WO2020228260A1 - 医用共聚酯及其制备方法 - Google Patents

医用共聚酯及其制备方法 Download PDF

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WO2020228260A1
WO2020228260A1 PCT/CN2019/115507 CN2019115507W WO2020228260A1 WO 2020228260 A1 WO2020228260 A1 WO 2020228260A1 CN 2019115507 W CN2019115507 W CN 2019115507W WO 2020228260 A1 WO2020228260 A1 WO 2020228260A1
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medical
copolyester
preparation
hydroxyethyl
terephthalic acid
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PCT/CN2019/115507
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English (en)
French (fr)
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沈志森
裘世杰
吴益栋
邓红霞
崔翔
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宁波市医疗中心李惠利医院
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Publication of WO2020228260A1 publication Critical patent/WO2020228260A1/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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6856—Dicarboxylic acids and dihydroxy compounds

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  • the invention relates to the technical field of materials, in particular to a medical copolyester and a preparation method thereof.
  • the polymer material is mainly polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • Tg glass transition temperature
  • the sterilization temperature of medical utensils such as square plates and trays made of PET is low, generally 50°C ⁇ 60°C, which cannot be steamed. Or boiling water disinfection, resulting in low disinfection efficiency and poor disinfection effect of medical utensils.
  • the medical copolyester is combined with terephthalic acid or its ester compound and triphenyldiether tetracarboxylic diimide-bisN -Hydroxyethyl, 1,3-propanediol and 1,4-cyclohexanedimethanol are obtained by melt polycondensation.
  • the preparation method is simple and has excellent heat resistance. The sterilization temperature of medical utensils made of it can reach 100°C and Above, the disinfection effect is good and the efficiency is high.
  • a preparation method of medical copolyester includes the following steps:
  • the first intermediate product is subjected to a polycondensation reaction to obtain a medical copolyester.
  • step (1) the molar ratio of the terephthalic acid or its ester to the triphenyldiether tetracarboxylic diimide-bis-N-hydroxyethyl is 1:( 0.1 ⁇ 0.3).
  • step (1) the sum of the molar amount of the 1,3-propanediol and the 1,4-cyclohexanedimethanol and the molar amount of the terephthalic acid or its ester The ratio is (1.2 ⁇ 2.0):1.
  • step (1) the molar ratio of the 1,4-cyclohexanedimethanol to the terephthalic acid or its esterified compound is (0.14-0.5):1.
  • step (1) the temperature of the esterification reaction is 160°C to 200°C, and the time is 2 hours to 6 hours.
  • the esterification catalyst includes at least one of anhydrous zinc acetate and tetrabutyl titanate.
  • step (2) the polycondensation reaction is carried out in a vacuum environment, the temperature is 270°C to 300°C, and the time is 2 hours to 6 hours.
  • the vacuum degree of the vacuum environment is not higher than 200Pa.
  • a polycondensation catalyst is also added, and the polycondensation catalyst includes antimony trioxide, isobutyl titanate, tetrabutyl titanate, antimony acetate, and dibutyl tin oxide. At least one of them.
  • a medical copolyester obtained by the above-mentioned preparation method, and the structural formula of the medical copolyester is shown in the following formula (2):
  • x, y, and z are all integers of 2-20, and n is an integer of 20-200.
  • the present invention adopts rigid triphenyldiether tetracarboxylic diimide-bis-N-hydroxyethyl and dimethyl terephthalate, 1,3-propanediol, 1,4-cyclohexanedimethanol melt polycondensation to obtain high
  • the molecular weight medical copolyester has a simple preparation method, can be controlled well, is easy to implement, and is suitable for large-scale industrial production.
  • the medical copolyester has a rigid imide structure, which can effectively increase the glass transition temperature of the medical copolyester, so that the medical copolyester not only has excellent mechanical properties such as strength, modulus, and toughness. , Also has excellent high temperature resistance.
  • medical utensils such as square plates, trays and the like prepared by using the medical copolyester can be sterilized by steam or boiling water, and the sterilization temperature can reach 100° C. and above, which effectively improves the sterilization effect and sterilization efficiency.
  • Figure 1 is a DSC chart of the medical copolyester of Example 1.
  • the medical copolyester provided by the present invention and its preparation method will be further described below.
  • the invention provides a medical copolyester and a preparation method thereof, which are mainly used to replace polyethylene terephthalate to prepare square plates, trays and other medical utensils, so that the medical utensils can realize high-temperature rapid disinfection and boiling water retorting and disinfection, and improve Disinfection effect and disinfection efficiency.
  • the preparation method of medical copolyester provided by the present invention mainly includes the following steps:
  • the first intermediate product is subjected to a polycondensation reaction to obtain a medical copolyester.
  • the structure of triphenyldiether tetracarboxylic diimide-bisN-hydroxyethyl has a rigid imide structure, which is combined with terephthalic acid or its esters and 1,3-propanediol Melt polycondensation can effectively increase the glass transition temperature of the obtained medical copolyester.
  • the obtained medical copolyester begins to become brittle.
  • 1,4-cyclohexane Dimethanol uses the conformational transformation of the cyclohexane unit in the structure of 1,4-cyclohexane dimethanol to improve the toughness of the obtained medical copolyester.
  • 1,4-cyclohexanedimethanol has better rigidity than 1,3-propanediol. Therefore, adding a small amount of 1,4-cyclohexanedimethanol can also interact with triphenyldiether tetracarboxylic diimide.
  • -Double N-hydroxyethyl has a synergistic effect to further increase the glass transition temperature of the medical copolyester. Therefore, the finally obtained medical copolyester not only has excellent mechanical properties such as strength, modulus, and toughness, but also has excellent high temperature resistance.
  • 1,3-propanediol was selected as the diol reaction monomer is that 1,3-propanediol has good devolatilization performance under high temperature and high vacuum, so it can ensure the polycondensation reaction during polycondensation. It went smoothly, and a high molecular weight medical copolyester was prepared.
  • the esterification products of terephthalic acid include dimethyl terephthalate and the like. Considering the better reactivity of dimethyl terephthalate, dimethyl terephthalate is preferably used.
  • step (1) terephthalic acid or its esters, triphenyldiether tetracarboxylic diimide-bis-N-hydroxyethyl, 1,3-propanediol and 1,4-cyclohexanedimethanol
  • the molar ratio of the four raw materials is very important and directly determines whether the medical copolyester can be prepared and the properties of the obtained medical copolyester.
  • the molar ratio of the terephthalic acid or its ester compound to the triphenyldiether tetracarboxylic diimide-bis-N-hydroxyethyl is 1:(0.1 ⁇ 0.3), preferably 1:(0.12 ⁇ 0.25).
  • the molar ratio of the sum of the molar amounts of the 1,3-propanediol and the 1,4-cyclohexanedimethanol to the terephthalic acid or its ester compound is (1.2-2.0):1.
  • the molar ratio of the 1,4-cyclohexanedimethanol to the terephthalic acid or its ester is (0.14 ⁇ 0.5):1, preferably (0.15 to 0.4):1.
  • the esterification catalyst includes at least one of anhydrous zinc acetate and tetrabutyl titanate.
  • the amount of the esterification catalyst is 0.05% to 0.5% of the molar amount of the terephthalic acid or its esterified compound, preferably 0.15% to 0.2%.
  • the temperature of the esterification reaction is 160°C to 200°C, and the time is 2 hours to 6 hours.
  • step (2) the polycondensation reaction is carried out in a vacuum environment, the temperature is 270°C to 300°C, preferably 270°C to 290°C, and the time is 2 hours to 6 hours, preferably 3.5 hours to 5 hours.
  • the vacuum degree of the vacuum environment is not higher than 100 Pa.
  • the polycondensation reaction further includes adding a polycondensation catalyst to the first intermediate product, and the polycondensation catalyst includes antimony trioxide, isobutyl titanate, tetrabutyl titanate, antimony acetate, At least one of dibutyltin oxide.
  • the amount of the polycondensation reaction catalyst is 0.05% to 0.5% of the molar amount of the terephthalic acid or its ester compound, preferably 0.15% to 0.2%.
  • the esterification catalyst when the esterification catalyst is tetrabutyl titanate, the esterification catalyst can also be used as a polycondensation reaction catalyst. At this time, the first intermediate product can be directly subjected to the polycondensation reaction of step (2). However, after the esterification reaction, the esterification catalyst will partially fail. Therefore, when the esterification catalyst and the polycondensation reaction catalyst are the same, a part of the polycondensation reaction catalyst may be added to the first intermediate product before the polycondensation reaction in step (2).
  • a stabilizer or antioxidant or a mixture of stabilizer and antioxidant is also added.
  • the amount of the stabilizer is 0.01% to 0.5%, preferably 0.15% to 0.2% of the molar amount of the terephthalic acid or its ester, and the amount of the antioxidant is the p-benzene
  • the molar amount of dicarboxylic acid or its ester is 0.05% to 0.5%, preferably 0.1% to 0.15%.
  • the stabilizer can reduce the oxidative cleavage of ester bonds, aliphatic chains and carbon-carbon bonds under oxygen and prevent thermal decomposition.
  • the stabilizer includes phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite At least one of ester, ammonium phosphite, and ammonium dihydrogen phosphate.
  • Antioxidants can capture oxygen free radicals and eliminate trace amounts of oxygen, thereby reducing the occurrence of thermal decomposition reactions and oxidation side reactions.
  • the antioxidant includes at least one of antioxidant-1010, antioxidant-1076, and antioxidant-168.
  • the present invention uses rigid triphenyldiether tetracarboxylic diimide-bis-N-hydroxyethyl and dimethyl terephthalate, 1,3-propanediol, 1,4-cyclohexanedimethanol melt polycondensation
  • the high molecular weight medical copolyester is obtained, the preparation method is simple, can be controlled well, is easy to implement, and is suitable for large-scale industrial production.
  • the present invention also provides a medical copolyester obtained by the above preparation method, and the structural formula of the medical copolyester is shown in the following formula (2):
  • x, y, and z are all integers of 2-20, and n is an integer of 20-200.
  • the medical copolyester has a rigid imide structure, which can effectively increase the glass transition temperature of the medical copolyester, so that the glass transition temperature of the medical copolyester reaches 100°C to 120°C. Therefore, the medical copolyester not only has excellent mechanical properties such as strength, modulus, and toughness, but also has excellent high temperature resistance. Therefore, medical utensils such as square plates and trays prepared by using the medical copolyester can be sterilized by steam or boiling water, and the sterilization temperature can reach 100°C to 120°C, which can effectively improve the sterilization effect and sterilization efficiency.
  • the molecular weights of all polymers are tested by Agilent PL-GPC220, and the columns are two PLgel 5 ⁇ m Mixed-D 300*7.5mm in series.
  • the mobile phase is chloroform
  • the test temperature is 40°C
  • the sample concentration is 1mg/mL
  • the flow rate is 1mL/min
  • the standard sample is PS(3070 -258000g/mol).
  • the thermal analysis was performed using differential scanning calorimetry (Mettler Toledo DSC) at a heating rate of 10°C/min in a N 2 atmosphere, and the temperature range was 25°C to 300°C.
  • the relative number average molecular mass of the medical copolyester is 28000 g/moL, and the relative weight average molecular mass is 51200 g/moL.
  • the relative number average molecular weight of the medical copolyester is 27000g/moL, and the relative weight average molecular weight is 49200g/moL.
  • 1H-NMR confirmed that the triphenyl ether tetracarboxylic diimide-bisN-hydroxyethyl
  • the molar ratio of the structural unit to the terephthalic acid structural unit 1.5:100, the glass transition temperature is 108°C, the tensile strength is 65MPa, and the tensile modulus is 1770MPa.
  • the relative number average molecular weight of the medical copolyester is 31000g/moL, and the relative weight average molecular weight is 48200g/moL.
  • 1 H-NMR confirms that the triphenyl ether tetracarboxylic diimide-bisN-hydroxyethyl
  • the molar ratio of the structural unit of the base to the structural unit of terephthalic acid 20:100, the glass transition temperature is 112°C, the tensile strength is 68MPa, and the tensile modulus is 1820MPa.
  • the relative number average molecular weight of the medical copolyester is 18700g/moL, and the relative weight average molecular weight is 32100g/moL.
  • 1 H-NMR confirmed that the triphenyl ether tetracarboxylic diimide-bisN-hydroxyethyl
  • the molar ratio of the structural unit of the base to the structural unit of terephthalic acid is 24:100, the glass transition temperature is 116°C, the tensile strength is 72 MPa, and the tensile modulus is 1850 MPa.
  • the relative number average molecular weight of the medical copolyester is 16900g/moL, and the relative weight average molecular weight is 29800g/moL.
  • 1 H-NMR determined that the triphenyl ether tetracarboxylic diimide-bisN-hydroxyethyl
  • the molar ratio of the structural unit of the base to the structural unit of terephthalic acid is 27:100, the glass transition temperature is 119°C, the tensile strength is 73 MPa, and the tensile modulus is 1910 MPa.
  • the relative number average molecular weight of the copolyester is 25500g/moL
  • the relative weight average molecular weight is 43700g/moL
  • the glass transition temperature is 72°C
  • the tensile strength is 55MPa
  • the tensile modulus is 1650MPa.
  • Comparative Example 1 From the comparative analysis of Comparative Example 1 and Examples 1 to 5, it can be seen that in Comparative Example 1, since triphenyldiether tetracarboxylic diimide-bis-N-hydroxyethyl is not added, there is no imide in the obtained copolyester. Amine structure, low glass transition temperature.
  • the relative number average molecular mass of the copolyester is 28000 g/moL, and the relative weight average molecular mass is 51200 g/moL.
  • 1 H-NMR determined that the molar ratio of the structural unit of triphenyldiether tetracarboxylic diimide-bis-N-hydroxyethyl to the structural unit of terephthalic acid was 10:100, and the glass transition temperature was 98°C.
  • the tensile strength of the copolyester is 45 MPa, and the tensile modulus is 1420 MPa.

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Abstract

本申请涉及医用共聚酯及其制备方法，所述医用共聚酯的制备方法包括以下步骤：(1)将对苯二甲酸或其酯化物、三苯二醚四甲酸二酰亚胺-双N-羟乙基、1,3-丙二醇、1,4-环己烷二甲醇和酯化催化剂混合，并进行酯化反应，得到第一中间产物，其中，所述三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构式如下式(1)所示; (2)将所述第一中间产物进行缩聚反应，得到医用共聚酯。

Description

医用共聚酯及其制备方法
相关申请
本申请要求2019年5月15日申请的，申请号为201910400789.2，名称为“医用共聚酯及其制备方法”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本发明涉及材料技术领域，特别是涉及一种医用共聚酯及其制备方法。
背景技术
目前，方盘、托盘等医用器皿大多采用金属和高分子材料制成。其中，高分子材料主要为聚对苯二甲酸乙二酯(PET)。但是，PET的玻璃化转变温度(Tg)约为67℃～81℃，所以，采用PET制成的方盘、托盘等医用器皿的消毒温度低，一般为50℃～60℃，无法进行水蒸气或沸水消毒，从而导致医用器皿的消毒效率低和消毒效果差。
发明内容
基于此，有必要针对上述问题，提供一种医用共聚酯及其制备方法；所述医用共聚酯通过对苯二甲酸或其酯化物与三苯二醚四甲酸二酰亚胺-双N-羟乙基，1,3-丙二醇和1,4-环己烷二甲醇熔融缩聚得到，制备方法简单，具有优异的耐热性，用其制成的医用器皿的消毒温度可以达到100℃及以上，消毒效果好，效率高。
一种医用共聚酯的制备方法，包括以下步骤：
(1)将对苯二甲酸或其酯化物、三苯二醚四甲酸二酰亚胺-双N-羟乙基、1,3-丙二醇、1,4-环己烷二甲醇和酯化催化剂混合，并进行酯化反应，得到第一中间产物，其中，所述三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构式如下式(1)所示：
Figure PCTCN2019115507-appb-000001
(2)将所述第一中间产物进行缩聚反应，得到医用共聚酯。
在其中一个实施例中，步骤(1)中，所述对苯二甲酸或其酯化物与所述三苯二醚四甲酸二酰亚胺-双N-羟乙基的摩尔比为1:(0.1～0.3)。
在其中一个实施例中，步骤(1)中，所述1,3-丙二醇和所述1,4-环己烷二甲醇的摩尔量之和与所述对苯二甲酸或其酯化物的摩尔比为(1.2～2.0):1。
在其中一个实施例中，步骤(1)中，所述1,4-环己烷二甲醇与所述对苯二甲酸或其酯化物的摩尔比为(0.14～0.5):1。
在其中一个实施例中，步骤(1)中，所述酯化反应的温度为160℃～200℃，时间为2小时～6小时。
在其中一个实施例中，步骤(1)中，所述酯化催化剂包括无水乙酸锌、钛酸四丁酯中的至少一种。
在其中一个实施例中，步骤(2)中，所述缩聚反应于真空环境下进行，温度为270℃～300℃，时间为2小时～6小时。
在其中一个实施例中，所述真空环境的真空度不高于200Pa。
在其中一个实施例中，步骤(2)中，还加入缩聚反应催化剂，所述缩聚反应催化剂包括三氧化二锑、钛酸异丁酯、钛酸四丁酯、乙酸锑、二丁基氧化锡中的至少一种。
一种医用共聚酯，如上述所述制备方法得到，所述医用共聚酯的结构式如下式(2)所示：
Figure PCTCN2019115507-appb-000002
其中，x、y、z均为2～20的整数，n为20～200的整数。
本发明采用刚性的三苯二醚四甲酸二酰亚胺-双N-羟乙基与对苯二甲酸二甲酯、1,3-丙二醇、1,4-环己烷二甲醇熔融缩聚得到高分子量的医用共聚酯，制备方法简单，可控制好，易于实施，适合大规模工业化生产。而且，该医用共聚酯中具有刚性的酰亚胺结构，可以有效的提高该医用共聚酯的玻璃化转变温度，使得该医用共聚酯不仅具有优异的强度、模量、韧性等力学性能，还具有优异的耐高温性。从而，采用该医用共聚酯制备的方盘、托盘等医用器皿可以进行水蒸气或沸水消毒，消毒温度可以达到100℃及以上，有效提高了消毒效果和消毒效率。
附图说明
图1是实施例1的医用共聚酯的DSC图谱。
具体实施方式
以下将对本发明提供的医用共聚酯及其制备方法作进一步说明。
本发明提供一种医用共聚酯及其制备方法，主要用于替代聚对苯二甲酸乙二醇酯制备方盘、托盘等医用器皿，使医用器皿可以实现高温快速消毒和开水蒸煮消毒，提高消毒效果和消毒效率。
本发明提供的医用共聚酯的制备方法，主要包括以下步骤：
(1)将对苯二甲酸或其酯化物、三苯二醚四甲酸二酰亚胺-双N-羟乙基、1,3-丙二醇、1,4-环己烷二甲醇和酯化催化剂混合，并进行酯化反应，得到第一中间产物，其中，所述三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构式如下式(1)所示：
Figure PCTCN2019115507-appb-000003
(2)将所述第一中间产物进行缩聚反应，得到医用共聚酯。
本发明的制备方法中，三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构中具有刚性的酰亚胺结构，与对苯二甲酸或其酯化物和1,3-丙二醇熔融缩聚，可以有效提高所获得的医用共聚酯的玻璃化转变温度。但是，随着三苯二醚四甲酸二酰亚胺-双N-羟乙基的用量的增加，所获得的医用共聚酯开始变脆，因此，本发明还加入1,4-环己烷二甲醇，利用1,4-环己烷二甲醇的结构中的环己烷单元船椅构象转变，提高所获得的医用共聚酯的韧性。而且，1,4-环己烷二甲醇具有比1,3-丙二醇更好的刚性，所以，添加少量的1,4-环己烷二甲醇还可与三苯二醚四甲酸二酰亚胺-双N-羟乙基起到协同作用，进一步提高医用共聚酯的玻璃化转变温度。从而，使最终获得的医用共聚酯不仅具有优异的强度、模量、韧性等力学性能，还具有优异的耐高温性。
另外，之所以选择1,3-丙二醇作为二元醇反应单体，是因为1,3-丙二醇在高温和高真空度下具有较好的脱挥性能，所以，在缩聚时可确保缩聚反应的顺利进行，从而制备得到高分子量的医用共聚酯。
而所述对苯二甲酸的酯化物中，包括对苯二甲酸二甲酯等。考虑到对苯二甲酸二甲酯的反应活性较好，优选采用对苯二甲酸二甲酯。
所以，步骤(1)中，对苯二甲酸或其酯化物、三苯二醚四甲酸二酰亚胺-双 N-羟乙基、1,3-丙二醇和1,4-环己烷二甲醇四种原料的摩尔比至关重要，直接决定是否能够制备得到医用共聚酯以及所获得的医用共聚酯的性能。
其中，三苯二醚四甲酸二酰亚胺-双N-羟乙基含量太低时，医用共聚酯的玻璃化转变温度提高较少，而三苯二醚四甲酸二酰亚胺-双N-羟乙基含量太高时，缩聚时无法获得高分子量的医用共聚酯，医用共聚酯的分子量低，韧性差。所以，所述对苯二甲酸或其酯化物与所述三苯二醚四甲酸二酰亚胺-双N-羟乙基的摩尔比为1:(0.1～0.3)，优选为1:(0.12～0.25)。
所述1,3-丙二醇和所述1,4-环己烷二甲醇的摩尔量之和与所述对苯二甲酸或其酯化物的摩尔比为(1.2～2.0):1。其中，为了更好的提高医用共聚酯的玻璃化转变温度以及韧性的改善，所述1,4-环己烷二甲醇与所述对苯二甲酸或其酯化物的摩尔比为(0.14～0.5):1，优选为(0.15～0.4):1。
另外，步骤(1)中，所述酯化催化剂包括无水乙酸锌、钛酸四丁酯中的至少一种。优选的，所述酯化催化剂的用量为所述对苯二甲酸或其酯化物的摩尔量的0.05％～0.5％，优选为0.15％～0.2％。所述酯化反应的温度为160℃～200℃，时间为2小时～6小时。
步骤(2)中，所述缩聚反应于真空环境下进行，温度为270℃～300℃，优选为270℃～290℃，时间为2小时～6小时，优选为3.5小时～5小时。优选的，所述真空环境的真空度不高于100Pa。
具体的，在进行缩聚反应时，还包括向所述第一中间产物中添加缩聚反应催化剂，所述缩聚反应催化剂包括三氧化二锑、钛酸异丁酯、钛酸四丁酯、乙酸锑、二丁基氧化锡中的至少一种。优选的，所述缩聚反应催化剂的用量为所述对苯二甲酸或其酯化物的摩尔量的0.05％～0.5％，优选为0.15％～0.2％。
可以理解，当酯化催化剂为钛酸四丁酯时，酯化催化剂也可用作缩聚反 应催化剂。此时，可直接将第一中间产物进行步骤(2)的缩聚反应。但考虑到酯化反应后，酯化催化剂会部分失效。因此，在酯化催化剂和缩聚反应催化剂相同的情况下，可在进行步骤(2)的缩聚反应之前，向第一中间产物中补加部分缩聚反应催化剂即可。
具体的，在进行缩聚反应时，还加入稳定剂或抗氧剂，或者稳定剂和抗氧剂的混合物。优选的，所述稳定剂的用量为所述对苯二甲酸或其酯化物的摩尔量的0.01％～0.5％，优选为0.15％～0.2％，所述抗氧剂的用量为所述对苯二甲酸或其酯化物的摩尔量的0.05％～0.5％，优选为0.1％～0.15％。
其中，稳定剂可以减少酯键、脂肪链和碳碳键等在氧气下产生氧化断裂，防止热分解的发生。所述稳定剂包括磷酸、亚磷酸、次亚磷酸、焦磷酸、磷酸铵、磷酸三甲酯、磷酸二甲酯、磷酸三苯酯、磷酸二苯酯、亚磷酸三苯酯、亚磷酸二苯酯、亚磷酸铵、磷酸二氢铵中至少一种。
抗氧剂可以捕捉氧自由基，消除微量的氧气，从而减少热分解反应和氧化副反应的发生。所述抗氧剂包括抗氧剂-1010、抗氧剂-1076、抗氧剂-168中至少一种。
因此，本发明采用刚性的三苯二醚四甲酸二酰亚胺-双N-羟乙基与对苯二甲酸二甲酯、1,3-丙二醇、1,4-环己烷二甲醇熔融缩聚得到高分子量的医用共聚酯，制备方法简单，可控制好，易于实施，适合大规模工业化生产。
本发明还提供一种如上述制备方法得到的医用共聚酯，所述医用共聚酯的结构式如下式(2)所示：
Figure PCTCN2019115507-appb-000004
其中，x、y、z均为2～20的整数，n为20～200的整数。
该医用共聚酯中具有刚性的酰亚胺结构，可以有效的提高医用共聚酯的玻璃化转变温度，使医用共聚酯的玻璃化转变温度达到100℃～120℃。所以，使得该医用共聚酯不仅具有优异的强度、模量、韧性等力学性能，还具有优异的耐高温性。从而，采用该医用共聚酯制备的方盘、托盘等医用器皿可以进行水蒸气或沸水消毒，消毒温度可以达到100℃～120℃，可有效提高消毒效果和消毒效率。
以下，将通过以下具体实施例对所述医用共聚酯及其制备方法做进一步的说明。
实施例中，核磁共振氢谱 1H-NMR采用Bruker 400 AVANCE Ⅲ Spectrometer型仪器上测定，400MHz，CF 3COOD。
实施例中，所有聚合物的分子量采用Agilent PL-GPC220测试，柱子为两根PLgel 5μm Mixed-D 300*7.5mm串联。流动相为氯仿，测试温度为40℃，样品溶解溶剂为邻氯苯酚:氯仿＝1:1(v/v)，样品浓度为1mg/mL，流动速率为1mL/min，标样为PS(3070-258000g/mol)。
实施例中，热分析使用差示扫描量热(Mettler Toledo DSC)以10℃/min的升温速率，在N 2气氛进行，温度范围为25℃～300℃。
实施例1：
将对苯二甲酸二甲酯97.0g、三苯二醚四甲酸二酰亚胺-双N-羟乙基24.4g，1,3-丙二醇57.0g和1,4-环己烷二甲醇21.6g加入到聚合反应器，然后加入基于对苯二甲酸二甲酯的摩尔量的0.15％的无水乙酸锌。在惰性气氛下，180℃，反应4h，得到第一中间产物。
向第一中间产物中加入基于对苯二甲酸二甲酯的摩尔量的0.2％的三氧化二锑，0.15％的磷酸三苯酯和0.1％的抗氧剂1010，真空度逐渐降低到100Pa以 下，逐步升温到270℃，反应3.5h，得到医用共聚酯。
经检测，该医用共聚酯的相对数均分子质量为28000g/moL，相对重均分子质量为51200g/moL。 1H-NMR确定三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构单元与对苯二甲酸结构单元的摩尔比＝10:100，该医用共聚酯的DSC曲线如图1所示，玻璃化转变温度为104℃。该医用共聚酯的拉伸强度为60MPa，拉伸模量为1680MPa。
实施例2：
将对苯二甲酸二甲酯97.0g、三苯二醚四甲酸二酰亚胺-双N-羟乙基36.6g，1,3-丙二醇55.1g和1,4-环己烷二甲醇21.6g加入到聚合反应器，然后加入基于对苯二甲酸二甲酯的摩尔量的0.20％的钛酸四丁酯。在惰性气氛下，190℃，反应4h，得到第一中间产物。
向第一中间产物中加入基于对苯二甲酸二甲酯的摩尔量0.20％的磷酸三苯酯和0.1％的抗氧剂1010，真空度逐渐降低到80Pa以下，逐步升温到280℃，反应4.0h得到医用共聚酯。
经检测，该医用共聚酯的相对数均分子质量为27000g/moL，相对重均分子质量为49200g/moL，1H-NMR确定三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构单元与对苯二甲酸结构单元的摩尔比＝1.5:100，玻璃化转变温度为108℃，拉伸强度为65MPa，拉伸模量为1770MPa。
实施例3：
将对苯二甲酸二甲酯97.0g、三苯二醚四甲酸二酰亚胺-双N-羟乙基48.8g，1,3-丙二醇53.2g和1,4-环己烷二甲醇21.6g加入到聚合反应器，然后加入基于对苯二甲酸二甲酯的摩尔量的0.15％的无水乙酸锌。在惰性气氛下，200℃，反应2h，得到第一中间产物。
向第一中间产物中加入基于对苯二甲酸二甲酯的摩尔量的0.15％的三氧化二锑，0.20％的磷酸三苯酯和0.15％的抗氧剂1010，真空度逐渐降低到100Pa以下，逐步升温到285℃，反应5.0h得到医用共聚酯。
经检测，该医用共聚酯的相对数均分子质量为31000g/moL，相对重均分子质量为48200g/moL， 1H-NMR确定三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构单元与对苯二甲酸结构单元的摩尔比＝20:100，玻璃化转变温度为112℃，拉伸强度为68MPa，拉伸模量为1820MPa。
实施例4：
将对苯二甲酸二甲酯97.0g、三苯二醚四甲酸二酰亚胺-双N-羟乙基61g，1,3-丙二醇49.0g和1,4-环己烷二甲醇36.6g加入到聚合反应器，然后加入基于对苯二甲酸二甲酯的摩尔量的0.15％的无水乙酸锌。在惰性气氛下，160℃，反应4h，得到第一中间产物。
向第一中间产物中加入基于对苯二甲酸二甲酯的摩尔量的0.15％的钛酸四丁酯，0.20％的磷酸三乙酯和0.1％的抗氧剂176，真空度逐渐降低到60Pa以下，逐步升温到290℃，反应4.0h得到医用共聚酯。
经检测，该医用共聚酯的相对数均分子质量为18700g/moL，相对重均分子质量为32100g/moL， 1H-NMR确定三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构单元与对苯二甲酸结构单元的摩尔比＝24:100，玻璃化转变温度为116℃，拉伸强度为72MPa，拉伸模量为1850MPa。
实施例5：
将对苯二甲酸二甲酯97.0g、三苯二醚四甲酸二酰亚胺-双N-羟乙基68.3g，1,3-丙二醇,45.6g和1,4-环己烷二甲醇42.3g加入到聚合反应器，然后加入基于对苯二甲酸二甲酯的摩尔量的0.15％的无水乙酸锌。在惰性气氛下， 200℃，反应6h，得到第一中间产物。
向第一中间产物中加入基于对苯二甲酸二甲酯的摩尔量的0.15％的1,3-丙二醇锑，0.20％的磷酸三苯酯和0.1％的抗氧剂176，真空度逐渐降低到60Pa以下，逐步升温到295℃，反应4.0h得到医用共聚酯。
经检测，该医用共聚酯的相对数均分子质量为16900g/moL，相对重均分子质量为29800g/moL， 1H-NMR确定三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构单元与对苯二甲酸结构单元的摩尔比＝27:100，玻璃化转变温度为119℃，拉伸强度为73MPa，拉伸模量为1910MPa。
对比例1：
将对苯二甲酸二甲酯97.0g，1,3-丙二醇48g和1,4-环己烷二甲醇21.6g加入到聚合反应器，然后加入基于对苯二甲酸二甲酯的摩尔量的0.15％的无水乙酸锌。在惰性气氛下，180℃，反应4h，得到第一中间产物。
向第一中间产物中加入基于对苯二甲酸二甲酯的摩尔量的0.15％的三氧化二锑，0.20％的磷酸三苯酯和0.1％的抗氧剂1010，真空度逐渐降低到60Pa以下，逐步升温到285℃，反应4.0h得到共聚酯。
经检测，该共聚酯的相对数均分子质量为25500g/moL，相对重均分子质量为43700g/moL，玻璃化转变温度为72℃，拉伸强度为55MPa，拉伸模量为1650MPa。
由对比例1与实施例1～5对比分析可知，对比例1中由于没有加入三苯二醚四甲酸二酰亚胺-双N-羟乙基，因此，获得的共聚酯中没有酰亚胺结构，玻璃化转变温度低。
对比例2：
将对苯二甲酸二甲酯97.0g、三苯二醚四甲酸二酰亚胺-双N-羟乙基24.4g， 1,3-丙二醇57.0g加入到聚合反应器，然后加入基于对苯二甲酸二甲酯的摩尔量的0.15％的无水乙酸锌。在惰性气氛下，180℃，反应4h，得到第一中间产物。
向第一中间产物中加入基于对苯二甲酸二甲酯的摩尔量的0.2％的三氧化二锑，0.15％的磷酸三苯酯和0.1％的抗氧剂1010，真空度逐渐降低到100Pa以下，逐步升温到270℃，反应3.5h，得到共聚酯。
经检测，该共聚酯的相对数均分子质量为28000g/moL，相对重均分子质量为51200g/moL。 1H-NMR确定三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构单元与对苯二甲酸结构单元的摩尔比＝10:100，玻璃化转变温度为98℃。该共聚酯的拉伸强度为45MPa，拉伸模量为1420MPa。
由对比例2与实施例1～5对比分析可知，对比例2中由于没有加入1,4-环己烷二甲醇，其获得的共聚酯的玻璃化转变温度也低于实施例1～5获得的共聚酯的玻璃化转变温度。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种医用共聚酯的制备方法，其特征在于，包括以下步骤：
    (1)将对苯二甲酸或其酯化物、三苯二醚四甲酸二酰亚胺-双N-羟乙基、1,3-丙二醇、1,4-环己烷二甲醇和酯化催化剂混合，并进行酯化反应，得到第一中间产物，其中，所述三苯二醚四甲酸二酰亚胺-双N-羟乙基的结构式如下式(1)所示：
    Figure PCTCN2019115507-appb-100001
    (2)将所述第一中间产物进行缩聚反应，得到医用共聚酯。
  2. 根据权利要求1所述的医用共聚酯的制备方法，其特征在于，步骤(1)中，所述对苯二甲酸或其酯化物与所述三苯二醚四甲酸二酰亚胺-双N-羟乙基的摩尔比为1:(0.1～0.3)。
  3. 根据权利要求1所述的医用共聚酯的制备方法，其特征在于，步骤(1)中，所述1,3-丙二醇和所述1,4-环己烷二甲醇的摩尔量之和与所述对苯二甲酸或其酯化物的摩尔比为(1.2～2.0):1。
  4. 根据权利要求3所述的医用共聚酯的制备方法，其特征在于，步骤(1)中，所述1,4-环己烷二甲醇与所述对苯二甲酸或其酯化物的摩尔比为(0.14～0.5):1。
  5. 根据权利要求1所述的医用共聚酯的制备方法，其特征在于，步骤(1)中，所述酯化反应的温度为160℃～200℃，时间为2小时～6小时。
  6. 根据权利要求1所述的医用共聚酯的制备方法，其特征在于，步骤(1)中，所述酯化催化剂包括无水乙酸锌、钛酸四丁酯中的至少一种。
  7. 根据权利要求1所述的医用共聚酯的制备方法，其特征在于，步骤(2)中，所述缩聚反应于真空环境下进行，温度为270℃～300℃，时间为2小时～6 小时。
  8. 根据权利要求7所述的医用共聚酯的制备方法，其特征在于，所述真空环境的真空度不高于200Pa。
  9. 根据权利要求1所述的医用共聚酯的制备方法，其特征在于，步骤(2)中，还加入缩聚反应催化剂，所述缩聚反应催化剂包括三氧化二锑、钛酸异丁酯、钛酸四丁酯、乙酸锑、二丁基氧化锡中的至少一种。
  10. 一种医用共聚酯，其特征在于，如权利要求1～9任一项所述制备方法得到，所述医用共聚酯的结构式如下式(2)所示：
    Figure PCTCN2019115507-appb-100002
    其中，x、y、z均为2～20的整数，n为20～200的整数。
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