WO2024036583A1 - 热塑性聚酯及其制备方法与应用 - Google Patents

热塑性聚酯及其制备方法与应用 Download PDF

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WO2024036583A1
WO2024036583A1 PCT/CN2022/113458 CN2022113458W WO2024036583A1 WO 2024036583 A1 WO2024036583 A1 WO 2024036583A1 CN 2022113458 W CN2022113458 W CN 2022113458W WO 2024036583 A1 WO2024036583 A1 WO 2024036583A1
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thermoplastic polyester
polyester according
glycol
catalyst
temperature
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French (fr)
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陈立
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Shenzhen Smoore Technology Ltd
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Shenzhen Smoore Technology Ltd
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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
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from 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
    • C08G63/02—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

Definitions

  • the invention relates to the field of polymer materials, and in particular to a thermoplastic polyester and its preparation method and application.
  • Thermoplastic polyester materials usually refer to linear polyester materials obtained through esterification and polycondensation processes using dibasic acids and glycols.
  • Common thermoplastic polyesters include polyethylene terephthalate resin (PET) and poly(p-ethylene glycol).
  • PET polyethylene terephthalate resin
  • PBT Butylene phthalate
  • PET polyethylene terephthalate resin
  • PBT Butylene phthalate
  • traditional thermoplastic polyester has the following problems: (1) The material is semi-crystalline, and during the injection molding process, the existence of crystallization effect results in low transparency of the injection molded parts; (2) The material has low heat resistance and does not function well at high temperatures. At 70°C, the parts are easily deformed by heat, making it difficult to meet the application requirements of food containers or structural parts.
  • PETG polyethylene terephthalate-1,4-cyclohexane dimethanol
  • PC Bisphenol A-based polycarbonate
  • BPA bisphenol A
  • the American company Eastman has developed a highly sterically hindered glycol monomer: 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO), and a combination of CBDO and 1,4-cyclobutanediol.
  • a copolyester material prepared by co-condensation of hexane dimethanol (CHDM) and dimethyl terephthalate.
  • CHDM hexane dimethanol
  • the copolyester material has high transparency, with a visible light transmittance greater than 90%; good heat resistance, with a glass transition temperature higher than 100°C; high toughness, good chemical resistance, and does not contain or release BPA.
  • CBDO monomer is only produced by a very small number of chemical companies, and it is difficult to control the processing process.
  • Eastman has the capability of mass production and processing.
  • thermoplastic polyester which thermoplastic polyester has high transparency, high heat resistance, high toughness and high molecular weight at the same time.
  • thermoplastic polyester prepared from raw materials through esterification reaction and cocondensation polymerization reaction
  • the raw materials include diols and dicarboxylic acids
  • the glycol is a mixture of tricyclodecane dimethanol and other aliphatic glycols.
  • the other aliphatic glycol is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, n-butanediol, n-pentyl glycol, neopentyl glycol, 1, One or more of 3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol.
  • the molar percentage of the tricyclodecanedimethanol is about 5% to about 60%, and the molar percentage of the other aliphatic glycols is about 40% to about 95%.
  • the dicarboxylic acid is selected from one or more of terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid and furandicarboxylic acid.
  • the molar ratio of the diol to the dicarboxylic acid is about 1.05:1 to about 2:1.
  • thermoplastic polyester includes one or more of structural unit A and structural unit B;
  • the structural unit A is a structural unit of the structural unit A.
  • the structural unit B is
  • thermoplastic polyester meets one or more of the following conditions:
  • the intrinsic viscosity is about 0.5dL/g to about 0.9dL/g;
  • the glass transition temperature is about 90°C to about 150°C.
  • thermoplastic polyester as described above in catering containers, kitchen appliances, optical base films or electronic cigarette oil storage devices.
  • thermoplastic polyester as described above, including the following steps:
  • the ester, the phosphorus stabilizer and the second catalyst are mixed to perform a copolycondensation reaction.
  • the conditions for the esterification reaction include: a temperature of about 160°C to about 265°C, a pressure of about 1 to about 3 atmospheres, and a time of about 120 min to about 300 min.
  • the cocondensation polymerization reaction conditions include: a temperature of about 250°C to about 300°C, and a time of about 90 min to about 300 min.
  • the second catalyst is selected from one or more of titanium-containing compounds, aluminum-containing compounds, tin-containing compounds and germanium-containing compounds.
  • first and second are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as “first” and “second” may explicitly or implicitly include at least one of these features.
  • plurality means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.
  • everal means at least one, such as one, two, etc., unless otherwise expressly and specifically limited.
  • compositions and methods/processes of the present application comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein. No distinction is made herein between the terms “efficacy”, “performance”, “effect” and “efficacy”.
  • thermoplastic polyester which is prepared from raw materials through esterification reaction and co-condensation polymerization reaction
  • Raw materials include diols and dicarboxylic acids
  • the glycol is a mixture of tricyclodecane dimethanol and other aliphatic glycols.
  • Tricyclodecane dimethanol (TCD-DM) is a special alicyclic diol. It is synthesized by hydroformylation of dicyclopentadiene to synthesize tricyclodecane dimethanol, which is further catalytically hydrogenated to synthesize tricyclodecane dimethanol. Cyclodecanedimethanol (TCD-DM) has now achieved industrial mass production. Due to the lower raw material cost of dicyclopentadiene, the monomer cost of TCD-DM has potential advantages.
  • tricyclodecanedimethanol is compounded with another aliphatic diol as the mixed diol raw material in the copolyester, so that the mixed diol has the characteristics of greater rigidity and spatial non-planar structure, and is consistent with
  • the copolyester can have excellent visible light transmittance and improve the transparency of thermoplastic polyester; at the same time, the mixture of tricyclodecanedimethanol and aliphatic diol can further improve the transparency of the thermoplastic polyester.
  • the heat resistance of thermoplastic polyester is reflected in the significant increase in the glass transition temperature and heat deformation temperature of thermoplastic polyester.
  • the heat deformation temperature of the thermoplastic polyester provided in this application can reach 80°C to 110°C, and the conformation of the alicyclic ring The transformation in turn provides the copolyester with better toughness.
  • the mixed glycol compounded with tricyclodecanedimethanol and aliphatic glycol has high reactivity and can reduce steric hindrance to a certain extent, thereby effectively promoting its ester with dicarboxylic acid.
  • Chemicalization or transesterification reaction can further obtain high molecular weight thermoplastic polyester, and finally realize the thermoplastic polyester to achieve the properties of high molecular weight, high toughness, high heat resistance and high transparency.
  • thermoplastic polyester of the present application also has a cost advantage.
  • the other aliphatic glycol is selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, n-butanediol, n-pentyl glycol, neopentyl glycol, 1,3-propanediol, One or more of cyclohexanedimethanol and 1,4-cyclohexanedimethanol.
  • Dihydric alcohols containing aliphatic cyclic structures are special dihydroxy compounds.
  • the unique cyclic structure can improve the heat resistance, weather resistance, hardness and other properties of polymer materials. They are odorless and have low toxicity.
  • 1,4-cyclohexanedimethanol is an alicyclic diol containing a six-membered ring and an important monomer for the synthesis of various high-performance polyester materials such as PCT, PETG, and PCTG.
  • the molar percentage of tricyclodecanedimethanol ranges from about 5% to about 60%, and the molar percentage of other aliphatic glycols ranges from about 40% to about 95%.
  • the dicarboxylic acid is selected from one or more of terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid and furandicarboxylic acid.
  • the molar ratio of glycol to dicarboxylic acid is about 1.05:1 to about 2:1.
  • the molar ratio of glycol to dicarboxylic acid includes but is not limited to 1.05:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6: 1. 1.7:1, 1.8:1, 1.9:1, 2:1.
  • thermoplastic polyester includes one or more of structural unit A and structural unit B;
  • Structural unit B is
  • the thermoplastic polyester has an intrinsic viscosity of about 0.5 dL/g to about 0.9 dL/g.
  • thermoplastic polyester includes but is not limited to 0.5dL/g, 0.6dL/g, 0.7dL/g, 0.8dL/g, and 0.9dL/g.
  • thermoplastic polyester has a glass transition temperature of about 90°C to about 150°C.
  • the glass transition temperature (Tg) of the thermoplastic polyester resin of the present application can be adjusted within a wide range. By increasing the TCDDM chain link content, a copolyester with a higher Tg can be produced, and by adjusting the proportion of glycol , adjust mechanical properties and heat resistance.
  • the thermoplastic polyester resin of the present application has a glass transition temperature similar to or higher than traditional copolyesters (>100°C), and also has higher Young's modulus, tensile strength, impact toughness, and mechanical properties. Better performance.
  • thermoplastic polyester in catering containers, kitchen appliances, optical base films or electronic cigarette oil storage devices.
  • catering containers include but are not limited to baby bottles and water cups; kitchen appliances include but are not limited to mixing cups and juicers.
  • thermoplastic polyester This application also provides a method for preparing the above-mentioned thermoplastic polyester, which includes the following steps:
  • thermoplastic polyester in another embodiment, includes the following steps:
  • the raw materials are mixed with the first catalyst to cause an esterification reaction between at least one hydroxyl group in the diol and at least one carboxyl group in the dicarboxylic acid to prepare an ester.
  • thermoplastic polyester in another embodiment, includes the following steps:
  • the ester, the phosphorus stabilizer and the second catalyst are mixed to cause at least one hydroxyl group in the ester and at least one carboxyl group in the ester to undergo a cocondensation reaction.
  • the conditions for the esterification reaction include: a temperature of about 160°C to about 265°C, a pressure of about 1 to about 3 atmospheres, and a time of about 120 min to about 300 min.
  • the cocondensation polymerization reaction conditions include: a temperature of about 250°C to about 300°C, and a time of about 90 min to about 300 min.
  • the cocondensation polymerization reaction is performed under reduced pressure.
  • the vacuum degree of the cocondensation polymerization reaction is gradually reduced to about 20 Pa to about 100 Pa.
  • the first catalyst is selected from dibutyltin oxide.
  • the second catalyst is selected from one or more of titanium-containing oxides, aluminum-containing oxides, tin-containing oxides and germanium-containing oxides.
  • the second catalyst is selected from one or more of antimony trioxide, dibutyltin oxide, n-butyl titanate, and isopropyl titanate.
  • the phosphorus stabilizer is selected from one or more of trimethyl phosphate, triphenyl phosphate, triethyl phosphite, trilauryl phosphite, and triisoctyl phosphite.
  • thermoplastic polyester in another embodiment, includes the following steps:
  • the ester and phosphorus stabilizers with the catalyst, and perform a cocondensation polymerization reaction at a temperature of 250°C to 300°C, a time of 90min to 240min, and reduced pressure; where the catalyst is selected from titanium-containing compounds, aluminum-containing compounds, and compounds containing One or more of tin compounds and germanium-containing compounds.
  • thermoplastic polyester in another embodiment, includes the following steps:
  • thermoplastic polyester of the present application and its preparation method will be further described in detail below with reference to specific examples.
  • the raw materials used in the following examples are all commercially available products unless otherwise specified.
  • IV intrinsic viscosity
  • Thermal properties The DSC equipment of the American TA Company was used to measure the glass transition temperature of the sample, using a temperature program of primary heating-cooling-second heating. The test temperature range was room temperature to 250°C, and the temperature rising and cooling rate was 10°C/min. Isothermal time 3min;
  • Tensile properties An injection molding machine was used to prepare dumbbell-shaped specimens with a width of 4 mm and a thickness of 2 mm, and were measured after being placed at room temperature for 1 week. According to the ASTM D638 standard, a universal material testing machine was used to conduct tensile testing at 25°C and a tensile rate of 10mm/min. Test 5 specimens for each sample, and take the average value as the test result.
  • thermoplastic polyester specifically as follows:
  • the copolyester has an intrinsic viscosity of 0.78dL/g and a glass transition temperature of 106°C. Cutting off at 700nm, the visible light transmittance is 91%, the tensile strength is 55MPa, and the elongation at break is >200%.
  • thermoplastic polyester specifically as follows:
  • transesterification product is polycondensed for 2 hours under the conditions of 260 ⁇ 270°C and absolute pressure ⁇ 200Pa to obtain copolyester material.
  • the copolyester has an intrinsic viscosity of 0.63dL/g and a glass transition temperature of 115°C. Cutting off at 700nm, the visible light transmittance is 90%, the tensile strength is 62MPa, and the elongation at break is 110%.
  • thermoplastic polyester specifically as follows:
  • terephthalic acid, 1,4-cyclohexanedimethanol, ethylene glycol, and tricyclodecanedimethanol into the reactor in a molar ratio of 1:0.4:0.8:0.2, and then add terephthalic acid in a molar amount of 1 ⁇ of dibutyltin oxide, under nitrogen protection conditions, gradually raise the temperature to 185°C for esterification, react for 3 hours, and then add terephthalic acid molar amount of 0.6 ⁇ of catalyst antimony trioxide and 1.0 ⁇ of stabilizer triphosphate.
  • Phenyl ester gradually raise the temperature to 270°C, gradually reduce the vacuum degree to 30Pa, and react for 3.0 hours to obtain copolyester.
  • the copolyester has an intrinsic viscosity of 0.72dL/g, a glass transition temperature of 120°C, a cutoff of 700nm, a visible light transmittance of 89%, and a spline elongation at break of 140%.
  • thermoplastic polyester specifically as follows:
  • Terephthalic acid, ethylene glycol, and tricyclodecanedimethanol were added into the reactor at a molar ratio of 1:0.8:0.5, and then dibutyltin oxide with a molar amount of terephthalic acid of 1 ⁇ was added, and the mixture was heated under nitrogen protection conditions. , gradually raise the temperature to 185°C for esterification, react for 3 hours, then add the catalyst antimony trioxide with a molar amount of 0.6 ⁇ of terephthalic acid, and the stabilizer triphenyl phosphate of 1.0 ⁇ , gradually raise the temperature to 270°C, and gradually increase the vacuum degree. Lowered to 30Pa, reacted for 3.0h, and obtained copolyester.
  • the copolyester has an intrinsic viscosity of 0.66dL/g, a glass transition temperature of 102°C, a cutoff of 700nm, a visible light transmittance of 89%, and a spline elongation at break of 60%.
  • thermoplastic polyester specifically as follows:
  • transesterification product is polycondensed for 2 hours under the conditions of 260 ⁇ 270°C and absolute pressure ⁇ 200Pa to obtain copolyester material.
  • the copolyester has an intrinsic viscosity of 0.65dL/g and a glass transition temperature of 120°C. Cutting off at 700nm, the visible light transmittance is 90%, the tensile strength is 48MPa, and the elongation at break is 80%.
  • thermoplastic polyester specifically as follows:
  • transesterification product is polycondensed for 2 hours under the conditions of 260 ⁇ 270°C and absolute pressure ⁇ 200Pa to obtain copolyester material.
  • the copolyester has an intrinsic viscosity of 0.63dL/g and a glass transition temperature of 120°C. Cutting off at 700nm, the visible light transmittance is 86%, the tensile strength is 44MPa, and the elongation at break is 10%.
  • thermoplastic polyester specifically as follows:
  • transesterification product is polycondensed for 2 hours under the conditions of 260 ⁇ 270°C and absolute pressure ⁇ 200Pa to obtain copolyester material.
  • the copolyester has an intrinsic viscosity of 0.68dL/g and a glass transition temperature of 84°C. Cutting off at 700nm, the visible light transmittance is 89%, the tensile strength is 42MPa, and the elongation at break is 100%.

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  • Health & Medical Sciences (AREA)
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Abstract

一种热塑性聚酯及其制备方法和应用。热塑性聚酯由二元醇与二元羧酸经酯化反应与共缩聚反应制备得到，所述二元醇为三环癸二甲醇与其它脂肪族二元醇的混合物。该热塑性聚酯兼具高分子量、高韧性、高耐热性和高透明性的性能且原料成本低。

Description

热塑性聚酯及其制备方法与应用 技术领域
本发明涉及高分子材料领域，特别是涉及一种热塑性聚酯及其制备方法与应用。
背景技术
热塑性聚酯材料通常指的是以二元酸和二元醇通过酯化和缩聚工艺获得的线性聚酯材料，常见的热塑性聚酯包括聚对苯二甲酸乙二醇树脂(PET)和聚对苯二甲酸丁二醇酯(PBT)，产量大，用途广，多用作高性能薄膜和纤维。但传统的热塑性聚酯存在如下问题：(1)材料具有半结晶性，在注塑加工过程中，结晶效应的存在导致注塑制件透明度较低；(2)材料的耐热性低，在温度高于70℃时制件易受热变形，从而难以满足食品容器或结构件的应用要求。
传统技术公开了一种聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(PETG)共聚酯及其制备方法，虽然对透明度进行了改性，然而PETG材料的耐热性低，玻璃化温度通常在80℃左右，当使用温度接近70℃时，其结构容易发生热变形，从而限制了其在需要耐高温领域的应用。
还有传统技术公开了一种利用第三单体1,4-环己烷二甲醇(CHDM)、对苯二甲酸(TPA)与异山梨醇(ISB)进行共聚的制备方法，可以获得耐热透明的共聚酯材料，但是异山梨醇的反应活性较低，分子量提升困难，高温易发生副反应，导致最终制备得到的共聚酯材料颜色容易发黄、材料韧性不足且加工性能较差。
基于双酚A的聚碳酸酯(PC)是一种常见的高透明且耐热好的聚合物材料，且具有优异的透明性、尺寸稳定性、耐热性与韧性，但是其在高温时会释放双酚A(BPA)，被禁止用于奶瓶等食品接触产品，同时PC材料的耐化性也比较差，限 制了其应用。
美国伊斯曼公司研制出一种高位阻二元醇单体：2,2,4,4-四甲基-1,3-环丁二醇(CBDO)，以及由CBDO与1,4-环己烷二甲醇(CHDM)、对苯二甲酸二甲酯共缩聚制备而成的共聚酯材料。该共聚酯材料的透明度高，可见光透过率大于90％；耐热好，玻璃化转变温度高于100℃；韧性高，耐化性好，并且不包含也不释放BPA，作为安全的、高透明且耐高温的聚合物材料，在婴儿奶瓶、水杯、厨电产品、电子烟油仓材料等领域中获得了广泛的应用。但是，CBDO单体仅由极少数化工公司生产，加工过程工艺控制难度大，目前仅伊士曼具备量产加工的能力。
发明内容
根据本申请的各种实施例，提供了一种热塑性聚酯，所述热塑性聚酯同时具有高透明性、高耐热性、高韧性与高分子量。
本申请通过如下技术方案实现。
一种热塑性聚酯，以原料经酯化反应与共缩聚反应制备得到；
所述原料包括二元醇与二元羧酸；
所述二元醇为三环癸二甲醇与其它脂肪族二元醇的混合物。
在其中一个实施例中，所述其它脂肪族二元醇选自乙二醇、1,2-丙二醇、1,3-丙二醇、正丁二醇、正戊二醇、新戊二醇、1,3-环己烷二甲醇与1,4-环己烷二甲醇中的一种或多种。
在其中一个实施例中，所述二元醇中，所述三环癸二甲醇的摩尔百分数为约5％至约60％，所述其它脂肪族二元醇的摩尔百分数为约40％至约95％。
在其中一个实施例中，所述二元羧酸选自对苯二甲酸、2,6-萘二甲酸、间苯二甲酸与呋喃二甲酸中的一种或多种。
在其中一个实施例中，所述二元醇与所述二元羧酸的摩尔比为约1.05:1至 约2:1。
在其中一个实施例中，所述热塑性聚酯包括结构单元A与结构单元B中的一种或多种；
所述结构单元A为
Figure PCTCN2022113458-appb-000001
所述结构单元B为
Figure PCTCN2022113458-appb-000002
在其中一个实施例中，所述热塑性聚酯满足如下条件中的一个或多个：
(1)特性粘度为约0.5dL/g至约0.9dL/g；
(2)玻璃化转变温度为约90℃至约150℃。
本申请还提供一种如上所述的热塑性聚酯在餐饮容器、厨房电器、光学基膜或电子烟油仓装置中的应用。
本申请还提供一种如上所述的热塑性聚酯的制备方法，包括如下步骤：
将所述原料与第一催化剂混合，进行酯化反应，制备酯；
将所述酯、磷类稳定剂与第二催化剂混合，进行共缩聚反应。
在其中一个实施例中，酯化反应的条件包括：温度为约160℃至约265℃，压力为约1至约3个大气压，时间为约120min至约300min。
在其中一个实施例中，共缩聚反应的条件包括：温度为约250℃至约300℃，时间为约90min至约300min。
在其中一个实施例中，所述第二催化剂选自含钛化合物、含铝化合物、含锡化合物与含锗化合物中的一种或多种。
本申请的一个或多个实施例的细节在下面的附图和描述中提出。本申请的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
具体实施方式
为了便于理解本申请，下面将参照相关实施例对本申请进行更全面的描述。实施例中给出了本申请的较佳实施方式。但是，本申请可以以许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本申请的公开内容的理解更加透彻全面。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在申请的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。在本申请的描述中，“若干”的含义是至少一个，例如一个，两个等，除非另有明确具体的限定。
当本文中公开一个数值范围时，上述范围视为连续，且包括该范围的最小值及最大值，以及这种最小值与最大值之间的每一个值。进一步地，当范围是指整数时，包括该范围的最小值与最大值之间的每一个整数。此外，当提供多个范围描述特征或特性时，可以合并该范围。换言之，除非另有指明，否则本文中所公开之所有范围应理解为包括其中所归入的任何及所有的子范围。
除非另外指明，所有百分比、分数和比率都是按本申请组合物的总质量计算的。除非另外指明，有关所列成分的所有质量均给予活性物质的含量，因此它们不包括在可商购获得的材料中可能包含的溶剂或副产物。本文术语“质量百分比含量”可用符号“％”表示。除非另外指明，在本文中所有的分子量都是以道 尔顿为单位表示的重均分子量。除非另外指明，在本文中所有配制和测试发生在25℃的环境。本文中“包括”、“包含”、“含”、“含有”、“具有”或其它变体意在涵盖非封闭式包括，这些术语之间不作区分。术语“包含”是指可加入不影响最终结果的其它步骤和成分。本申请的组合物和方法/工艺包含、由其组成和基本上由本文描述的必要元素和限制项以及本文描述的任一的附加的或任选的成分、组份、步骤或限制项组成。本文中术语“效能”、“性能”、“效果”、“功效”之间不作区分。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本申请。
本申请提供了一种热塑性聚酯，以原料经酯化反应与共缩聚反应制备得到；
原料包括二元醇与二元羧酸；
二元醇为三环癸二甲醇与其它脂肪族二元醇的混合物。
三环癸烷二甲醇(TCD-DM)是一种特殊脂环族二元醇，其合成方式为由双环戊二烯经氢甲酰化合成三环癸烷二甲醛，进一步催化加氢合成三环癸烷二甲醇(TCD-DM)，当前已实现工业量产。由于双环戊二烯较低的原料成本，TCD-DM的单体成本具有潜在的优势。
本申请将三环癸二甲醇与另一种脂肪族二元醇复配作为共聚酯中的混合二元醇原料，使混合二元醇具有较大的刚性和空间非平面结构的特点，与二元羧酸经酯化反应与缩聚反应后可以使共聚酯具有优异的可见光透过率，提升热塑性聚酯的透明度；同时，三环癸二甲醇与脂肪族二元醇混合后能进一步提升热塑性聚酯的耐热性，体现在热塑性聚酯的玻璃化转变温度与热变形温度均明显提高，本申请提供的热塑性聚酯的热变形温度可达80℃～110℃，并且脂环的构 象转变又为共聚酯提供了更好的韧性。此外，三环癸二甲醇与脂肪族二元醇复配后的混合二元醇具有高反应活性，并一定程度上能够减小空间位阻，从而可以高效地促进其与二元羧酸的酯化或酯交换反应，进一步地能够得到高分子量的热塑性聚酯，最终实现热塑性聚酯达到高分子量、高韧性、高耐热性和高透明性的性能兼顾。
进一步地，三环癸二甲醇已实现工业量产，其合成原料双环戊二烯成本较低，因此本申请的热塑性聚酯还具有成本上的优势。
在其中一个实施例中，其它脂肪族二元醇选自乙二醇、1,2-丙二醇、1,3-丙二醇、正丁二醇、正戊二醇、新戊二醇、1,3-环己烷二甲醇与1,4-环己烷二甲醇中的一种或多种。
含脂肪族环状结构的二元醇是特殊的二羟基化合物，独特的环状结构可以改善高分子材料的耐热、耐候、硬度等性能，并且无气味、毒性小。其中，1,4-环己烷二甲醇是一种含有六元环的脂环族二醇，是合成PCT、PETG、PCTG等多种高性能聚酯材料的重要单体。但是传统以1,4-环己烷二甲醇作为二元醇制备得到的共聚酯分子量提升困难，高温易发生副反应，导致最终制备得到的共聚酯材料颜色容易发黄、材料韧性不足且加工性能较差。
在其中一个实施例中，二元醇中，三环癸二甲醇的摩尔百分数为约5％至约60％，其它脂肪族二元醇的摩尔百分数为约40％至约95％。
在其中一个实施例中，二元羧酸选自对苯二甲酸、2,6-萘二甲酸、间苯二甲酸与呋喃二甲酸中的一种或多种。
在其中一个实施例中，二元醇与二元羧酸的摩尔比为约1.05:1至约2:1。
可以理解地，在本申请中，二元醇与二元羧酸的摩尔比包括但不限于1.05:1、1.1:1、1.2:1、1.3:1、1.4:1、1.5:1、1.6:1、1.7:1、1.8:1、1.9:1、2:1。
在其中一个实施例中，热塑性聚酯包括结构单元A与结构单元B中的一种或多种；
结构单元A为
Figure PCTCN2022113458-appb-000003
结构单元B为
Figure PCTCN2022113458-appb-000004
在其中一个实施例中，热塑性聚酯的特性粘度为约0.5dL/g至约0.9dL/g。
可以理解地，在本申请中，热塑性聚酯的特性粘度包括但不限于0.5dL/g、0.6dL/g、0.7dL/g、0.8dL/g、0.9dL/g。
在其中一个实施例中，热塑性聚酯的玻璃化转变温度为约90℃至约150℃。
本申请的热塑性聚酯树脂的玻璃化温度(Tg)可在很宽的范围内进行调节，可通过提高TCDDM链节含量，制得更高Tg的共聚酯，可通过调节二元醇的比例，调节力学性能和耐热性能。并且本申请的热塑性聚酯树脂相较于传统的共聚酯的玻璃化温度相近或更高(＞100℃)的同时，还具有更高的杨氏模量、拉伸强度与冲击韧性，力学性能更佳。
本申请还提供一种上述热塑性聚酯在餐饮容器、厨房电器、光学基膜或电子烟油仓装置中的应用。
可以理解地，在本申请中，餐饮容器包括但不限于婴儿奶瓶与水杯；厨房电器包括但不限于搅拌杯与果汁机。
本申请还提供一种上述热塑性聚酯的制备方法，包括如下步骤：
将原料与第一催化剂混合，进行酯化反应，制备酯；
将酯、磷类稳定剂与第二催化剂混合，进行共缩聚反应。
在另一个实施例中，上述热塑性聚酯的制备方法，包括如下步骤：
将原料与第一催化剂混合，使二元醇中的至少一个羟基与二元羧酸中的至少一个羧基进行酯化反应，制备酯。
在另一个实施例中，上述热塑性聚酯的制备方法，包括如下步骤：
将酯、磷类稳定剂与第二催化剂混合，使酯中的至少一个羟基与酯中的至少一个羧基进行共缩聚反应。
在其中一个实施例中，酯化反应的条件包括：温度为约160℃至约265℃，压力为约1至约3个大气压，时间为约120min至约300min。
在其中一个实施例中，共缩聚反应的条件包括：温度为约250℃至约300℃，时间为约90min至约300min。
在其中一个实施例中，共缩聚反应在减压条件下进行。
在另一个实施例中，共缩聚反应真空度逐步降至约20Pa至约100Pa。
在其中一个实施例中，第一催化剂选自氧化二丁基锡。
在其中一个实施例中，第二催化剂选自含钛氧化物、含铝氧化物、含锡氧化物与含锗氧化物中的一种或多种。
在另一个实施例中，第二催化剂选自三氧化二锑、氧化二丁基锡、钛酸正丁酯与钛酸异丙酯中的一种或多种。
在其中一个实施例中，磷类稳定剂选自磷酸三甲酯、磷酸三苯酯、亚磷酸三乙酯、亚磷酸三月桂醇酯与亚磷酸三异辛酯中的一种或多种。
在另一个实施例中，上述热塑性聚酯的制备方法，包括如下步骤：
将原料混合，在温度为160℃～265℃，压力为1至3个大气压，时间为120min～300min的条件下进行酯化反应，制备酯；
将酯、磷类稳定剂与催化剂混合，在温度为250℃～300℃，时间为90min～240min，减压的条件下进行共缩聚反应；其中，催化剂选自含钛化合物、含铝化合物、含锡化合物与含锗化合物中的一种或多种。
在另一个实施例中，上述热塑性聚酯的制备方法，包括如下步骤：
在反应器中，将混合二元醇与二元羧酸以摩尔比为(1.05～2)：1的配比，将二元醇和二元羧酸组成的物料搅拌，在160℃～265℃反应温度及1到3个大气压的反应压力下，120min～240min后完成酯化反应；在浆料中加入、或酯化完成后或缩聚前加入磷类稳定剂；然后向反应器中加入第二催化剂，在温度为250℃～300℃，及减压条件下反应90min～240min，得到所述改性共聚酯。
以下结合具体实施例对本申请的热塑性聚酯及其制备方法做进一步详细的说明。以下实施例中所用的原料，如无特别说明，均为市售产品。
对实施例制备得到的共聚酯材料的特性粘度、玻璃化转变温度、拉伸性能与透明度进行测试，具体包括如下分析方法：
特性粘度：共聚酯样品的特性粘度(IV)采用杭州中旺自动黏度仪测定，测试温度为25℃，溶剂为苯酚/四氯乙烷(质量比w/w＝3/2)；
热性能：采用美国TA公司的DSC设备测定样品的玻璃化转变温度，采用一次升温-降温-二次升温的温度程序，测试温度范围为室温至250℃，升、降温速率为10℃/min，等温时间3min；
拉伸性能：采用注塑机制备宽4mm、厚2mm的哑铃型样条，室温下放置1周后测定。根据ASTM D638标准，采用万能材料试验机，在25℃和10mm/min的拉伸速率条件下进行拉伸测试。每个样品测试5个样条，取其平均值作为测试结果。
实施例1
本实施例提供一种热塑性聚酯的制备方法，具体如下：
将对苯二甲酸、三环癸二甲醇TCDDM、乙二醇、1,4-环己烷二甲醇按照摩尔1:0.20:0.6:0.3加入到反应器中，逐步升温至180℃进行酯化，反应3.0h，然后加入摩尔量0.8‰的缩聚催化剂三氧化二锑，1.0‰的稳定剂磷酸三甲酯，逐步升温至230℃，真空度逐步降到50Pa，反应3h，得到共聚酯材料。
本实施例的共聚酯材料物性测试结果如下所示：
该共聚酯的特性粘度为0.78dL/g，玻璃化转变温度为106℃。截止700nm，可见光透过率为91％，拉伸强度为55MPa，断裂伸长率＞200％。
实施例2
本实施例提供一种热塑性聚酯的制备方法，具体如下：
(1)向N 2氛围的反应器中加入对苯二甲酸2mol、三环癸二甲醇1mol，新戊二醇0.2mol和1,4-环己烷二甲醇0.5mol，乙二醇0.8mol，催化剂氧化二丁基锡0.40g，稳定剂磷酸三苯酯0.30g，混合均匀，并且然后用氮气加压至2.0kg/cm 2的压力，于200℃反应1h，210℃反应2h，得到酯交换产物；
(2)酯交换产物在260～270℃、绝对压力≤200Pa的条件下缩聚2h，得到共聚酯材料。
本实施例的共聚酯材料物性测试结果如下所示：
该共聚酯的特性粘度为0.63dL/g，玻璃化转变温度为115℃。截止700nm，可见光透过率为90％，拉伸强度为62MPa，断裂伸长率为110％。
实施例3
本实施例提供一种热塑性聚酯的制备方法，具体如下：
将对苯二甲酸、1,4-环己烷二甲醇、乙二醇、三环癸二甲醇按照摩尔比1:0.4:0.8:0.2加入到反应器中，然后加入对苯二甲酸摩尔量1‰的二丁基氧化锡，在氮气保护条件下，逐步升温至185℃进行酯化，反应3h，然后加入对苯二甲酸摩尔量0.6‰的催化剂三氧化二锑，1.0‰的稳定剂磷酸三苯酯，逐步升温至270℃，真空度逐步降到30Pa，反应3.0h，得到共聚酯。
对本实施例制备得到的共聚酯材料的特性粘度、玻璃化转变温度、拉伸性能与透明度进行测试，
该共聚酯的特性粘度为0.72dL/g，玻璃化转变温度为120℃，截止700nm，可见光透过率为89％，样条断裂伸长率为140％。
实施例4
本实施例提供一种热塑性聚酯的制备方法，具体如下：
将对苯二甲酸、乙二醇、三环癸二甲醇按照摩尔比1:0.8:0.5加入到反应器中，然后加入对苯二甲酸摩尔量1‰的二丁基氧化锡，在氮气保护条件下，逐步升温至185℃进行酯化，反应3h，然后加入对苯二甲酸摩尔量0.6‰的催化剂三氧化二锑，1.0‰的稳定剂磷酸三苯酯，逐步升温至270℃，真空度逐步降到30Pa，反应3.0h，得到共聚酯。
对本实施例制备得到的共聚酯材料的特性粘度、玻璃化转变温度、拉伸性能与透明度进行测试，
该共聚酯的特性粘度为0.66dL/g，玻璃化转变温度为102℃，截止700nm，可见光透过率为89％，样条断裂伸长率为60％。
实施例5
本实施例提供一种热塑性聚酯的制备方法，具体如下：
(1)向N 2氛围的反应器中加入呋喃二甲酸2mol、三环癸二甲醇1mol，1,4-环己烷二甲醇0.5mol，乙二醇0.8mol，催化剂氧化二丁基锡0.40g，稳定剂磷酸三苯酯0.30g，混合均匀，并且然后用氮气加压至2.0kg/cm 2的压力，于200℃反应1h，210℃反应2h，得到酯交换产物；
(2)酯交换产物在260～270℃、绝对压力≤200Pa的条件下缩聚2h，得到共聚酯材料。
本实施例的共聚酯材料物性测试结果如下所示：
该共聚酯的特性粘度为0.65dL/g，玻璃化转变温度为120℃。截止700nm，可见光透过率为90％，拉伸强度为48MPa，断裂伸长率为80％。
对比例1
本实施例提供一种热塑性聚酯的制备方法，具体如下：
(1)向反应器中加入对苯二甲酸2mol、三环癸二甲醇1mol，乙二醇0.8mol，催化剂氧化二丁基锡0.35g，稳定剂磷酸三苯酯0.25g，混合均匀，并且然后用氮气加压至2.0kg/cm 2的压力，于200℃反应1h，210℃反应2h，得到酯交换产物；
(2)酯交换产物在260～270℃、绝对压力≤200Pa的条件下缩聚2h，得到共聚酯材料。
本对比例的共聚酯材料物性测试结果如下所示：
该共聚酯的特性粘度为0.63dL/g，玻璃化转变温度为120℃。截止700nm，可见光透过率为86％，拉伸强度为44MPa，断裂伸长率为10％。
对比例2
本实施例提供一种热塑性聚酯的制备方法，具体如下：
(1)反应器中加入对苯二甲酸2mol、1,4-环己烷二甲醇1mol，乙二醇1.6mol，催化剂氧化二丁基锡0.40g，稳定剂磷酸三苯酯0.30g，混合均匀，并且然后用氮气加压至2.0kg/cm 2的压力，于200℃反应1h，210℃反应2h，得到酯交换产物；
(2)酯交换产物在260～270℃、绝对压力≤200Pa的条件下缩聚2h，得到共聚酯材料。
本对比例的共聚酯材料物性测试结果如下所示：
该共聚酯的特性粘度为0.68dL/g，玻璃化转变温度为84℃。截止700nm，可见光透过率为89％，拉伸强度为42MPa，断裂伸长率为100％。
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申请的几种实施方式，便于具体和详细地理解本申请的技术方案，但并不能因此而理解为对申请专利保护范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。应当理解，本领域技术人员在本申请提供的技术方案的基础上，通过合乎逻辑的分析、推理或者有限的试验得到的技术方案，均在本申请所附权利要求的保护范围内。因此，本申请专利的保护范围应以所附权利要求的内容为准，说明书可以用于解释权利要求的内容。

Claims (12)

  1. 一种热塑性聚酯，其特征在于，以原料经酯化反应与共缩聚反应制备得到；
    所述原料包括二元醇与二元羧酸；
    所述二元醇为三环癸二甲醇与其它脂肪族二元醇的混合物。
  2. 根据权利要求1所述的热塑性聚酯，其特征在于，所述其它脂肪族二元醇选自乙二醇、1,2-丙二醇、1,3-丙二醇、正丁二醇、正戊二醇、新戊二醇、1,3-环己烷二甲醇与1,4-环己烷二甲醇中的一种或多种。
  3. 根据权利要求1～2任一项所述的热塑性聚酯，其特征在于，所述二元醇中，所述三环癸二甲醇的摩尔百分数为约5％至约60％，所述其它脂肪族二元醇的摩尔百分数为约40％至约95％。
  4. 根据权利要求1～3任一项所述的热塑性聚酯，其特征在于，所述二元羧酸选自对苯二甲酸、2,6-萘二甲酸、间苯二甲酸与呋喃二甲酸中的一种或多种。
  5. 根据权利要求1～4任一项所述的热塑性聚酯，其特征在于，所述二元醇与所述二元羧酸的摩尔比为约1.05:1至约2:1。
  6. 根据权利要求1～5任一项所述的热塑性聚酯，其特征在于，所述热塑性聚酯包括结构单元A与结构单元B中的一种或多种；
    所述结构单元A为
    Figure PCTCN2022113458-appb-100001
    所述结构单元B为
    Figure PCTCN2022113458-appb-100002
  7. 根据权利要求1～6任一项所述的热塑性聚酯，其特征在于，所述热塑性聚 酯满足如下条件中的一个或多个：
    (1)特性粘度为约0.5dL/g至约0.9dL/g；
    (2)玻璃化转变温度为约90℃至约150℃。
  8. 权利要求1～7任一项所述的热塑性聚酯在餐饮容器、厨房电器、光学基膜或电子烟油仓装置中的应用。
  9. 一种权利要求1～7任一项所述的热塑性聚酯的制备方法，其特征在于，包括如下步骤：
    将所述原料与第一催化剂混合，进行酯化反应，制备酯；
    将所述酯、磷类稳定剂与第二催化剂混合，进行共缩聚反应。
  10. 根据权利要求9所述的热塑性聚酯的制备方法，其特征在于，酯化反应的条件包括：温度为约160℃至约265℃，压力为约1至约3个大气压，时间为约120min至约300min。
  11. 根据权利要求9～10任一项所述的热塑性聚酯的制备方法，其特征在于，共缩聚反应的条件包括：温度为约250℃至约300℃，时间为约90min至约300min。
  12. 根据权利要求9～11任一项所述的热塑性聚酯的制备方法，其特征在于，所述第二催化剂选自含钛化合物、含铝化合物、含锡化合物与含锗化合物中的一种或多种。
PCT/CN2022/113458 2022-08-19 2022-08-19 热塑性聚酯及其制备方法与应用 Ceased WO2024036583A1 (zh)

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