WO2019010767A1 - 一种pbat-pla共聚酯的共聚合成方法 - Google Patents

一种pbat-pla共聚酯的共聚合成方法 Download PDF

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WO2019010767A1
WO2019010767A1 PCT/CN2017/099437 CN2017099437W WO2019010767A1 WO 2019010767 A1 WO2019010767 A1 WO 2019010767A1 CN 2017099437 W CN2017099437 W CN 2017099437W WO 2019010767 A1 WO2019010767 A1 WO 2019010767A1
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pbat
pla
catalyst
prepolymer
copolyester
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PCT/CN2017/099437
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English (en)
French (fr)
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阮刘文
李万鑫
汤永彬
何新宇
杨文军
冒彬
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河南谷润聚合物有限公司
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Priority to US16/314,404 priority Critical patent/US10875958B2/en
Priority to EP17905898.7A priority patent/EP3453731B1/en
Publication of WO2019010767A1 publication Critical patent/WO2019010767A1/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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • C08G63/02—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
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy 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
    • 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
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • 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 relates to the technical field of biodegradable materials, in particular to a method for copolymerizing and synthesizing PBAT-PLA copolyester.
  • polylactic acid has the disadvantages of low elongation at break, poor impact strength, and poor toughness. It lacks elasticity and flexibility, and it is difficult to meet certain practical requirements, which limits its application. Therefore, it is necessary to toughen and modify polylactic acid, and the conventional methods include physical modification and chemical modification.
  • the prior art uses a PBAT-PLA blend prepared by a process in which PBAT is directly blended with polylactic acid to increase the elongation, impact strength and toughness of the polylactic acid.
  • PBAT-PLA copolymerization method a diisocyanate group is introduced as a chain extender, and the toxicity of the diisocyanate limits the application of the method.
  • lactide is opened by a hydroxyl polymer to obtain PBAT-PLA is obtained.
  • lactide needs to be purified and has high production cost.
  • the object of the present invention is to provide a copolymerization synthesis method of PBAT-PLA copolyester, which is harmless, non-toxic, environmentally friendly and low in cost.
  • the weight ratio of the prepolymer PBAT to the prepolymer PLA is from 1 to 10:1 to 10.
  • the prepolymer PBAT is prepared by adding adipic acid, dimethyl terephthalate and 1,4-butanediol to the reaction vessel, the adipic acid, terephthalic acid
  • the molar ratio of dimethyl ester to 1,4-butanediol is 1 ⁇ 2:1 ⁇ 2:2 ⁇ 4; protected by nitrogen, heated to 140-160 ° C; after the material in the reactor is completely melted, the catalyst is added A; vacuuming to 0.02-0.06Mpa, reaction 1-2h; then ramping to 210-230 ° C in l_2h, vacuum control at 500-1000Pa, continue reaction 1-5h; after discharge to get prepolymer PBAT .
  • the amount of catalyst A is from 0.01% to 0.5% of the total amount of the reactants.
  • the catalyst A is a titanium-based catalyst
  • the titanium-based catalyst is tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium chloride, titanium dioxide, and the catalyst A is One or more of the titanium-based catalysts.
  • the catalyst A is: tetrabutyl titanate.
  • the prepolymer PLA is prepared by adding L-lactic acid into the reaction vessel, replacing it with nitrogen three times, heating to 110-130 ° C, gradually controlling the vacuum degree to 0.02-0.08 Mpa, and stirring the reaction. After 4 hours, the composite catalyst B was added, and the temperature was raised to 160-190 ° C in a period of 1 to 2 h, and the reaction was carried out to 500-1000 Pa, and the reaction was continued for 1 to 5 hours; then, the prepolymer polylactic acid was obtained by discharging.
  • the amount of the main catalyst in the composite catalyst B is 0.01%-0.5% of the total amount of the reactants, and the molar ratio of the promoter to the main catalyst in the composite catalyst B is 1:1.
  • the main catalyst is a Sn-based catalyst or a Zn-based catalyst
  • the Sn-based catalyst comprises stannous octoate, stannous chloride dihydrate, stannous oxide and stannous chloride anhydrate, tetraphenyltin
  • the Zn-based catalyst includes zinc powder, diethyl zinc, zinc octoate, zinc oxide, and zinc chloride
  • the main catalyst is one or more of the Sn-based catalysts or one or more of the Zn-based catalysts
  • the cocatalyst is an organic sulfonic acid compound, including methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, p-toluenesulfonic acid and p-chlorobenzenesulfonic acid; the cocatalyst is in the organic sulfonic acid compound One or more.
  • the main catalyst is: stannous chloride dihydrate, and the cocatalyst is p-toluenesulfonic acid.
  • Figure 1 is a gel permeation chromatogram of the molecular weight of the PBAT-PLA copolyester prepared in Examples 1-3 of the present invention.
  • the invention provides a copolymerization synthesis method of PBAT-PLA copolyester, comprising the following steps: prepolymer PBAT and prepolymer PLA are uniformly blended and then put into a high vacuum reaction kettle, the degree of vacuum is 5-100 Pa, and heated to 100. The reaction was carried out at -110 ° C for 0.5-1 h; then the temperature was raised to 145-155 ° C in l_2 h, and the reaction was continued for 5-10 h to obtain a product PBAT-PLA copolyester having a weight average molecular weight of 100,000 to 250,000. Among them, the degree of vacuum is preferably controlled at 20 to 80 Pa, and more preferably controlled at 40 to 60 Pa.
  • the weight ratio of the prepolymer PBAT to the prepolymer PLA is from 1 to 10:1 to 10.
  • the prepolymer PBAT is prepared by introducing adipic acid, dimethyl terephthalate and 1,4-butanediol, the adipic acid, dimethyl terephthalate and 1, in the reaction vessel.
  • the molar ratio of 4-butanediol is 1 ⁇ 2:1 ⁇ 2:2 ⁇ 4; protected by nitrogen, heated to 140-16CTC; after the material in the reactor is completely melted, catalyst A is added; vacuum is drawn to 0.02-0.06 Mpa, reaction l_2h; after that, the temperature is raised to 210_230 ° C in l_2h, the degree of vacuum is controlled at 500-1000 Pa, and the reaction is continued for l_5h; then the prepolymer PBAT is obtained, and the weight average molecular weight is 40,000-90000.
  • the amount of the catalyst A is from 0.01% to 0.5% of the total amount of the reactants.
  • the catalyst A is a titanium-based catalyst
  • the titanium-based catalyst is tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium chloride, titanium dioxide, and the catalyst A is in the titanium catalyst.
  • the catalyst A is: tetrabutyl titanate.
  • the prepolymer PLA of the present invention is prepared by adding L-lactic acid into the reaction vessel, replacing it with nitrogen three times, heating to 110-130 ° C, gradually controlling the vacuum degree to 0.02-0.08 Mpa, and stirring the reaction for 1-4 h;
  • the composite catalyst B was added, and the temperature was raised to 160-190 ° C in a range of 1 - 2 h, and the reaction was carried out to 500-1000 Pa, and the reaction was continued for 1-5 h. Thereafter, the prepolymer polylactic acid was obtained by discharging to obtain a weight average molecular weight of 30,000 to 80,000.
  • the amount of the main catalyst in the composite catalyst B is 0.01%-0.5% of the total amount of the reactants, and the molar ratio of the promoter to the main catalyst in the composite catalyst B is 1:1.
  • the main catalyst is a Sn-based catalyst or a Zn-based catalyst
  • the Sn-based catalyst comprises stannous octoate, stannous chloride dihydrate, stannous oxide and stannous chloride anhydrate, tetraphenyltin
  • the Zn-based catalyst includes a zinc powder, diethyl zinc, zinc octoate, zinc oxide, and zinc chloride
  • the main catalyst being one or more of the Sn-based catalysts or one or more of the Zn-based catalysts
  • the cocatalyst is an organic sulfonic acid compound, including methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, p-toluenesulfonic acid, and p-chlorobenzenesulfonic acid; the cocatalyst is one of the organic sulfonic acid compounds or A variety.
  • the main catalyst is: stannous chloride hydrate, and the cocatalyst is p-toluenesulfonic acid.
  • PBAT prepolymer in step a and the PLA prepolymer in step b are uniformly blended, put into a high vacuum reactor, evacuated to 100 Pa, heated to 100 ° C for 0.5 h, and the reactant is The temperature was raised to 145 ° C in 2 h, and the reaction was continued for 5 h to obtain the final product PBAT-PLA, which was white in color.
  • the PBAT-PLA copolyester prepared in this example had a weight average molecular weight of 100,000.
  • the molar ratio of PBAT prepolymer to PLA prepolymer was 1:10.
  • PBAT prepolymer in step a and the PLA prepolymer in step b are uniformly blended and put into a high vacuum reactor, vacuumed to 5 Pa, heated to 110 ° C for 1 h, and the reaction is at lh. The internal gradient was raised to 155 ° C, and the reaction was continued for 10 h to obtain the final product PBAT-PLA, which was white in color.
  • the PBAT-PLA copolyester prepared in this example had a weight average molecular weight of 250,000.
  • the molar ratio of PBAT prepolymer to PLA prepolymer was: 10:1.
  • Step a and step b are the same as in the first embodiment.
  • the catalyst A is titanium chloride
  • the catalyst B is diethyl zinc and methanesulfonic acid.
  • PBAT prepolymer in step a and the PLA prepolymer in step b are uniformly blended and put into a high vacuum reactor, vacuumed to 80 Pa, heated to 108 ° C for 0.5 h, and the reactant is The gradient was raised to 145 ° C in 1.5 h, and the reaction was continued for 10 h to obtain the final product PBAT-PLA, which was white in color.
  • the PBAT-PLA copolyester has a weight average molecular weight of 200,000.
  • the molar ratio of PBAT prepolymer to PLA prepolymer was: 3:7.
  • Step a and step b are the same as in the second embodiment.
  • the catalyst A is tetraisopropyl titanate
  • the catalyst B in the step b is tetraphenyltin and p-chlorobenzenesulfonic acid.
  • PBAT prepolymer in step a and the PLA prepolymer in step b are uniformly blended and put into a high vacuum reactor, vacuumed to 40 Pa, heated to 110 ° C for 1 h, and the reactant is at 1.5.
  • the gradient in h was raised to 145 ° C, and the reaction was continued for 8 h to obtain the final product PBAT-PLA, which was white in color.
  • the PBAT-PLA copolyester has a weight average molecular weight of 220,000.
  • the molar ratio of PBAT prepolymer to PLA prepolymer is: 4:6
  • Step a and step b are the same as in the third embodiment.
  • the catalyst A is tetrabutyl titanate and tetraisopropyl titanate
  • the catalyst B in the step b is zinc powder and 1-propanesulfonic acid.
  • PBAT prepolymer in step a and the PLA prepolymer in step b are uniformly blended, put into a high vacuum reactor, evacuated to 60 Pa, heated to 11 CTC for 1 h, and the reaction is in 1.5 h. The gradient was warmed to 155 ° C and the reaction was continued for 10 h to give the final product PBAT-PLA.
  • the PBAT-PLA copolyester has a weight average molecular weight of 150,000.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

本发明提供一种PBAT-PLA共聚酯的共聚合成方法，包括以下步骤：将预聚物PBAT和预聚物PLA共混均匀后投入高真空反应釜中，真空度在5-100Pa，加热至100-110℃反应0.5-1h；之后在1-2h内梯度升温至145-155℃，继续反应5-10h，得到产物PBAT-PLA共聚酯，重均分子量为100000-250000。本发明提供的PBAT-PLA共聚酯的共聚合成方法，无害无毒环保且成本低。

Description

[援引加入(细则20.6) 17.10.2017]　一种PBAT-PLA共聚酯的共聚合成方法 技术领域
[援引加入(细则20.6) 17.10.2017]　
本发明涉及生物降解材料技术领域，尤其涉及一种PBAT-PLA共聚酯的共聚合成方法。
背景技术
[援引加入(细则20.6) 17.10.2017]　
聚乳酸集资源可再生性、生物完全降解性、以及生物相容性、可加工性、透明性于一身，被誉为本世纪最有发展前途的生物化工合成高分子新型绿色环保材料。
[援引加入(细则20.6) 17.10.2017]　
然而聚乳酸存在断裂伸长率低、冲击强度差、韧性差的缺点，缺乏弹性和柔性，难以满足某些实际使用要求，限制了它的应用。因此需要对聚乳酸进行增韧改性，传统的方法包括物理改性和化学改性的方法。
[援引加入(细则20.6) 17.10.2017]　
现有技术采用PBAT与聚乳酸直接共混加工的工艺制备的PBAT-PLA共混物，以增加聚乳酸的伸长率、冲击强度和韧性。现有技术一PBAT-PLA的共聚方法中，会引入二异氰酸酯基团作为扩链剂，二异氰酸酯的毒性限制了该方法的应用。现有技术二，通过羟基聚合物引发丙交酯开环得到PBAT-PLA的方法，然而丙交酯需要提纯、生产成本高。
发明内容
[援引加入(细则20.6) 17.10.2017]　
本发明的目的是提供一种PBAT-PLA共聚酯的共聚合成方法，无害无毒环保且成本低。
[援引加入(细则20.6) 17.10.2017]　
为了解决上述技术问题，本发明提供的PBAT-PLA共聚酯的共聚合成方法是这样实现的：
[援引加入(细则20.6) 17.10.2017]　
一种PBAT-PLA共聚酯的共聚合成方法，包括以下步骤：
[援引加入(细则20.6) 17.10.2017]　
将预聚物PBAT和预聚物PLA共混均匀后投入高真空反应釜中，真空度在5-100Pa,加热至100-110°C反应0.5_lh;之后在1-2h内梯度升温至145-155°C，继续反应5-10h，得到产物PBAT-PLA共聚酯，重均分子量为100000-250000。
[援引加入(细则20.6) 17.10.2017]　
可选的，所述预聚物PBAT和所述预聚物PLA的重量比为1〜10:1〜10。
[援引加入(细则20.6) 17.10.2017]　
可选的，所述预聚物PBAT由以下方法制备：在反应釜中投入己二酸、对苯二甲酸二甲酯和1，4-丁二醇，所述己二酸、对苯二甲酸二甲酯和1，4-丁二醇的摩尔比为1〜2：1〜2：2〜4；通氮气保护，加热到140-160°C;待反应釜中物料完全熔融后，加入催化剂A;抽真空至0.02-0.06Mpa，反应1-2h;之后在l_2h内梯度升温至210-230°C，真空度控制在500-1000Pa，继续反应1-5h;之后出料得到预聚物PBAT。
[援引加入(细则20.6) 17.10.2017]　
可选的，催化剂A的用量为反应物总量的0.01%-0.5%。
[援引加入(细则20.6) 17.10.2017]　
可选的，所述催化剂A为钛系催化剂，所述钛系催化剂为钛酸四丁酯、钛酸四乙酯、钛酸四异丙酯、氯化钛、二氧化钛，所述催化剂A为所述钛系催化剂中的一种或多种。
[援引加入(细则20.6) 17.10.2017]　
可选的，所述催化剂A为：钛酸四丁酯。
[援引加入(细则20.6) 17.10.2017]　
可选的，所述预聚物PLA由以下方法制备：在反应釜中投入L-乳酸，氮气置换三次后加热到110-130°C，逐步将真空度控制在0.02-0.08Mpa，搅拌反应l-4h;之后加入复合催化剂B，在l_2h内梯度升温至160-190°C，抽真空至500-1000Pa,继续反应l_5h;之后出料得到预聚物聚乳酸。
[援引加入(细则20.6) 17.10.2017]　
可选的，所述复合催化剂B中主催化剂的用量为反应物总量的0.01%-0.5%，复合催化剂B中助催化剂与主催化剂的摩尔比为：1:1。
[援引加入(细则20.6) 17.10.2017]　
可选的，所述主催化剂为Sn基催化剂或Zn基催化剂，Sn基催化剂包括辛酸亚锡、二水氯化亚锡、氧化亚锡和氯化亚锡脱水物、四苯基锡，所述Zn基催化剂包括锌粉末、二乙基锌、辛酸锌、氧化锌和氯化锌；所述主催化剂为所述Sn基催化剂的一种或多种或为所述Zn基催化剂的一种或多种；所述助催化剂为有机磺酸化合物，包括甲磺酸、乙磺酸、1-丙磺酸、对甲苯磺酸和对氯苯磺酸；所述助催化剂为所述有机磺酸化合物中的一种或多种。
[援引加入(细则20.6) 17.10.2017]　
可选的，所述主催化剂为：二水氯化亚锡，所述助催化剂为对甲苯磺酸。
[援引加入(细则20.6) 17.10.2017]　
本发明提供的PBAT-PLA共聚酯的共聚合成方法，预聚物PBAT和预聚物PLA投入到高真空反应釜中，控制真空度，最终制得重均分子量为100000-250000的PBAT-PLA共聚酯。本发明相对于现有技术一二异氰酸酯引发PLA和PBAT之间的扩链反应得到聚合物相比，本发明在真空度5-lOOPa下直接使用预聚物PBAT和预聚物PLA直接共聚合成PBAT-PLA共聚酯，没有添加扩链剂二异氰酸酯及任何其他溶剂，避免了二异氰酸酯及其他溶剂对人体及环境带来的危害。相对于现有技术二使用丙交酯开环得到PBAT-PLA，本发明生产成本低。
附图说明
[援引加入(细则20.6) 17.10.2017]　
图1是本发明实施例1-3制备的PBAT-PLA共聚酯的表征分子量的凝胶渗透色谱图。
具体实施方式
[援引加入(细则20.6) 17.10.2017]　
为了使本发明的目的、技术方案及优点更加清楚明白，以下实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
[援引加入(细则20.6) 17.10.2017]　
己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物（PBAT，Polybutyleneadipate-co-terephthalate),聚乳酸(PLA,polylacticacid)。
[援引加入(细则20.6) 17.10.2017]　
本发明提供一种PBAT-PLA共聚酯的共聚合成方法，包括以下步骤：预聚物PBAT和预聚物PLA共混均匀后投入高真空反应釜中，真空度在5-100Pa，加热至100-110°C反应0.5-lh;之后在l_2h内梯度升温至145-155°C，继续反应5_10h，得到产物PBAT-PLA共聚酯，重均分子量为100000-250000。其中，真空度优选控制在20-80Pa，更优选地控制在40-60Pa。
[援引加入(细则20.6) 17.10.2017]　
本发明共聚合成反应中，预聚物PBAT和所述预聚物PLA的重量比为1〜10:1〜10。
[援引加入(细则20.6) 17.10.2017]　
预聚物PBAT由以下方法制备：在反应釜中投入己二酸、对苯二甲酸二甲酯和1，4-丁二醇，所述己二酸、对苯二甲酸二甲酯和1，4-丁二醇的摩尔比为1〜2：1〜2：2〜4；通氮气保护，加热到140-16CTC;待反应釜中物料完全熔融后，加入催化剂A;抽真空至0.02-0.06Mpa,反应l_2h;之后在l_2h内梯度升温至210_230°C，真空度控制在500-1000Pa，继续反应l_5h;之后出料得到预聚物PBAT，重均分子量为40000-90000。
[援引加入(细则20.6) 17.10.2017]　
其中，催化剂A的用量为反应物总量的0.01%-0.5%。
[援引加入(细则20.6) 17.10.2017]　
其中，所述催化剂A为钛系催化剂，钛系催化剂为钛酸四丁酯、钛酸四乙酯、钛酸四异丙酯、氯化钛、二氧化钛，催化剂A为所述钛系催化剂中的一种或多种。 优选地，催化剂A为：钛酸四丁酯。
[援引加入(细则20.6) 17.10.2017]　
本发明预聚物PLA由以下方法制备：在反应釜中投入L-乳酸，氮气置换三次后加热到110-130°C，逐步将真空度控制在0.02-0.08Mpa，搅拌反应1-4h;之后加入复合催化剂B，在l_2h内梯度升温至160-190°C，抽真空至500-1000Pa，继续反应1-5h;之后出料得到预聚物聚乳酸，重均分子量为30000-80000。
[援引加入(细则20.6) 17.10.2017]　
其中，复合催化剂B中主催化剂的用量为反应物总量的0.01%-0.5%，复合催化剂B中助催化剂与主催化剂的摩尔比为：1:1。
[援引加入(细则20.6) 17.10.2017]　
其中，主催化剂为Sn基催化剂或Zn基催化剂，Sn基催化剂包括辛酸亚锡、二水合氯化亚锡、氧化亚锡和氯化亚锡脱水物、四苯基锡，所述Zn基催化剂包括锌粉末、二乙基锌、辛酸锌、氧化锌和氯化锌；所述主催化剂为所述Sn基催化剂的一种或多种或为所述Zn基催化剂的一种或多种；所述助催化剂为有机磺酸化合物，包括甲磺酸、乙磺酸、1-丙磺酸、对甲苯磺酸和对氯苯磺酸；所述助催化剂为所述有机磺酸化合物中的一种或多种。
[援引加入(细则20.6) 17.10.2017]　
优选地，主催化剂为：水合氯化亚锡，助催化剂为对甲苯磺酸。
[援引加入(细则20.6) 17.10.2017]　
为进一步说明本发明，以下结合实施例对本发明提供PBAT-PLA共聚酯的共聚合成方法进行详细的说明。
[援引加入(细则20.6) 17.10.2017]　
实施例一
[援引加入(细则20.6) 17.10.2017]　
a.在反应釜中投入己二酸146g、对苯二甲酸二甲酯194g、1，4-丁二醇216g，通氮气保护，加热到140度，待反应釜中物料完全熔融后，加入钛酸四丁酯0.556g。抽真空至0.06Mpa,反应2h;之后在lh内梯度升温至230°C，真空度控制在1000Pa，继续反应5h;之后出料得到预聚物ΡΒΑΤ,重均分子量为60000;
[援引加入(细则20.6) 17.10.2017]　
b.在反应釜中投入L-乳酸90g，通氮气保护，加热到110°C，并逐步将真空度控制在0.08Mpa,搅拌反应4h;之后加入二水氯化亚锡9mg和对苯二甲酸6.6mg，在2h内梯度升温至160°C，抽真空至1000Pa，继续反应5h;之后出料得到预聚物PLA，重均分子量为50000;
[援引加入(细则20.6) 17.10.2017]　
c.将步骤a中的PBAT预聚物和步骤b中的PLA预聚物共混均匀后投入高真空反应釜中，抽真空至100Pa，加热至100°C反应0.5h后，将反应物在2h内梯度升温至145°C，继续反应5h，得到最终产物PBAT-PLA，颜色雪白。如图1所示曲线A，计算得到本实施例制备的PBAT-PLA共聚酯重均分子量为100000。PBAT预聚物和PLA预聚物的摩尔比为:1：10。
[援引加入(细则20.6) 17.10.2017]　
实施例二：
[援引加入(细则20.6) 17.10.2017]　
a.在反应釜中投入己二酸146g、对苯二甲酸二甲酯97g、1,4-丁二醇135g，通氮气保护，加热到160°C，待反应釜中物料完全熔融后，加入钛酸四丁酯37.8mgo抽真空至0.02Mpa，反应2h;之后在2h内梯度升温至220°C，真空度控制在500Pa，继续反应4h;之后出料得到预聚物ΡΒΑΤ,重均分子量为90000;
[援引加入(细则20.6) 17.10.2017]　
b.在反应釜中投入L-乳酸90g，通氮气保护，加热到120°C，并逐步将真空度控制在0.02Mpa，搅拌反应2h;之后加入二水氯化亚锡180mg和对苯二甲酸132mg,在2h内梯度升温至175°C，抽真空至800Pa，继续反应4h;之后出料得到预聚物PLA，重均分子量为80000;
[援引加入(细则20.6) 17.10.2017]　
c.将步骤a中的PBAT预聚物和步骤b中的PLA预聚物共混均匀后投入高真空反应釜中，抽真空至5Pa，加热至110°C反应lh后，将反应物在lh内梯度升温至155°C，继续反应10h，得到最终产物PBAT-PLA，颜色雪白。如图1所示曲线B，计算得到本实施例制备的PBAT-PLA共聚酯重均分子量为250000。 PBAT预聚物和PLA预聚物的摩尔比为：10:1。
[援引加入(细则20.6) 17.10.2017]　
实施例三：
[援引加入(细则20.6) 17.10.2017]　
a.在反应釜中投入己二酸73g、对苯二甲酸二甲酯194g、1，4-丁二醇135g，通氮气保护，加热到150°C，待反应釜中物料完全熔融后，加入钛酸四丁酯2.01g0抽真空至0.04Mpa，反应2h;之后在lh内梯度升温至210°C，真空度控制在800Pa，继续反应lh;之后出料得到预聚物PBAT,重均分子量为40000。
[援引加入(细则20.6) 17.10.2017]　
b.在反应釜中投入L-乳酸90g,通氮气保护，加热到130°C，并逐步将真空度控制在0.06Mpa，搅拌反应lh;之后加入二水合氯化亚锡274mg和对苯二甲酸176mg,在2h内梯度升温至190°C，抽真空至500Pa，继续反应lh;之后出料得到预聚物PLA，重均分子量为30000;
[援引加入(细则20.6) 17.10.2017]　
c.将步骤a中的PBAT预聚物和步骤b中的PLA预聚物共混均匀后投入高真空反应釜中，抽真空至20Pa，加热至105°C反应lh后，将反应物在2h内梯度升温至150°C，继续反应6h，得到最终产物PBAT-PLA,颜色雪白。如图1所示曲线C，计算得到本实施例制备的PBAT-PLA共聚酯重均分子量为180000。PBAT预聚物和PLA预聚物的摩尔比为：5:5。
[援引加入(细则20.6) 17.10.2017]　
实施例四
[援引加入(细则20.6) 17.10.2017]　
步骤a和步骤b同实施例一，步骤a中催化剂A为氯化钛，步骤b中催化剂B为二乙基锌和甲磺酸。
[援引加入(细则20.6) 17.10.2017]　
c.将步骤a中的PBAT预聚物和步骤b中的PLA预聚物共混均匀后投入高真空反应釜中，抽真空至80Pa，加热至108°C反应0.5h后，将反应物在1.5h内梯度升温至145°C，继续反应10h，得到最终产物PBAT-PLA，颜色雪白。PBAT-PLA共聚酯重均分子量为200000。PBAT预聚物和PLA预聚物的摩尔比为：3:7。
[援引加入(细则20.6) 17.10.2017]　
实施例五
[援引加入(细则20.6) 17.10.2017]　
步骤a和步骤b同实施例二，步骤a中催化剂A为钛酸四异丙酯，步骤b中催化剂B为四苯基锡和对氯苯磺酸。
[援引加入(细则20.6) 17.10.2017]　
c.将步骤a中的PBAT预聚物和步骤b中的PLA预聚物共混均匀后投入高真空反应釜中，抽真空至40Pa，加热至110°C反应lh后，将反应物在1.5h内梯度升温至145°C，继续反应8h，得到最终产物PBAT-PLA,颜色雪白。PBAT-PLA共聚酯重均分子量为220000。PBAT预聚物和PLA预聚物的摩尔比为：4:6
[援引加入(细则20.6) 17.10.2017]　
实施例六
[援引加入(细则20.6) 17.10.2017]　
步骤a和步骤b同实施例三，步骤a中催化剂A为钛酸四丁酯和钛酸四异丙酯，步骤b中催化剂B为锌粉末和1-丙磺酸。
[援引加入(细则20.6) 17.10.2017]　
c.将步骤a中的PBAT预聚物和步骤b中的PLA预聚物共混均匀后投入高真空反应釜中，抽真空至60Pa，加热至11CTC反应lh后，将反应物在1.5h内梯度升温至155°C，继续反应10h，得到最终产物PBAT-PLA，颜色雪白。PBAT-PLA共聚酯重均分子量为150000。
[援引加入(细则20.6) 17.10.2017]　
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. [根据细则26改正17.10.2017]　
    一种PBAT-PLA共聚酯的共聚合成方法，其特征在于，包括以下步骤-将预聚物PBAT和预聚物PLA共混均匀后投入高真空反应釜中，真空度在5-100Pa，加热至100-110°C反应0.5-lh;之后在l_2h内梯度升温至145-155°C，继续反应5-10h,得到产物PBAT-PLA共聚酯，重均分子量为100000-250000。
  2. [根据细则26改正17.10.2017]　
    根据权利要求1所述的PBAT-PLA共聚酯的共聚合成方法，其特征在于，所述预聚物PBAT和所述预聚物PLA的重量比为1〜10:1〜10。
  3. [根据细则26改正17.10.2017]　
    根据权利要求1或2所述的PBAT-PLA共聚酯的共聚合成方法，其特征在于，所述预聚物PBAT由以下方法制备：在反应釜中投入己二酸、对苯二甲酸二甲酯和1，4-丁二醇，所述己二酸、对苯二甲酸二甲酯和1,4-丁二醇的摩尔比为1〜2：1〜2：2〜4；通氮气保护，加热到140-160Ό;待反应釜中物料完全熔融后，加入催化剂A;抽真空至0.02-0.06Mpa，反应l_2h;之后在1-2h内梯度升温至210_230°C，真空度控制在500-1000Pa，继续反应l_5h;之后出料得到预聚物PBAT。
  4. [根据细则26改正17.10.2017]　
    根据权利要求3所述的PBAT-PLA共聚酯的共聚合成方法，其特征在于，催化剂A的用量为反应物总量的0.01%-0.5%。
  5. [根据细则26改正17.10.2017]　
    根据权利要求4所述的PBAT-PLA共聚酯的共聚合成方法，其特征在于，所述催化剂A为钛系催化剂，所述钛系催化剂为钛酸四丁酯、钛酸四乙酯、钛酸四异丙酯、氯化钛、二氧化钛，所述催化剂A为所述钛系催化剂中的一种或多种。
  6. [根据细则26改正17.10.2017]　
    根据权利要求5所述的PBAT-PLA共聚酯的共聚合成方法，其特征在于，所述催化剂A为：钛酸四丁酯。
  7. [根据细则26改正17.10.2017]　
    根据权利要求1或2所述的PBAT-PLA共聚酯的共聚合成方法，其特征在于，所述预聚物PLA由以下方法制备：在反应釜中投入L-乳酸，氮气置换三次后加热到110-130°C,逐步将真空度控制在0.02-0.08Mpa，搅拌反应1-4h;之后加入复合催化剂B，在1-2h内梯度升温至160-190°C，抽真空至500_1000Pa，继续反应1-5h;之后出料得到预聚物聚乳酸。
  8. [根据细则26改正17.10.2017]　
    根据权利要求7所述的PBAT-PLA共聚酯的共聚合成方法，其特征在于，所述复合催化剂B中主催化剂的用量为反应物总量的0.01%-0.5%，复合催化剂B中助催化剂与主催化剂的摩尔比为：1:1。
  9. [根据细则26改正17.10.2017]　
    根据权利要求8所述的PBAT-PLA共聚酯的共聚合成方法，其特征在于，所述主催化剂为Sn基催化剂或Zn基催化剂，Sn基催化剂包括辛酸亚锡、二水氯化亚锡、氧化亚锡和氯化亚锡脱水物、四苯基锡，所述Zn基催化剂包括锌粉末、二乙基锌、辛酸锌、氧化锌和氯化锌；所述主催化剂为所述Sn基催化剂的一种或多种或为所述Zn基催化剂的一种或多种；所述助催化剂为有机磺酸化合物，包括甲磺酸、乙磺酸、1-丙磺酸、对甲苯磺酸和对氯苯磺酸；所述助催化剂为所述有机磺酸化合物中的一种或多种。
  10. [根据细则26改正17.10.2017]　
    根据权利要求9所述的PBAT-PLA共聚酯的共聚合成方法，其特征在于，所述主催化剂为：二水氯化亚锡，所述助催化剂为对甲苯磺酸。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10287735A (ja) * 1997-04-10 1998-10-27 Kanebo Ltd ポリ乳酸組成物およびその製造方法ならびに該組成物の成形品
CN102838734A (zh) * 2012-09-25 2012-12-26 中国科学院长春应用化学研究所 一种聚乳酸嵌段共聚物及其制备方法
WO2013073819A1 (ko) * 2011-11-18 2013-05-23 에스케이케미칼 주식회사 내충격성 및 내열성이 우수한 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드 및 이를 이용한 성형제품
CN103589124A (zh) * 2012-08-14 2014-02-19 上海杰事杰新材料(集团)股份有限公司 一种全生物降解pla/pbat复合薄膜及其制备方法
CN103788346A (zh) * 2012-10-29 2014-05-14 中国石油化工股份有限公司 生物可降解聚酯及其制备方法
KR20140075468A (ko) * 2012-12-11 2014-06-19 삼성정밀화학 주식회사 생분해성 수지 조성물 및 생분해성 포장재
CN105440267A (zh) * 2014-08-29 2016-03-30 中国科学院长春应用化学研究所 一种脂肪族-芳香族-聚乳酸无规共聚物及其制备方法
CN105524262A (zh) * 2016-01-12 2016-04-27 中国科学院长春应用化学研究所 一种聚（对苯二甲酸己二酸丁二醇）酯及其聚乳酸嵌段共聚物的制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199279B (zh) * 2010-03-26 2014-01-22 东丽纤维研究所（中国）有限公司 利用复合催化剂制备聚乳酸与聚乙二醇共聚物的方法
CN103819884A (zh) * 2012-11-16 2014-05-28 上海载和实业投资有限公司 新型耐热高韧聚乳酸复合材料及其制备方法
CN105778449A (zh) * 2016-04-26 2016-07-20 常州大学 一种聚乳酸/聚(对苯二甲酸丁二醇-co-己二酸丁二醇)酯的相容剂及制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10287735A (ja) * 1997-04-10 1998-10-27 Kanebo Ltd ポリ乳酸組成物およびその製造方法ならびに該組成物の成形品
WO2013073819A1 (ko) * 2011-11-18 2013-05-23 에스케이케미칼 주식회사 내충격성 및 내열성이 우수한 폴리유산 수지 및 공중합 폴리에스테르 수지 블렌드 및 이를 이용한 성형제품
CN103589124A (zh) * 2012-08-14 2014-02-19 上海杰事杰新材料(集团)股份有限公司 一种全生物降解pla/pbat复合薄膜及其制备方法
CN102838734A (zh) * 2012-09-25 2012-12-26 中国科学院长春应用化学研究所 一种聚乳酸嵌段共聚物及其制备方法
CN103788346A (zh) * 2012-10-29 2014-05-14 中国石油化工股份有限公司 生物可降解聚酯及其制备方法
KR20140075468A (ko) * 2012-12-11 2014-06-19 삼성정밀화학 주식회사 생분해성 수지 조성물 및 생분해성 포장재
CN105440267A (zh) * 2014-08-29 2016-03-30 中国科学院长春应用化学研究所 一种脂肪族-芳香族-聚乳酸无规共聚物及其制备方法
CN105524262A (zh) * 2016-01-12 2016-04-27 中国科学院长春应用化学研究所 一种聚（对苯二甲酸己二酸丁二醇）酯及其聚乳酸嵌段共聚物的制备方法

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