WO2015018015A1 - Method for synthesis of polylactide polyol from lactide and polyol - Google Patents

Method for synthesis of polylactide polyol from lactide and polyol Download PDF

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Publication number
WO2015018015A1
WO2015018015A1 PCT/CN2013/081035 CN2013081035W WO2015018015A1 WO 2015018015 A1 WO2015018015 A1 WO 2015018015A1 CN 2013081035 W CN2013081035 W CN 2013081035W WO 2015018015 A1 WO2015018015 A1 WO 2015018015A1
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Prior art keywords
lactide
polyol
polylactide
tin
catalyst
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PCT/CN2013/081035
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French (fr)
Chinese (zh)
Inventor
杨义浒
方文拓
徐杰
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深圳市光华伟业实业有限公司
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Priority to PCT/CN2013/081035 priority Critical patent/WO2015018015A1/en
Publication of WO2015018015A1 publication Critical patent/WO2015018015A1/en

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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
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • 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 invention belongs to the technical field of organic polymers, and particularly relates to a method for obtaining a polylactide polyol by a method in which lactide and a polyol are used as a direct raw material by ring-opening polymerization of lactide. Background technique
  • Polylactic acid polyols can be used to improve the flexibility, fluidity, low-temperature impact resistance, formability, etc. of acrylic, polyester, vinyl, etc. in terms of resin modification.
  • adhesives polylactide is used.
  • the polyurethane adhesive prepared from alcohol has better color, hydrolytic stability and uniformity than other polyether and polyester. In terms of polyurethane, it has strong cohesive strength and adhesion, and has high strength and resistance. Grinding.
  • polylactide polyols have biodegradable properties, which can reduce the pressure on the environment and have broad application prospects.
  • the present invention is directed to the deficiencies of the prior art, and provides a method for synthesizing polylactide polyol from lactide and polyol.
  • the method is simple in process, simple in operation, suitable for industrial production applications, and has no "three wastes" emissions.
  • Lactide purification The crude lactide is purified to obtain lactide having a content of 99.5% or more and an optical purity of 99% or more.
  • a preferred technical solution of the present invention is: prior to the polymerization, the lactide is purified, and the content of the lactide after purification is required to be 99.5% or more, the light purity is above 99.0%, and the moisture requirement is below 1000 ppm.
  • the catalyst added during the polymerization is at least one of a zinc-based catalyst, a tin-based catalyst or an organic catalyst, and the amount thereof is 0.5/1000 to 1/1000 of the weight of the lactide.
  • Preferred is zinc lactate, zinc oxide, zinc powder, diethyl zinc, tin lactate, tin oxide, tin dioxide, stannous oxide, stannous lactate, stannous octoate, stannous chloride, tin powder, propionic acid or titanic acid.
  • a more preferred catalyst is stannous octoate, or butyl titanate, tin oxide and zinc lactate in a 1:1:1 mixed catalyst.
  • the method for purifying the crude lactide in the step A is recrystallization, vacuum distillation or melt crystallization, or a combination of two or more of the above purification methods. It is preferred to first recrystallize and remelt the crystal.
  • the raw material polyol in the present invention may be 1, 4-butanediol, ethylene glycol, neopentyl glycol, diethylene glycol, trimethylolpropane or the like. Preference is given to 1,4 butanediol.
  • the process route for producing polylactide polyol of the present invention uses purified lactide and polyol as direct raw materials, which is different from polylactide and alcohol as direct raw materials, and produces polylactide polyol by transesterification.
  • the present invention has the following features:
  • Polymerization of lactide and polyol as raw materials to form polylactide polyol can obtain lower polylactide polyols with viscosity average molecular weights of 100, 300, 500, 800, etc., and polylactic acid and polyol as raw materials.
  • Polylactide polyols have a relatively high molecular weight, and the product has poor fluidity and is difficult to use.
  • Polylactide polyol with narrow molecular weight distribution can be obtained by polymerization of lactide and polyol as raw materials, and polylactide polyol obtained by transesterification contains more oligomer by-products, and the molecular weight distribution will be More wide.
  • the polylactide polyol is polymerized by using lactide and polyol as raw materials, and the production conditions are mild.
  • the transesterification reaction of polylactide and polyol as raw materials to produce polylactide polyol needs to be carried out under molten conditions. The conditions are harsh.
  • the gradient heating method of the invention can make the lactide ring-opening polymerization at a lower temperature, increase the conversion rate of lactide, and reduce the loss of lactide due to sublimation, so that the lactide can be kept at the time of feeding.
  • the weight ratio of the polyol avoids the decrease in the molecular weight of the synthesized polylactide polyol and the theoretically designed molecular weight due to the reduction of lactide, and the stability of the quality of the synthetic product can be ensured.
  • the invention adopts gradient heating and adjustment of reaction time under different temperature conditions, can reduce the amount of lactide monomer in the product, thereby avoiding the influence of lactide monomer on product quality.
  • the crude lactide is first purified.
  • the purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 122.0 g to 500 ml three-necked flask, and then added thereto.
  • Reagent grade 1,4-butanediol 200.0g then add lactide stannous acid stannous acid with a lactide mass of 0.5/1000, evacuate under vacuum, and raise the temperature to 140 ° C at 140 ° under nitrogen protection conditions.
  • the reaction was carried out for 1 hour under C conditions, and the temperature was raised to 170 ° C for 3 hours. After the reaction, a polyglycolide polyol having a viscosity average molecular weight of 100.2 was obtained.
  • Example 2 Example 2:
  • the crude lactide is first purified.
  • the purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 232.2 g to 500 ml three-necked flask, and then added thereto.
  • Reagent grade ethylene glycol 100.0g then add lactide lactate mass 0.5 / 1000 catalyst stannous lactate, vacuum to nitrogen replacement, under nitrogen protection conditions, raise the temperature to 140 ° C, at 140 ° C conditions Lh, raise the temperature to 170 ° C for 3 h.
  • a polyglycolide polyol having a viscosity average molecular weight of 302.0 was obtained.
  • the crude lactide is first purified.
  • the purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 227.1 g to 500 ml three-necked flask, and then added thereto.
  • the crude lactide is first purified.
  • the purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of 1000 ppm or less, and a purified lactide to obtain a desired lactide of 262.5 g to 500 ml.
  • 33.3 g of reagent grade 1,4-butanediol was then added thereto, and then a catalyst having a lactide mass of 0.5/1000 was added, and the catalyst was butyl titanate, tin oxide and zinc lactate in terms of weight ratio.
  • the crude lactide is first purified.
  • the purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 200.1 g to 500 ml three-necked flask, and then added thereto.
  • Reagent grade diethylene glycol 20.01g then add the lactide mass of 0.5/1000 catalyst stannous octoate, vacuum to nitrogen replacement, under nitrogen protection conditions, raise the temperature to 140 ° C, at 140 ° C
  • the reaction was carried out for 2 h under the conditions, and the temperature was raised to 170 ° C for 4 h.
  • a polylacticide polyol having a viscosity average molecular weight of 989.1 was obtained.
  • the crude lactide is first purified.
  • the purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 212.1 g to 500 ml three-necked flask, and then added thereto.
  • Reagent grade 1,4-butanediol 10.01g then add the lactide stannous octoate with a lactide mass of 0.75/1000, evacuate under vacuum, and raise the temperature to 140 ° C at 140 ° under nitrogen protection.
  • the reaction was carried out for 2 h under C conditions, and the temperature was raised to 170 ° C for 4 h. After the reaction, a viscosity average molecular weight of 1956.8 polylactide polyol was obtained.
  • Example 7 Example 7:
  • the crude lactide is first purified.
  • the purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 238.9 g to 500 ml three-necked flask, and then added thereto.
  • Reagent grade trimethylolpropane 3.0g then add lactide stearate stannous acid with a lactide mass of 1/1000, vacuum under nitrogen replacement, raise the temperature to 14CTC under nitrogen protection, and react for 2h under 14CTC conditions. The temperature was raised to 170 ° C for 4 h. After the reaction, a viscosity average molecular weight of 4942.7 was obtained.
  • Polylactide polyol Polylactide polyol.

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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)

Abstract

The invention relates to a method for obtaining a polylactide polyol by ring-opening polymerization of lactide with lactide and a polyol as direct raw materials. The method includes the following steps: A, lactide purification: a lactide crude product is purified to obtain lactide with a content of more than 99.5% and an optical purity of more than 99%; B, synthesis of polylactide polyol: the purified lactide and the polyol are added into a reaction kettle, then a catalyst is added, in a weight ratio to lactide of 0.5/1000-1/1000, into the reaction kettle for polymerization, and polylactide polyol with a viscosity average molecular weight of 100-5000 is obtained, wherein the catalyst is a composite catalyst of one or more of zinc lactate, zinc oxide, zinc powder, diethyl zinc, tin lactate, tin oxide, tin dioxide, stannous oxide, stannous lactate, stannous octoate, stannous chloride, tin powder, propanoic acid or tetrabutyl titanate. The method of the invention has a simple process and easy operation, is suitable for industrialized production applications, and has no 'three wastes' emissions.

Description

一种由丙交酯和多元醇合成聚丙交酯多元醇的方法 技术领域  Method for synthesizing polylactide polyol from lactide and polyol
本发明属于有机高分子技术领域， 具体涉及一种由丙交酯与多元醇为直接原料， 通 过丙交酯开环聚合的方式得到聚丙交酯多元醇的方法。 背景技术  The invention belongs to the technical field of organic polymers, and particularly relates to a method for obtaining a polylactide polyol by a method in which lactide and a polyol are used as a direct raw material by ring-opening polymerization of lactide. Background technique
聚乳酸多元醇在树脂改性方面,可以用来改善丙烯酸、聚脂、乙烯基等树脂的柔韧性、 流动性、 低温耐冲击性、 成型性等； 在粘合剂方面， 用聚丙交酯多元醇制得的聚氨酯胶 粘剂比起用其他聚醚和聚酯为原料生产的有更好的色泽、 水解稳定性和均匀性； 在聚氨 酯方面， 内聚强度和附着力强， 具有较高的强度、 耐磨性。  Polylactic acid polyols can be used to improve the flexibility, fluidity, low-temperature impact resistance, formability, etc. of acrylic, polyester, vinyl, etc. in terms of resin modification. In the case of adhesives, polylactide is used. The polyurethane adhesive prepared from alcohol has better color, hydrolytic stability and uniformity than other polyether and polyester. In terms of polyurethane, it has strong cohesive strength and adhesion, and has high strength and resistance. Grinding.
同时聚丙交酯多元醇具有生物降解的特性， 可以减少对环境的压力， 具有广阔的应 用前景。  At the same time, polylactide polyols have biodegradable properties, which can reduce the pressure on the environment and have broad application prospects.
聚丙交酯多元醇合成技术： 中国专利 CN102686670A公开了一种聚乳酸树脂与多元 醇进行酯交换合成聚丙交酯多元醇的方法。 所有公开的专利中均没有采用丙交酯与多元 醇为原料， 通过开环聚合反应生产聚丙交酯多元醇。 发明内容  Polylactide polyol synthesis technology: Chinese patent CN102686670A discloses a method for transesterification of a polylactic acid resin with a polyol to synthesize a polylactide polyol. In all of the published patents, lactide and a polyol are not used as raw materials to produce a polylactide polyol by ring-opening polymerization. Summary of the invention
本发明就是针对现有技术的不足， 提供一种由丙交酯和多元醇合成聚丙交酯多元醇 的方法， 该方法工艺简单， 操作简易， 适合工业化生产应用， 且无"三废"排放。  The present invention is directed to the deficiencies of the prior art, and provides a method for synthesizing polylactide polyol from lactide and polyol. The method is simple in process, simple in operation, suitable for industrial production applications, and has no "three wastes" emissions.
本发明的技术解决方案是这样实现的： 它包括以下步骤：  The technical solution of the present invention is implemented as follows: It comprises the following steps:
A、丙交酯纯化： 对粗品丙交酯进行纯化， 得到含量在 99.5%以上， 光学纯度在 99% 以上的丙交酯。  A. Lactide purification: The crude lactide is purified to obtain lactide having a content of 99.5% or more and an optical purity of 99% or more.
B、 聚乳酸多元醇元醇合成： 将纯化后丙交酯与多元醇按重量比 1:1.64-1:0.0126加 入反应釜， 然后按丙交酯的重量比 0.5/1000~1/1000的比例加入催化剂， 连续搅拌条件下 反应， 得到 100-5000粘均分子量的聚丙交酯多元醇。  B. Polylactic acid polyol alcohol synthesis: The purified lactide and polyol are added to the reaction kettle at a weight ratio of 1:1.64-1:0.0126, and then the ratio of lactide to weight ratio is 0.5/1000 to 1/1000. The catalyst is added and reacted under continuous stirring to obtain a polylactide polyol having a viscosity average molecular weight of 100 to 5,000.
本发明较好的技术解决方案是： 在聚合之前， 先纯化丙交酯， 要求纯化后的丙交酯 含量在 99.5%以上、 光纯在 99.0%以上， 水分要求在 lOOOppm以下。 其中： 聚合过程中加入的催化剂为锌类催化剂、 锡类催化剂或有机催化剂中的至少 一种， 其加入量为丙交酯重量的 0.5/1000~1/1000。 优选乳酸锌、 氧化锌、 锌粉、 二乙基 锌、 乳酸锡、 氧化锡、 二氧化锡、 氧化亚锡、 乳酸亚锡、 辛酸亚锡、 氯化亚锡、 锡粉、 丙酸或钛酸丁酯中的一种或多种的复合催化剂。 更优选的催化剂为辛酸亚锡， 或钛酸丁 酯、 氧化锡与乳酸锌按照 1:1:1的混合催化剂。 A preferred technical solution of the present invention is: prior to the polymerization, the lactide is purified, and the content of the lactide after purification is required to be 99.5% or more, the light purity is above 99.0%, and the moisture requirement is below 1000 ppm. Wherein: the catalyst added during the polymerization is at least one of a zinc-based catalyst, a tin-based catalyst or an organic catalyst, and the amount thereof is 0.5/1000 to 1/1000 of the weight of the lactide. Preferred is zinc lactate, zinc oxide, zinc powder, diethyl zinc, tin lactate, tin oxide, tin dioxide, stannous oxide, stannous lactate, stannous octoate, stannous chloride, tin powder, propionic acid or titanic acid. A composite catalyst of one or more of butyl esters. A more preferred catalyst is stannous octoate, or butyl titanate, tin oxide and zinc lactate in a 1:1:1 mixed catalyst.
其中： 步骤 A中对粗品丙交酯进行纯化的方法是重结晶、 减压精馏或熔融结晶， 或 者是上述纯化方法中的两种及两种以上的组合。 优选先重结晶再熔融结晶。  Wherein: the method for purifying the crude lactide in the step A is recrystallization, vacuum distillation or melt crystallization, or a combination of two or more of the above purification methods. It is preferred to first recrystallize and remelt the crystal.
本发明中的原料多元醇可以是 1， 4-丁二醇、 乙二醇、 新戊二醇、 一縮二乙二醇、 三羟甲基丙烷等。 优选 1,4丁二醇。  The raw material polyol in the present invention may be 1, 4-butanediol, ethylene glycol, neopentyl glycol, diethylene glycol, trimethylolpropane or the like. Preference is given to 1,4 butanediol.
与现有的技术相比， 本发明的技术优势在于：  Compared with the prior art, the technical advantages of the present invention are:
1、本发明生产聚丙交酯多元醇的工艺路线当中采用纯化丙交酯和多元醇作为直接原 料， 有别于采用聚丙交酯和醇作为直接原料， 通过酯交换生产聚丙交酯多元醇， 相比较 而言， 本发明具有以下特点：  1. The process route for producing polylactide polyol of the present invention uses purified lactide and polyol as direct raw materials, which is different from polylactide and alcohol as direct raw materials, and produces polylactide polyol by transesterification. In comparison, the present invention has the following features:
a、 以丙交酯和多元醇为原料聚合生成聚丙交酯多元醇可以得到粘均分子量 100、 300、 500、 800 等较低的聚丙交酯多元醇， 而采用聚乳酸和多元醇为原料制备聚丙交酯 多元醇分子量都较高， 产品流动性差， 使用也比较困难。  a. Polymerization of lactide and polyol as raw materials to form polylactide polyol can obtain lower polylactide polyols with viscosity average molecular weights of 100, 300, 500, 800, etc., and polylactic acid and polyol as raw materials. Polylactide polyols have a relatively high molecular weight, and the product has poor fluidity and is difficult to use.
b、 以丙交酯和多元醇为原料聚合反应可以得到分子量分布较窄的聚丙交酯多元醇， 而通过酯交换得到的聚丙交酯多元醇含有较多的低聚物副产物， 分子量分布会比较宽。  b. Polylactide polyol with narrow molecular weight distribution can be obtained by polymerization of lactide and polyol as raw materials, and polylactide polyol obtained by transesterification contains more oligomer by-products, and the molecular weight distribution will be More wide.
c、 以丙交酯和多元醇为原料聚合生成聚丙交酯多元醇， 生产条件较温和， 以聚丙交 酯和多元醇为原料进行酯交换反应生产聚丙交酯多元醇需在熔融条件下进行， 条件较苛 刻。  c. The polylactide polyol is polymerized by using lactide and polyol as raw materials, and the production conditions are mild. The transesterification reaction of polylactide and polyol as raw materials to produce polylactide polyol needs to be carried out under molten conditions. The conditions are harsh.
2、 本发明采用梯度升温的方式可以使丙交酯现在较低温度下开环聚合， 提高丙交酯 的转化率， 减少丙交酯因升华而出现损失， 这样可以保持投料时丙交酯与多元醇的重量 比， 避免因丙交酯减少导致合成的聚丙交酯多元醇的分子量与理论设计的分子量偏低， 可以确保合成产品的品质的稳定性。  2. The gradient heating method of the invention can make the lactide ring-opening polymerization at a lower temperature, increase the conversion rate of lactide, and reduce the loss of lactide due to sublimation, so that the lactide can be kept at the time of feeding. The weight ratio of the polyol avoids the decrease in the molecular weight of the synthesized polylactide polyol and the theoretically designed molecular weight due to the reduction of lactide, and the stability of the quality of the synthetic product can be ensured.
3、 本发明分采用梯度升温及对不同温度条件下反应时间的调整， 可以减少产品中丙 交酯单体的量， 从而避免了丙交酯单体对产品品质的影响。 具体实施方式 3. The invention adopts gradient heating and adjustment of reaction time under different temperature conditions, can reduce the amount of lactide monomer in the product, thereby avoiding the influence of lactide monomer on product quality. detailed description
下面结合具体实施方式对本发明做进一步的详细描述。  The present invention will be further described in detail below in conjunction with the specific embodiments.
实例一： Example 1:
先将粗品丙交酯进行纯化。 纯化后的丙交酯要求丙交酯含量在 99.5%以上、 光纯在 99.0%以上， 水分要求在 lOOOppm以下， 加入纯化后达到要求的丙交酯 122.0g到 500ml 三口烧瓶中， 然后向其中加入试剂级 1,4-丁二醇 200.0g， 然后加入丙交酯质量 0.5/1000 的催化剂辛酸亚锡， 抽真空进行氮气置换， 在氮气保护条件下， 升高温度到 140°C， 在 140°C条件下反应 lh，升高温度到 170°C反应 3h。反应完后得到粘均分子量为 100.2聚丙 交酯多元醇。 实例二：  The crude lactide is first purified. The purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 122.0 g to 500 ml three-necked flask, and then added thereto. Reagent grade 1,4-butanediol 200.0g, then add lactide stannous acid stannous acid with a lactide mass of 0.5/1000, evacuate under vacuum, and raise the temperature to 140 ° C at 140 ° under nitrogen protection conditions. The reaction was carried out for 1 hour under C conditions, and the temperature was raised to 170 ° C for 3 hours. After the reaction, a polyglycolide polyol having a viscosity average molecular weight of 100.2 was obtained. Example 2:
先将粗品丙交酯进行纯化。 纯化后的丙交酯要求丙交酯含量在 99.5%以上、 光纯在 99.0%以上， 水分要求在 lOOOppm以下， 加入纯化后达到要求的丙交酯 232.2g到 500ml 三口烧瓶中， 然后向其中加入试剂级乙二醇 100.0g， 然后加入丙交酯质量 0.5/1000的催 化剂乳酸亚锡， 抽真空进行氮气置换， 在氮气保护条件下， 升高温度到 140°C， 在 140°C 条件下反应 lh， 升高温度到 170°C反应 3h。 得到粘均分子量为 302.0聚丙交酯多元醇。 实例三：  The crude lactide is first purified. The purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 232.2 g to 500 ml three-necked flask, and then added thereto. Reagent grade ethylene glycol 100.0g, then add lactide lactate mass 0.5 / 1000 catalyst stannous lactate, vacuum to nitrogen replacement, under nitrogen protection conditions, raise the temperature to 140 ° C, at 140 ° C conditions Lh, raise the temperature to 170 ° C for 3 h. A polyglycolide polyol having a viscosity average molecular weight of 302.0 was obtained. Example three:
先将粗品丙交酯进行纯化。 纯化后的丙交酯要求丙交酯含量在 99.5%以上、 光纯在 99.0%以上， 水分要求在 lOOOppm以下， 加入纯化后达到要求的丙交酯 227.1g到 500ml 三口烧瓶中，然后向其中加入试剂级新戊二醇 50.0g，然后加入丙交酯质量 0.5/1000的催 化剂， 催化剂为二乙基锌、 乳酸锡、 氧化锡按照重量比 1 1 的混合物， 然后抽真空进 行氮气置换， 在氮气保护条件下， 升高温度到 140°C， 在 140°C条件下反应 lh， 升高温 度到 170°C反应 3h。 反应完后得到粘均分子量为 510.0聚丙交酯多元醇。 实例四：  The crude lactide is first purified. The purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 227.1 g to 500 ml three-necked flask, and then added thereto. Reagent grade neopentyl glycol 50.0g, then adding lactide mass 0.5/1000 catalyst, the catalyst is diethyl zinc, tin lactate, tin oxide according to the weight ratio of 1 1 mixture, then vacuuming for nitrogen replacement, in nitrogen Under the protective conditions, the temperature was raised to 140 ° C, the reaction was carried out at 140 ° C for 1 h, and the temperature was raised to 170 ° C for 3 h. After the completion of the reaction, a polylactide polyol having a viscosity average molecular weight of 510.0 was obtained. Example four:
先将粗品丙交酯进行纯化。 纯化后的丙交酯要求丙交酯含量在 99.5%以上、 光纯在 99.0%以上， 水分要求在 lOOOppm以下， 加入纯化后达到要求的丙交酯 262.5g到 500ml 三口烧瓶中， 然后向其中加入试剂级 1,4-丁二醇 33.3g， 然后加入丙交酯质量 0.5/1000的 催化剂， 所述的催化剂为钛酸丁酯、 氧化锡与乳酸锌按照重量比为 1:1:1 的混合物； 抽 真空进行氮气置换， 在氮气保护条件下， 升高温度到 140°C， 在 140°C条件下反应 2h， 升高温度到 170°C反应 3h。 反应完后得到粘均分子量为 815.6聚丙交酯多元醇。 实例五： The crude lactide is first purified. The purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of 1000 ppm or less, and a purified lactide to obtain a desired lactide of 262.5 g to 500 ml. In a three-necked flask, 33.3 g of reagent grade 1,4-butanediol was then added thereto, and then a catalyst having a lactide mass of 0.5/1000 was added, and the catalyst was butyl titanate, tin oxide and zinc lactate in terms of weight ratio. It is a 1:1:1 mixture; vacuum is applied for nitrogen replacement, and under nitrogen protection, the temperature is raised to 140 ° C, the reaction is carried out at 140 ° C for 2 h, and the temperature is raised to 170 ° C for 3 h. After the reaction, a viscosity average molecular weight of 815.6 polylactide polyol was obtained. Example 5:
先将粗品丙交酯进行纯化。 纯化后的丙交酯要求丙交酯含量在 99.5%以上、 光纯在 99.0%以上， 水分要求在 lOOOppm以下， 加入纯化后达到要求的丙交酯 200.1g到 500ml 三口烧瓶中，然后向其中加入试剂级一縮二乙二醇 20.01g，然后加入丙交酯质量 0.5/1000 的催化剂辛酸亚锡， 抽真空进行氮气置换， 在氮气保护条件下， 升高温度到 140°C， 在 140°C条件下反应 2h，升高温度到 170°C反应 4h。得到粘均分子量为 989.1聚丙交酯多元 醇。 实例六：  The crude lactide is first purified. The purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 200.1 g to 500 ml three-necked flask, and then added thereto. Reagent grade diethylene glycol 20.01g, then add the lactide mass of 0.5/1000 catalyst stannous octoate, vacuum to nitrogen replacement, under nitrogen protection conditions, raise the temperature to 140 ° C, at 140 ° C The reaction was carried out for 2 h under the conditions, and the temperature was raised to 170 ° C for 4 h. A polylacticide polyol having a viscosity average molecular weight of 989.1 was obtained. Example six:
先将粗品丙交酯进行纯化。 纯化后的丙交酯要求丙交酯含量在 99.5%以上、 光纯在 99.0%以上， 水分要求在 lOOOppm以下， 加入纯化后达到要求的丙交酯 212.1g到 500ml 三口烧瓶中， 然后向其中加入试剂级 1,4-丁二醇 10.01g， 然后加入丙交酯质量 0.75/1000 的催化剂辛酸亚锡， 抽真空进行氮气置换， 在氮气保护条件下， 升高温度到 140°C， 在 140°C条件下反应 2h， 升高温度到 170°C反应 4h。 反应完后得到粘均分子量为 1956.8聚 丙交酯多元醇。 实例七：  The crude lactide is first purified. The purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 212.1 g to 500 ml three-necked flask, and then added thereto. Reagent grade 1,4-butanediol 10.01g, then add the lactide stannous octoate with a lactide mass of 0.75/1000, evacuate under vacuum, and raise the temperature to 140 ° C at 140 ° under nitrogen protection. The reaction was carried out for 2 h under C conditions, and the temperature was raised to 170 ° C for 4 h. After the reaction, a viscosity average molecular weight of 1956.8 polylactide polyol was obtained. Example 7:
先将粗品丙交酯进行纯化。 纯化后的丙交酯要求丙交酯含量在 99.5%以上、 光纯在 99.0%以上， 水分要求在 lOOOppm以下， 加入纯化后达到要求的丙交酯 238.9g到 500ml 三口烧瓶中， 然后向其中加入试剂级三羟甲基丙烷 3.0g， 然后加入丙交酯质量 1/1000的 催化剂辛酸亚锡，抽真空进行氮气置换，在氮气保护条件下，升高温度到 14CTC，在 14CTC 条件下反应 2h， 升高温度到 170°C反应 4h。 反应完后得到粘均分子量为 4942.7。 聚丙交 酯多元醇。  The crude lactide is first purified. The purified lactide requires a lactide content of 99.5% or more, a light purity of 99.0% or more, a moisture requirement of less than 1000 ppm, and a purified lactide to obtain a desired lactide 238.9 g to 500 ml three-necked flask, and then added thereto. Reagent grade trimethylolpropane 3.0g, then add lactide stearate stannous acid with a lactide mass of 1/1000, vacuum under nitrogen replacement, raise the temperature to 14CTC under nitrogen protection, and react for 2h under 14CTC conditions. The temperature was raised to 170 ° C for 4 h. After the reaction, a viscosity average molecular weight of 4942.7 was obtained. Polylactide polyol.

Claims

权利要求书 claims
1、 一种由丙交酯和多元醇合成聚丙交酯多元醇的方法， 它包括以下步骤： 1. A method for synthesizing polylactide polyol from lactide and polyol, which includes the following steps:
A、丙交酯纯化： 对粗品丙交酯进行纯化， 得到含量在 99.5%以上， 光学纯度在 99% 以上的丙交酯； A. Purification of lactide: Purify crude lactide to obtain lactide with a content of more than 99.5% and an optical purity of more than 99%;
B、 聚丙交酯多元醇合成： 将纯化后的丙交酯与多元醇加入反应釜， 然后按丙交酯 的重量比为 0.5/1000~1/1000的比例加入催化剂进行聚合反应， 得到 100-5000粘均分子 量的聚丙交酯多元醇， 所述的催化剂为乳酸锌、 氧化锌、 锌粉、 二乙基锌、 乳酸锡、 氧 化锡、 二氧化锡、 氧化亚锡、 乳酸亚锡、 辛酸亚锡、 氯化亚锡、 锡粉、 丙酸或钛酸丁酯 中的一种或多种的复合催化剂。 B. Synthesis of polylactide polyol: Add the purified lactide and polyol to the reaction kettle, and then add the catalyst according to the weight ratio of lactide to 0.5/1000~1/1000 for polymerization reaction to obtain 100- Polylactide polyol with a viscosity average molecular weight of 5000, the catalyst is zinc lactate, zinc oxide, zinc powder, diethyl zinc, tin lactate, tin oxide, tin dioxide, stannous oxide, stannous lactate, stannous octoate One or more composite catalysts selected from tin, stannous chloride, tin powder, propionic acid or butyl titanate.
2、根据权利要求 1所述的一种由丙交酯和多元醇合成聚丙交酯多元醇的方法，其特 征在于： 纯化后的丙交酯水分在 lOOOppm以下。 2. A method for synthesizing polylactide polyol from lactide and polyol according to claim 1, characterized in that: the moisture content of the purified lactide is below 1000 ppm.
3、 根据权利要求 1所述的一种由丙交酯和多元醇合成聚丙交酯多元醇的方法，其特 征在于： 所述的的催化剂为辛酸亚锡。 3. A method for synthesizing polylactide polyol from lactide and polyol according to claim 1, characterized in that: the catalyst is stannous octoate.
4、根据权利要求 1所述的一种由丙交酯和多元醇合成聚丙交酯多元醇的方法，其特 征在于： 步骤 A中对粗品丙交酯进行纯化的方法是重结晶、 减压精馏或熔融结晶， 或者 是上述纯化方法中的几种及几种以上的组合。 4. A method for synthesizing polylactide polyol from lactide and polyol according to claim 1, characterized in that: the method for purifying crude lactide in step A is recrystallization, vacuum purification Distillation or melting crystallization, or a combination of several or more of the above purification methods.
5、 根据权利要求 1或 3所述的一种由丙交酯和多元醇合成聚丙交酯多元醇的方法， 其特征在于： 聚合反应时丙交酯与多元醇的重量比为 1:1.64-1:0.0126。 5. A method for synthesizing polylactide polyol from lactide and polyol according to claim 1 or 3, characterized in that: the weight ratio of lactide to polyol during polymerization reaction is 1:1.64- 1:0.0126.
6、根据权利要求 1所述的一种由丙交酯和多元醇合成聚丙交酯多元醇的方法，其特 征在于： 所述的多元醇是 1， 4-丁二醇、 乙二醇、 新戊二醇、 一縮二乙二醇或三羟甲基 丙烷。 6. A method for synthesizing polylactide polyol from lactide and polyol according to claim 1, characterized in that: the polyol is 1, 4-butanediol, ethylene glycol, new Pentylene glycol, diethylene glycol or trimethylolpropane.
7、根据权利要求 1所述的一种由丙交酯和多元醇合成聚丙交酯多元醇的方法，其特 征在于： 进行聚合反应时采用氮气保护， 反应过程中采取梯度升温， 在 14CTC条件下反 应 l-2h， 升高温度到 170°C反应 2-4h。 7. A method for synthesizing polylactide polyol from lactide and polyol according to claim 1, characterized in that: nitrogen protection is used during the polymerization reaction, and gradient heating is adopted during the reaction process, under the condition of 14 CTC React for 1-2 hours, raise the temperature to 170°C and react for 2-4 hours.
8、根据权利要求 1所述的一种由丙交酯和多元醇合成聚丙交酯多元醇的方法，其特 征在于： 所述的催化剂为钛酸丁酯、 氧化锡与乳酸锌按照重量比为 1:1:1的混合物。 8. A method for synthesizing polylactide polyol from lactide and polyol according to claim 1, characterized in that: the catalyst is butyl titanate, tin oxide and zinc lactate in a weight ratio of 1:1:1 mixture.
PCT/CN2013/081035 2013-08-08 2013-08-08 Method for synthesis of polylactide polyol from lactide and polyol WO2015018015A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040000729A1 (en) * 2002-07-01 2004-01-01 Daisuke Inomata Alignment marks of semiconductor device
CN101580582A (en) * 2009-05-06 2009-11-18 深圳市光华伟业实业有限公司 Method for preparing polylactic acid
CN101602840A (en) * 2009-07-22 2009-12-16 重庆大学 Based on D, Biodegradable shape-memory material of L-poly(lactic acid) and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040000729A1 (en) * 2002-07-01 2004-01-01 Daisuke Inomata Alignment marks of semiconductor device
CN101580582A (en) * 2009-05-06 2009-11-18 深圳市光华伟业实业有限公司 Method for preparing polylactic acid
CN101602840A (en) * 2009-07-22 2009-12-16 重庆大学 Based on D, Biodegradable shape-memory material of L-poly(lactic acid) and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QYAN, DAPING: "Synthesis and Thermal Stability of Poly (DL-Lactide", CHINESE JOURNAL OF APPLIED CHEMISTRY, vol. 17, no. 3, 30 June 2000 (2000-06-30) *

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