  • the addition amount is too small, the polymerization reaction proceeds slowly, the addition amount is too large, the PBS resin is more easily degraded, and the phosphorus element can improve the color of the product, but there is a certain relationship between the phosphorus element and the titanium-containing compound.
  • the amount of phosphorus added is too large, the activity of the catalyst is lowered, so that the polymerization rate is slowed, and the possibility of thermal degradation of the resin during the polymerization process is increased.
  • the amount of phosphorus added is too small, and the color of the product cannot be effectively improved.
  • the weight ratio of phosphorus element to titanium element in the PBS resin composition is from 0.6 to 10:1, the hydrolysis property of the PBS resin is improved, and the same The color of the PBS resin product also meets the requirements.
  • the present invention can adjust the weight ratio of the titanium element to the phosphorus element in the PBSA resin composition by controlling the amount of the titanium-containing compound and the phosphorus-containing compound added during the synthesis of the PBSA resin composition.
  • the content of phosphorus element and titanium element in the PBS resin composition of the present invention is measured by ICP-OES according to US EPA Method 3052:1996, and is measured by the following procedure: 0.1 g of the PBS resin composition is weighed, and 5 mL is added after pulverization. The nitric acid was completely immersed in the PBS resin composition, and then dropped into 1.0 mL of hydrogen peroxide for 2 minutes, sealed in a microwave digestion tank and digested at 210 ° C for 3 hours, cooled to room temperature, and then filtered using a 0.45 ⁇ m filter. The distilled water was diluted to 50 mL and tested by ICP-OES.
  • the PBS resin composition of the present invention has a melt index of 3.0 to 10.0 g/10 min at 190 ° C and a condition of 2.16 kg weight.
  • the phosphorus-containing compound of the present invention is selected from one or a mixture of triethyl phosphate, trimethyl phosphate, tributyl phosphate or triphenyl phosphate.
  • the titanium-containing compound of the present invention is selected from one or a mixture of n-butyl titanate or isopropyl titanate.
  • the PBS resin composition of the present invention is dried in a distilled water bath at 95 ° C for 12 hours and then dried in a 90 ° C environment for 3 hours, and the melt index change is less than 50.0 g/10 min.
  • a method for preparing a PBS resin composition comprising the steps of:
  • the present invention has the following advantages:
  • the PBS resin composition by controlling the weight ratio of titanium element to phosphorus element in the PBS resin composition to be in the range of 0.6-10:1, the PBS resin composition is treated in a 95 ° C distilled water water bath for 12 hours, and then dried in a 90 ° C environment for 3 hours.
  • the melt index change is less than 50.0 g/10 min.
  • the PBS resin composition of the present invention has significantly improved hydrolysis properties.
  • the present invention employs the following raw materials, but is not limited to these raw materials:
  • 1,4-succinic acid purity ⁇ 99.9, Shandong Jinyu Chemical Co., Ltd.;
  • 1,4-butanediol purity ⁇ 99.5, Shanxi Three-dimensional Group
  • N-butyl titanate purity ⁇ 99.0, Tianjin Komi reagent
  • Isopropyl titanate purity ⁇ 95.0, Aladdin reagent
  • Triphenyl phosphate purity ⁇ 98.0, Aladdin reagent
  • Trimethyl phosphate purity ⁇ 99.0, Aladdin reagent
  • Triethyl phosphate purity ⁇ 99.5, Aladdin reagent.
  • Table 1 Formulation succinic acid 1,4, 1,4-butanediol, mixed titanium-containing compound, at a pressure of 50-100kPa, a temperature of 180-250 deg.] C, held for 1-5 hours; CO 2 into the Adding a phosphorus-containing compound for 10-30 min; reducing the pressure to less than 100 Pa, heating to 230-250 ° C for 3-6 hours, filling with nitrogen, granulating to obtain a PBS resin composition, by controlling the titanium-containing compound and The phosphorus-containing compound is added in an amount to adjust the weight ratio of the titanium element to the phosphorus element in the PBS resin composition.
  • the content of phosphorus element and titanium element is measured by ICP-OES according to US EPA Method 3052:1996, and is measured by the following procedure: 0.1 g of the PBS resin composition is weighed, and 5 mL of nitric acid is added after pulverization to completely immerse the PBS resin. The composition was then dropped into 1.0 mL of hydrogen peroxide for 2 min, sealed in a microwave digestion tank and digested at 210 ° C for 3 hours, then cooled to room temperature, filtered through a 0.45 ⁇ m filter and diluted to 50 mL with distilled water, via ICP- OES test;
  • melt index 190 ° C, 2.16 kg weight condition test, first test the product in the example or the comparative example once melt index, then the above product in a 95 ° C distilled water bath treatment for 12 hours and then placed in a 90 ° C environment to dry The melt index of the PBS resin composition was again tested for 3 hours, and the melt index of the PBS resin composition after the water bath treatment was subtracted from the melt index of the PBS resin composition before the water bath treatment to obtain a melt index change value.
  • the PBS resin composition is subjected to a distilled water bath treatment at 95 ° C for 12 hours, and then dried at 90 ° C for 3 hours to change the melt index.
  • the titanium element/phosphorus element weight ratio in the PBS resin composition is from 0.6 to 10:1, and the melt index changes after being dried in a 90 ° C environment for 12 hours at 95 ° C in a distilled water bath for 3 hours. Less than 50.0 g/10 min indicates that the PBS resin composition has good hydrolysis properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

本发明公开了一种PBS树脂组合物及其制备方法，所述PBS树脂组合物包括下列组分： a PBS树脂 b钛元素 c磷元素其中，钛元素和磷元素重量比的范围为0.6-10：1，优选为0.7-4：1，更优选为1.25-1.5：1，钛元素的重量含量为20-200ppm，磷元素的重量含量为15-70ppm。本发明所述一种PBS树脂组合物，通过添加含钛化合物、含磷化合物，并控制PBS树脂组合物中钛元素和磷元素重量比的范围为0.6-10：1得到PBS树脂组合物，将所述PBS树脂组合物在95℃蒸馏水水浴处理12小时后置于90℃环境下烘干3小时，熔融指数变化小于50.0g/10min，具有明显改善的水解性能的特性。

Description

一种PBS树脂组合物及其制备方法 技术领域
本发明属于高分子材料改性领域，具体涉及一种具有良好水解性能的PBS树脂组合物。
背景技术
PBS(聚丁二酸丁二醇酯)树脂为生物降解树脂,可以完全降解为水和二氧化碳，从而减少了塑料垃圾的产生，其在超市购物袋、家用垃圾袋、农用地膜、包装薄膜等领域有广泛的应用前景。市面上出售的PBS树脂虽然符合绿色环保、可生物降解的要求，但其水解的速度过快导致PBS树脂不能长时间存储，往往在未充分使用前就已经开始分解，从而严重影响了PBS在各个领域内的应用。因此如何提供一种水解性能较好的PBS树脂成为当今社会亟待解决的问题。
发明内容
本发明的目的在于提供水解性能较好的一种PBS树脂组合物。
本发明的另一目的在于提供上述一种PBS树脂组合物的制备方法。
为了达到上述目的，采用以下技术方案：
一种PBS树脂组合物，包括下列组分：
(a)PBS树脂
(b)钛元素
(c)磷元素
其中，钛元素和磷元素重量比的范围为0.6-10：1，钛元素来自于含钛化合物，磷元素来自于含磷化合物。
其中，所述PBS树脂组合物中钛元素和磷元素重量比的范围优选为0.7-4：1，更优选为1.25-1.5：1。PBS树脂组合物中钛元素的重量含量优选为20-200ppm，磷元素的重量含量为15-70ppm。
钛元素对反应进行具有催化作用，添加量过小，聚合反应进行较慢，添加量过大，PBS树脂更易降解，磷元素可以改善产品颜色，但磷元素和含钛化合物之间会有一定的络合作用，磷元素添加量过多后催化剂的活性降低，使得聚合速度变慢，增加了聚合过程中树脂热降解的可能性，磷元素添加量过少产品颜色无法有效改善，通过大量实验发现，当PBS树脂组合物中磷元素和钛元素的重量比取0.6-10：1时，PBS树脂的水解性能得到改善，同 时PBS树脂产品的颜色也符合要求。
本发明可以通过控制PBSA树脂组合物合成过程中含钛化合物和含磷化合物的加入量，以调节PBSA树脂组合物中的钛元素和磷元素的重量比。
本发明所述PBS树脂组合物中磷元素和钛元素含量参照US EPA方法3052:1996，采用ICP-OES分析，按以下程序测得：称取0.1g所述PBS树脂组合物，粉碎后加入5mL硝酸使其完全浸没所述PBS树脂组合物，后滴入1.0mL过氧化氢反应2min，密封于微波消解罐中于210℃下消解3小时，冷却至室温后，使用0.45μm滤膜过滤后使用蒸馏水稀释至50mL，经ICP-OES测试。
本发明所述PBS树脂组合物的熔融指数在190℃，2.16kg砝码的条件测试时为3.0-10.0g/10min。
本发明所述含磷化合物选自磷酸三乙酯、磷酸三甲酯、磷酸三丁酯或磷酸三苯酯中一种或几种混合物。
本发明所述含钛化合物选自钛酸正丁酯或钛酸异丙酯中的一种或两种混合物。
本发明所述一种PBS树脂组合物，在95℃蒸馏水水浴处理12小时后置于90℃环境下烘干3小时，熔融指数变化小于50.0g/10min。
一种PBS树脂组合物的制备方法，包括如下步骤：
(1)将1,4-丁二酸、1,4-丁二醇、含钛化合物混合，在压力50-100kPa、温度180-250℃下，保持1-5小时；
(2)通入CO2后加入含磷化合物，保持10-30min；
(3)将步骤(2)得到的混合物的压力降低至小于100Pa，加热至230-250℃，保持3-6小时，充入氮气，造粒。
本发明和现有技术相比，具有以下好处：
本发明通过控制PBS树脂组合物中钛元素和磷元素重量比的范围为0.6-10：1，上述PBS树脂组合物在95℃蒸馏水水浴处理12小时后置于90℃环境下烘干3小时，熔融指数变化小于50.0g/10min。本发明所述PBS树脂组合物具有明显改善的水解性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的试试方式，但本发明的实施方式并不受下述实施例的限制。
本发明采用如下原料，但不仅限于这些原料：
1,4-丁二酸：纯度≥99.9，山东金宇化工有限责任公司；
1,4-丁二醇：纯度≥99.5，山西三维集团；
钛酸正丁酯：纯度≥99.0，天津科密欧试剂；
钛酸异丙酯：纯度≥95.0，阿拉丁试剂；
磷酸三苯酯：纯度≥98.0，阿拉丁试剂；
磷酸三甲酯：纯度≥99.0，阿拉丁试剂；
磷酸三乙酯：纯度≥99.5，阿拉丁试剂。
实施例1-13：PBS树脂组合物的制备：
按表1配方将1,4-丁二酸、1,4-丁二醇、含钛化合物混合，在压力50-100kPa、温度180-250℃下，保持1-5小时；通入CO2后加入含磷化合物，保持10-30min；将压力降低至小于100Pa，加热至230-250℃，保持3-6小时，充入氮气，造粒即得PBS树脂组合物，可以通过控制含钛化合物和含磷化合物的加入量，以调整PBS树脂组合物中钛元素和磷元素的重量比。
性能测试方法：
磷元素和钛元素含量参照US EPA方法3052:1996，采用ICP-OES分析，按以下程序测得：称取0.1g所述PBS树脂组合物，粉碎后加入5mL硝酸使其完全浸没所述PBS树脂组合物，后滴入1.0mL过氧化氢反应2min，密封于微波消解罐中于210℃下消解3小时，后冷却至室温后，使用0.45μm滤膜过滤后使用蒸馏水稀释至50mL，经ICP-OES测试；
熔融指数：190℃，2.16kg砝码的条件测试，首先将实施例或对比例中的产物测试一次熔融指数，然后将上述产物在95℃蒸馏水浴处理12小时后置于90℃环境下烘干3小时，再测试一次PBS树脂组合物的熔融指数，上述PBS树脂组合物经过水浴处理后的熔融指数减去上述PBS树脂组合物未经水浴处理前的的熔融指数得到熔融指数变化值。
表1 实施例1-13和对比例1-2中制备PBS树脂组合物所用到的到原料的质量(g)
Figure PCTCN2017113750-appb-000001
Figure PCTCN2017113750-appb-000002
表2 实施例1-13及对比例1-2各组分的配比及性能测试结果
Figure PCTCN2017113750-appb-000003
续表1
Figure PCTCN2017113750-appb-000004
本发明中所述PBS树脂组合物在95℃蒸馏水浴处理12小时后置于90℃环境下烘干3小时熔融指数会变化，变化值越小，证明PBS树脂组合物的水解性能越好。从表2中可以看出，PBS树脂组合物中钛元素/磷元素重量比为0.6-10：1，在95℃蒸馏水浴处理12小时后置于90℃环境下烘干3小时后熔融指数变化小于50.0g/10min，表明PBS树脂组合物具有良好的水解性能。而对比例1钛元素/磷元素重量比小于0.6及对比例2钛元素/磷元素重量比超出10时，熔融指数变化大于50.0g/10min，表明组合物水解性能较差。

Claims (10)

  1. 一种PBS树脂组合物，其特征在于，包括下列组分：
    a.PBS树脂
    b.钛元素
    c.磷元素。
  2. 根据权利要求1所述的一种PBS树脂组合物，其特征在于，PBS树脂组合物中钛元素和磷元素重量比的范围为0.6-10：1。
  3. 根据权利要求2所述的一种PBS树脂组合物，其特征在于，所述PBS树脂组合物中钛元素和磷元素重量比的范围为0.7-4：1，优选为1.25-1.5：1。
  4. 根据权利要求1所述的一种PBS树脂组合物，其特征在于，所述PBS树脂组合物中钛元素的重量含量为20-200ppm，所述PBS树脂组合物中磷元素的重量含量为15-70ppm。
  5. 根据权利要求1所述的一种PBS树脂组合物，其特征在于，PBS树脂组合物中磷元素和钛元素重量含量参照US EPA方法3052:1996，采用ICP-OES分析，按以下程序测得：称取0.1g所述PBS树脂组合物，粉碎后加入5mL硝酸使其完全浸没所述PBS树脂组合物，后滴入1.0mL过氧化氢反应2min，密封于微波消解罐中于210℃下消解3小时，冷却至室温后，使用0.45μm滤膜过滤后使用蒸馏水稀释至50mL，经ICP-OES测试。
  6. 根据权利要求1所述的一种PBS树脂组合物，其特征在于，所述PBS树脂组合物在190℃，2.16kg砝码的条件测试时，熔融指数为3.0-10.0 g/10min。
  7. 根据权利要求1所述的一种PBS树脂组合物，其特征在于：所述钛元素来自于含钛化合物，含钛化合物选自钛酸正丁酯或钛酸异丙酯中的一种或两种混合物。
  8. 根据权利要求1所述的一种PBS树脂组合物，其特征在于：所述磷元素来自于含磷化合物，含磷化合物选自磷酸三乙酯、磷酸三甲酯、磷酸三丁酯或磷酸三苯酯中一种或几种混合物。
  9. 根据权利要求1所述的一种PBS树脂组合物，其特征在于，PBS树脂组合物在95℃蒸馏水水浴处理12小时后置于90℃环境下烘干3小时，熔融指数变化小于50.0 g/10min。
  10. 权利要求1-8中任一项所述PBS树脂的制备方法，包括如下步骤：
    1.将1,4-丁二酸、1,4-丁二醇、含钛化合物混合，在压力50-100kPa、温度180-250℃下，保持1-5小时；
    2.通入CO2后加入含磷化合物，保持10-30min；
    3.将步骤2得到的混合物的压力降低至小于100Pa，加热至230-250℃，保持3-6小时，充入氮气，造粒。
PCT/CN2017/113750 2016-12-20 2017-11-30 一种pbs树脂组合物及其制备方法 WO2018113496A1 (zh)

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Families Citing this family (2)

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Publication number Priority date Publication date Assignee Title
CN108414502A (zh) * 2018-01-26 2018-08-17 昆明理工大学 一种测定血管中微量元素含量的方法
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1106640A2 (en) * 1999-12-11 2001-06-13 IRE Chemical Ltd Biodegradable copolyesters and their preparation
JP2006274253A (ja) * 2005-03-02 2006-10-12 Daicel Chem Ind Ltd 低分岐度高分子量脂肪族ポリエステル、その製造方法、成形品及びフィルム
CN102190868A (zh) * 2010-03-09 2011-09-21 富士胶片株式会社 聚酯树脂组合物,其制备方法,聚酯膜和太阳能电池发电组件
CN103974994A (zh) * 2012-02-06 2014-08-06 三星精密化学株式会社 聚酯树脂合成用催化剂及使用其的聚酯树脂的制备方法
CN105061744A (zh) * 2015-08-17 2015-11-18 中国石油天然气集团公司 聚丁二酸丁二醇酯的制备方法
CN105131269A (zh) * 2015-08-17 2015-12-09 中国石油天然气集团公司 环保型钛-磷配位复合催化剂的制备方法及采用该催化剂的pbs生产方法
EP3091046A1 (en) * 2013-12-30 2016-11-09 LOTTE Fine Chemical Co., Ltd. Composition for producing biodegradable polyester resin, and production method for biodegradable polyester resin
CN106832235A (zh) * 2017-02-08 2017-06-13 新疆蓝山屯河化工股份有限公司 纺丝用聚丁二酸丁二醇酯及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101671435B (zh) * 2008-09-08 2011-12-28 上海华明高技术（集团）有限公司 制备聚丁二酸丁二醇酯及其共聚酯的催化剂及其制备方法
JP2012012578A (ja) * 2010-06-04 2012-01-19 Fujifilm Corp ポリエステル樹脂組成物及びその製造方法、ポリエステルフィルム、並びに太陽電池発電モジュール
CN102617842B (zh) * 2012-03-29 2014-06-11 金发科技股份有限公司 一种锑/钛复合催化剂及其用于制备pet共聚酯的方法
CN107602824B (zh) * 2012-06-05 2020-11-13 基因组股份公司 聚酯和聚氨基甲酸酯的制造方法
CN102775590B (zh) * 2012-08-15 2014-11-12 金发科技股份有限公司 一种聚丁二酸丁二醇酯及其制备方法
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

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1106640A2 (en) * 1999-12-11 2001-06-13 IRE Chemical Ltd Biodegradable copolyesters and their preparation
JP2006274253A (ja) * 2005-03-02 2006-10-12 Daicel Chem Ind Ltd 低分岐度高分子量脂肪族ポリエステル、その製造方法、成形品及びフィルム
CN102190868A (zh) * 2010-03-09 2011-09-21 富士胶片株式会社 聚酯树脂组合物,其制备方法,聚酯膜和太阳能电池发电组件
CN103974994A (zh) * 2012-02-06 2014-08-06 三星精密化学株式会社 聚酯树脂合成用催化剂及使用其的聚酯树脂的制备方法
EP3091046A1 (en) * 2013-12-30 2016-11-09 LOTTE Fine Chemical Co., Ltd. Composition for producing biodegradable polyester resin, and production method for biodegradable polyester resin
CN105061744A (zh) * 2015-08-17 2015-11-18 中国石油天然气集团公司 聚丁二酸丁二醇酯的制备方法
CN105131269A (zh) * 2015-08-17 2015-12-09 中国石油天然气集团公司 环保型钛-磷配位复合催化剂的制备方法及采用该催化剂的pbs生产方法
CN106832235A (zh) * 2017-02-08 2017-06-13 新疆蓝山屯河化工股份有限公司 纺丝用聚丁二酸丁二醇酯及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3560995A4 *

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