WO2018113493A1 - 一种pbsa树脂组合物及其制备方法 - Google Patents

一种pbsa树脂组合物及其制备方法 Download PDF

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WO2018113493A1
WO2018113493A1 PCT/CN2017/113747 CN2017113747W WO2018113493A1 WO 2018113493 A1 WO2018113493 A1 WO 2018113493A1 CN 2017113747 W CN2017113747 W CN 2017113747W WO 2018113493 A1 WO2018113493 A1 WO 2018113493A1
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resin composition
pbsa resin
pbsa
titanium
phosphorus
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PCT/CN2017/113747
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English (en)
French (fr)
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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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Publication of WO2018113493A1 publication Critical patent/WO2018113493A1/zh

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    • 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
    • C08K5/49—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
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds

Definitions

  • the invention belongs to the field of polymer material modification, and particularly relates to a PBSA resin composition having good hydrolysis performance.
  • PBSA resin The performance of PBSA resin is close to that of PBS (polybutylene succinate).
  • PBS polybutylene succinate
  • PBSA has increased flexibility of molecular chain, reduced crystallinity, and is more easily biodegraded into water and carbon dioxide, thereby reducing
  • the production of plastic garbage has broad application prospects in the fields of supermarket shopping bags, household garbage bags, agricultural mulch films, packaging films and the like.
  • the commercially available PBSA resin is a green and biodegradable material, the hydrolysis rate can not be stored for a long time, and it often begins to decompose before it is fully used, which seriously affects the PBSA in various fields. application. Therefore, how to provide a PBSA resin composition 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 PBSA resin composition.
  • a PBSA resin composition comprising the following components:
  • the weight ratio of the titanium element to the phosphorus element ranges from 0.3 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 PBSA resin composition preferably ranges from 0.5 to 8:1, more preferably from 0.7 to 5:1.
  • the weight content of the titanium element is preferably from 10 to 200 ppm based on the total weight of the PBSA resin composition, and the weight content of the phosphorus element is from 1 to 700 ppm.
  • Titanium has a catalytic effect on the reaction.
  • the amount of addition is too small, the polymerization reaction is slow, the amount of addition is too large, PBSA resin is more easily degraded, and phosphorus can improve the color of the product, but there will be some difference between phosphorus and titanium-containing compounds.
  • For complexation when 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 PBSA resin composition is 0.3-10:1, the hydrolysis performance of the PBSA resin is changed. Good, while the color of PBSA resin products 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 PBSA 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 PBSA resin composition is weighed, and 5 mL is added after pulverization. The nitric acid was completely immersed in the PBSA resin, and 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, cooled to room temperature, filtered through a 0.45 ⁇ m filter and diluted with distilled water. Up to 50 mL, tested by ICP-OES.
  • the butyl succinate unit in the PBSA resin of the present invention has a weight content of 66 to 89% by weight, and the butylene adipate unit has a weight content of 11 to 34% by weight.
  • the PBSA 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 PBSA resin composition of the present invention is dried in a distilled water bath at 75 ° C for 24 hours, and then dried in an environment of 80 ° C for 6 hours, and the melt index change is less than 35.0 g/10 min.
  • a method for preparing a PBSA resin composition comprising the steps of:
  • step 2 Add 1,4-succinic acid to the mixture obtained in step 1, pass through CO2, hold at 180-240 ° C for 2-5 hours, then add phosphorus-containing compound for 10-30 min;
  • step 3 Reduce the pressure of the mixture obtained in step 2 to less than 100 Pa, heat to 230-250 ° C, hold for 3-6 hours, fill with nitrogen, and granulate.
  • the present invention has the following advantages:
  • the present invention can control the weight ratio of titanium element to phosphorus element in the PBSA resin composition to be in the range of 0.3-10:1, and the above PBSA resin composition is treated in a distilled water bath at 75 ° C for 24 hours, and then dried in an environment of 80 ° C for 6 hours.
  • the melt index change was less than 35.0 g/10 min.
  • the PBSA 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.
  • 1,6-adipate purity ⁇ 99.8, Chongqing Huafeng Group
  • 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.
  • 1,6 adipic acid, 1,4-butanediol, and titanium-containing compound are mixed, and maintained at a pressure of 50-100 kPa and a temperature of 180-250 ° C for 1-5 hours; Diacid, pass into CO2, hold at 180-240 ° C for 2-5 hours, then add phosphorus-containing compound for 10-30 min; reduce the pressure to less than 100 Pa, heat to 230-250 ° C, hold for 3-6 hours, charge Nitrogen, granulated, can be adjusted by adjusting the amount of the titanium-containing compound and the phosphorus-containing compound to adjust the weight ratio of the titanium element to the phosphorus element in the PBSA 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 PBSA resin composition is weighed, and 5 mL of nitric acid is added after pulverization to completely immerse it. The PBSA resin was poured 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. -OES test;
  • the PBSA resin composition is treated in a distilled water bath at 75 ° C for 24 hours and then dried at 80 ° C for 6 hours.
  • the melt index changes, and the smaller the change value, the better the hydrolysis performance of the PBSA resin composition.
  • the weight ratio of titanium element to phosphorus element in the PBSA resin composition is from 0.3 to 10:1, and the melt index changes after being treated in a distilled water bath at 75 ° C for 24 hours and then dried at 80 ° C for 6 hours. Less than 35.0 g/10 min indicates that the PBSA resin composition has good hydrolysis properties.
  • the weight ratio of the titanium element/phosphorus element of Comparative Example 1 is less than 0.3 and the weight ratio of the titanium element/phosphorus element of Comparative Example 2 exceeds 10
  • the melt index changes by more than 35.0 g/10 min, indicating that the hydrolysis property of the composition is poor.

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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)
  • Biological Depolymerization Polymers (AREA)

Abstract

本发明公开了一种PBSA树脂组合物及其制备方法，所述PBSA树脂组合物包括下列组分： a.PBSA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0.3-10：1，优选为0.5-8：1，更优选为0.7-5：1，钛元素的重量含量为10-200ppm，磷元素的重量含量为1-700ppm，所述PBSA树脂组合物中丁二酸丁二醇酯单元的重量含量为66-89wt％，己二酸丁二醇酯单元的重量含量为11-34wt％，本发明所述一种PBSA树脂组合物，通过添加含钛化合物、含磷化合物后，并控制PBSA树脂组合物中钛元素和磷元素重量比的范围为0.3-10：1得到PBSA树脂组合物，将所述PBSA树脂组合物在75℃蒸馏水水浴处理24小时后置于80℃环境下烘干6小时，熔融指数变化小于35.0g/10min，具有明显改善的水解性能的特性。

Description

一种PBSA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PBSA树脂组合物。
背景技术
PBSA树脂与PBS(聚丁二酸丁二醇酯)性能接近，在引入己二酸共聚单元后，PBSA其分子链的柔性增加，结晶度降低，更容易生物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PBSA树脂虽然是一种绿色环保的可生物降解的材料，但是水解的速度很快不能长时间存储，往往在未充分使用前就已经开始分解，严重影响了PBSA在各个领域内的应用。因此如何提供一种水解性能较好的PBSA树脂组合物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PBSA树脂组合物。
本发明的另一目的在于提供上述一种PBSA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PBSA树脂组合物，包括下列组分：
a.PBSA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0.3-10：1，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PBSA树脂组合物中钛元素和磷元素重量比的范围优选为0.5-8：1，更优选为0.7-5：1。基于PBSA树脂组合物的总重量，钛元素的重量含量优选为10-200ppm，磷元素的重量含量为1-700ppm。
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，PBSA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PBSA树脂组合物中磷元素和钛元素的重量比取0.3-10：1时，PBSA树脂的水解性能得到改 善，同时PBSA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PBSA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PBSA树脂组合物，粉碎后加入5mL硝酸使其完全浸没所述PBSA树脂，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PBSA树脂中丁二酸丁二醇酯单元的重量含量为66-89wt％，己二酸丁二醇酯单元的重量含量为11-34wt％。
本发明所述PBSA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PBSA树脂组合物，在75℃蒸馏水水浴处理24小时后置于80℃环境下烘干6小时，熔融指数变化小于35.0g/10min。
一种PBSA树脂组合物的制备方法，包括如下步骤：
1.将1,6己二酸、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.将1,4-丁二酸加到步骤1得到的混合物中，通入CO2，180-240℃下保持2-5小时后加入含磷化合物，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PBSA树脂组合物中钛元素和磷元素重量比的范围为0.3-10：1，上述PBSA树脂组合物在75℃蒸馏水水浴处理24小时后置于80℃环境下烘干6小时，熔融指数变化小于35.0g/10min。本发明所述PBSA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实施方式， 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。
1,6-己二酸：纯度≥99.8,重庆华峰集团；
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。
表1实施例1-19和对比例1-2中制备PBSA树脂组合物所用到的到原料的质量(g)
Figure PCTCN2017113747-appb-000001
Figure PCTCN2017113747-appb-000002
实施例1-19和对比例1-2：一种PBSA树脂组合物的制备：
按表1配方将1,6己二酸、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；加入1,4-丁二酸，通入CO2，180-240℃下保持2-5小时后加入含磷化合物，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，可以通过控制含钛化合物和含磷化合物的加入量，以调整PBSA树脂组合物中钛元素和磷元素的重量比。
性能评价方法：
(1)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PBSA树脂组合物，粉碎后加入5mL硝酸使其完全浸没所述PBSA树脂，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；
(2)熔融指数：190℃，2.16kg砝码的条件测试，制备得到本发明所述PBSA树脂组合物后测试一次熔融指数，然后将上述PBSA树脂组合物在75℃蒸馏水浴处理24小时后置于80℃环境下烘干6小时，再测试一次PBSA树脂组合物熔融指数，用上述PBSA树脂组合物经过水浴处理后的熔融指数减去上述PBSA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。
(3)PBSA树脂中丁二酸丁二醇酯和己二酸丁二醇酯的含量在最终得到的PBSA树脂组合物中使用核磁共振氢谱法确认。
表2实施例1-19及对比例1-2各组分的配比及性能测试结果
Figure PCTCN2017113747-appb-000003
Figure PCTCN2017113747-appb-000004
续表2
Figure PCTCN2017113747-appb-000005
Figure PCTCN2017113747-appb-000006
本发明中所述PBSA树脂组合物在75℃蒸馏水浴处理24小时后置于80℃环境下烘干6小时熔融指数会变化，变化值越小，证明PBSA树脂组合物的水解性能越好。
从表2中可以看出，PBSA树脂组合物中钛元素/磷元素重量比为0.3-10：1，在75℃蒸馏水浴处理24小时后置于80℃环境下烘干6小时后熔融指数变化小于35.0g/10min，表明PBSA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0.3及对比例2钛元素/磷元重量比超出10时，熔融指数变化大于35.0g/10min，表明组合物水解性能较差。

Claims (11)

  1. 一种PBSA树脂组合物，其特征在于，包括下列组分：
    a.PBSA树脂
    b.钛元素
    c.磷元素。
  2. 根据权利要求1所述的PBSA树脂组合物，其特征在于，PBSA树脂组合物中钛元素和磷元素重量比的范围为0.3-10：1。
  3. 根据权利要求2所述的一种PBSA树脂组合物，其特征在于，所述PBSA树脂组合物中钛元素和磷元素重量比的范围为0.5-8：1，优选为0.7-5：1。
  4. 根据权利要求1所述的一种PBSA树脂组合物，其特征在于，所述PBSA树脂组合物中钛元素的重量含量为10-200ppm，所述PBSA树脂组合物中磷元素的重量含量为1-700ppm。
  5. 根据权利要求1所述的一种PBSA树脂组合物，其特征在于，所述PBSA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PBSA树脂组合物，粉碎后加入5mL硝酸使其完全浸没所述PBSA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PBSA树脂组合物，其特征在于，所述PBSA树脂中丁二酸丁二醇酯单元的重量含量为66-89wt％，己二酸丁二醇酯单元的重量含量为11-34wt％。
  7. 根据权利要求1所述的一种PBSA树脂组合物，其特征在于，所述PBSA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。
  8. 根据权利要求1所述的一种PBSA树脂组合物，其特征在于：所述磷元素来自含磷化合物，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PBSA树脂组合物，其特征在于：所述含钛元素来自含钛化合物，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。
  10. 根据权利要求1所述的一种PBSA树脂组合物，其特征在于，在75℃蒸馏水水浴处理24小时后置于80℃环境下烘干6小时，PBSA树脂组合物的熔融指数变化小于35.0g/10min。
  11. 如权利要求1-10中任一项所述一种PBSA树脂组合物的制备方法，其特征在于，包括如下步骤：
    1.将1,6己二酸、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.将1,4-丁二酸加到步骤1得到的混合物中，通入CO2，180-240℃下保持2-5小时后加入含磷化合物，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/CN2017/113747 2016-12-21 2017-11-30 一种pbsa树脂组合物及其制备方法 WO2018113493A1 (zh)

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