阅读说明：本技术 一种基于酒石酸的聚己内酯材料的制备方法 (Preparation method of polycaprolactone material based on tartaric acid ) 是由 侯维敏 詹世平 方榆 宁琼 彭文婷 朱恺妮 于 2020-06-23 设计创作，主要内容包括：本发明公开了一种基于酒石酸的聚己内酯材料的制备方法,属于高分子材料合成领域。包括如下步骤：(1)称取干燥后的ε-己内酯和酒石酸；(2)采用酒石酸作为引发剂兼催化剂,投入反应烧瓶中,ε-己内酯按一定速率滴加进入反应烧瓶中,于一定反应温度,通入氮气保护下进行本体聚合；(3)反应一段时间后,产物经不良溶剂反复洗涤沉淀、减压过滤、真空干燥得聚己内酯材料。本发明采用本体聚合,酒石酸为引发剂兼催化剂,工艺简单,条件温和,所得产物纯度高,无毒安全,其生物安全性有效提高,可适用于绿色环保材料和医用材料领域。(The invention discloses a preparation method of a tartaric acid-based polycaprolactone material, belonging to the field of synthesis of high polymer materials. The method comprises the following steps: (1) weighing dried caprolactone and tartaric acid; (2) tartaric acid is used as an initiator and a catalyst and is put into a reaction flask, caprolactone is dripped into the reaction flask at a certain speed, and bulk polymerization is carried out at a certain reaction temperature under the protection of nitrogen; (3) after reacting for a period of time, repeatedly washing and precipitating the product by using a poor solvent, filtering under reduced pressure, and drying in vacuum to obtain the polycaprolactone material. The invention adopts bulk polymerization, uses tartaric acid as an initiator and a catalyst, has simple process and mild conditions, obtains the product with high purity, is nontoxic and safe, effectively improves the biological safety, and is suitable for the fields of green and environment-friendly materials and medical materials.)

1. A preparation method of a tartaric acid-based polycaprolactone material is characterized in that tartaric acid is used as an initiator and a catalyst, and specifically comprises the following steps: (1) weighing dried caprolactone and tartaric acid; (2) dripping caprolactone into tartaric acid, and carrying out bulk polymerization reaction at a certain reaction temperature under the protection of nitrogen; (3) after reacting for a period of time, repeatedly washing and precipitating the product by using a poor solvent, filtering under reduced pressure, and drying in vacuum to obtain the polycaprolactone material.

2. The method for preparing a tartaric acid-based polycaprolactone material as claimed in claim 1, wherein the molar ratio of caprolactone to tartaric acid is 10-1000.

3. The method for preparing a tartaric acid-based polycaprolactone material as claimed in claim 1, wherein the tartaric acid is L-tartaric acid or D-tartaric acid or DL-tartaric acid.

4. The method for preparing a tartaric acid-based polycaprolactone material as claimed in claim 1, wherein the reaction temperature is 80-130 ℃.

5. The method for preparing a tartaric acid-based polycaprolactone material as claimed in claim 1, wherein the time of the bulk polymerization reaction is 4-10 hours.

6. The method for preparing a tartaric acid-based polycaprolactone material as claimed in claim 1, wherein the poor solvent is deionized water or ethanol or methanol.

7. The method of claim 1, wherein the number of washes is at least 3.

8. The method of claim 1, wherein the dropping of caprolactone into the tartaric acid is at a rate of 1 drop/sec.

Technical Field

The invention belongs to the field of synthesis of high polymer materials, and particularly relates to a preparation method of a tartaric acid-based polycaprolactone material.

Background

Polycaprolactone (PCL) is a biodegradable semi-crystalline biopolymer material obtained by ring-opening polymerization of caprolactone (-CL) in the presence of an initiator and a catalyst. PCL has been widely used in medicine, food, and the like because of its advantages such as degradability (complete degradation in natural environment within 6-12 months), solubility (solubility in most organic solvents), and crystallinity (crystallinity of about 45%). The biodegradable high molecular material Polycaprolactone (PCL) has good biocompatibility, shape memory function and biodegradability, and has wide application prospect in the fields of green environment-friendly materials and medical materials.

Tartaric acid, 2, 3-dihydroxybutanedioic acid, is present in a variety of plants, such as grapes and tamarind, and is also one of the major organic acids in wine. The antioxidant can be added into food to impart sour taste to the food. The tartaric acid is used as beverage additive and raw material for pharmaceutical industry.

The catalyst system adopted in the traditional method for synthesizing polycaprolactone mostly uses an initiating/catalyzing system based on organic aluminum, zinc, magnesium and tin compounds, IVB group metal catalysts or rare earth metal compounds, the problems of residual metal ions and over violent and uncontrollable reaction are often brought in the process of synthesizing polycaprolactone by using the catalyst, and the trace residual and potential toxicity of the catalyst limit the wide application of the catalyst in the field of biomedical materials.

Disclosure of Invention

The method aims to solve the problems of violent reaction in the catalytic process and metal residue in the polymer caused by the traditional metal catalyst. The invention provides a method for synthesizing a polycaprolactone material by using tartaric acid as an initiator and a catalyst for caprolactone bulk polymerization.

The technical scheme adopted by the invention is as follows:

a preparation method of a polycaprolactone material based on tartaric acid as an initiator and a catalyst comprises the following specific steps:

(1) weighing dried caprolactone and tartaric acid;

(2) dripping caprolactone into tartaric acid, and carrying out bulk polymerization reaction at a certain reaction temperature under the protection of nitrogen;

(3) after reacting for a period of time, repeatedly washing and precipitating the product by using a poor solvent, filtering under reduced pressure, and drying in vacuum to obtain the polycaprolactone material.

According to the scheme, the molar ratio of caprolactone to tartaric acid is 10-1000.

According to the scheme, the tartaric acid is L-tartaric acid or D-tartaric acid or DL-tartaric acid.

According to the scheme, the reaction temperature is 80-130 ℃.

According to the scheme, the reaction time is 4-10 hours.

According to the scheme, the poor solvent is deionized water or ethanol or methanol.

According to the scheme, the washing times are at least 3 times.

According to the scheme, the dropping speed of caprolactone into tartaric acid is 1 drop/second.

The reaction mechanism is as follows: the protons of the active hydrogen catalytic system attack the carbonyl oxygen in the caprolactone structure, enhancing the electrophilicity of the caprolactone carboxyl carbon, where upon encountering a nucleophile such as ROH, RO attacks the carbonyl carbon initiating caprolactone ring opening and forming a protonated alcohol, which in turn transfers protons to caprolactone and causes further initiation of caprolactone ring opening to form a chain extension reaction.

Compared with the prior art, the invention has the beneficial effects that:

the initiator and catalyst is nontoxic tartaric acid, which is commonly used as an additive in food, and the hydroxyl group and the carboxyl group in the chemical structure of the initiator play a role of the initiator to initiate the ring-opening polymerization of caprolactone, and the carboxyl group plays a role of catalyzing and accelerating the polymerization reaction. No toxic metal catalyst is added during the reaction, the reaction condition is mild, the obtained polymer does not contain heavy metal ions, the product is nontoxic and safe, the biological safety is effectively improved, the practical application limit is reduced, the application is wider, and the method is applicable to the fields of green environment-friendly materials and medical materials.

Compared with other processes (such as solution polymerization), caprolactone needs to be added with an organic solvent during the ring-opening polymerization reaction and the solvent remains in the post-treatment process, so that the purity of the product is reduced and the reaction efficiency is reduced. The invention adopts bulk polymerization, the process is simple, only monomers and initiators are contained in a polymerization system, and no dispersing medium such as organic solvent is needed to be added, the reaction system after polymerization only contains polymers and unreacted monomers, the post-treatment is simple, the unreacted monomers are dissolved in poor solvent for removal after the post-treatment, the polymers form precipitates, the purity of the products obtained by the reaction is high, and the reaction efficiency is high.

Detailed Description

The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.