WO2018103575A1 - 一种聚对苯二甲酸酯-共-癸二酸酯树脂及其制备方法 - Google Patents

一种聚对苯二甲酸酯-共-癸二酸酯树脂及其制备方法 Download PDF

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WO2018103575A1
WO2018103575A1 PCT/CN2017/113754 CN2017113754W WO2018103575A1 WO 2018103575 A1 WO2018103575 A1 WO 2018103575A1 CN 2017113754 W CN2017113754 W CN 2017113754W WO 2018103575 A1 WO2018103575 A1 WO 2018103575A1
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Prior art keywords
polyterephthalate
resin
peak
sebacate
temperature
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French (fr)
Inventor
王伟伟
袁志敏
蔡彤旻
黄险波
曾祥斌
苑仁旭
郭志龙
唐美军
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ZHUHAI WANGO CHEMICAL CO Ltd
Kingfa Science and Technology Co Ltd
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ZHUHAI WANGO CHEMICAL CO Ltd
Kingfa Science and Technology Co Ltd
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Priority to EP17878750.3A priority Critical patent/EP3553109A4/en
Publication of WO2018103575A1 publication Critical patent/WO2018103575A1/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
    • C08G63/02—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
    • C08G63/78—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
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

Definitions

  • the invention belongs to the field of polymer synthesis, and in particular relates to a polyterephthalate-co-sebacate resin and a preparation method thereof.
  • Poly terephthalate-co-sebacate resin is a copolymer of butylene phthalate and butylene terephthalate, polyterephthalate-co-sebacic acid
  • the ester resin contains a flexible fatty chain and a rigid aromatic chain, thus having high toughness and high temperature resistance, and due to the presence of ester bonds, it is simultaneously biodegradable, which is very active in the research of biodegradable plastics and market application.
  • One of the best degradable materials One of the best degradable materials.
  • the crystallization rate of the polyphthalate-co-sebacate resin affects the transparency of the film and also affects the processing of the film.
  • the crystallization rate is too slow, and the freshly blown film tends to be self-adhesive when it is wound onto the reel, and most of the sales and transportation needs to be wound onto the reel, which is not conducive to mass processing; the crystallization speed is too fast, and the transparency of the film is transparent. Will decline.
  • the prior art generally adds an opening agent and a slip agent to improve the above problems, as in the patent CN 103627151 B, 0.5-1% slip agent and 0.5-3% opening agent are added.
  • the slip agent is usually one or more of stearates, organic carboxylic acid amides or waxes, wherein the stearates are: calcium stearate, magnesium stearate, zinc stearate, Barium stearate, organic carboxylic acid amides are: erucamide, oleic acid amide, N, N-ethylene bis stearamide, waxes: polyethylene wax, oxidized polyethylene wax, paraffin wax; opening agent is usually used : silica, talc, calcium carbonate, whisker silicon, magnesium oxide, aluminum hydroxide or magnesium hydroxide.
  • the above slip agent and opening agent are non-food additives, which are disadvantageous for developing food packaging film.
  • DSC Differential Scanning Calorimetry
  • the performance parameters satisfy the following relationship:
  • T crystal peak half width / (T melting point - T crystallization temperature) 0.05 - 0.26;
  • the half width of the T crystal peak is the half width of the crystallization peak on the second cooling curve of the DSC test
  • the T melting point is the peak of the melting peak on the second heating curve of the DSC test
  • the T crystallization temperature is the second temperature drop of the DSC test. The peak of the crystallization peak on the curve.
  • the T-peak peak half-width / (T-melting-T crystallization temperature) actually reflects the crystallization behavior of the polyethylene terephthalate-co-sebacate resin.
  • the crystallization behavior is closely related to the crystal melting behavior and the structural characteristics of the molecular chain. There are many factors affecting the half-peak width, T-th melting point, and T-crystallization temperature of the T-crystal peak. For example, due to the difference in the ratio of raw material monomers, the degree of self-polymerization of the monomer, the change in molecular weight and molecular chain sequence structure, and whether the molecular segments are uniform.
  • the smooth processing can be smoothly processed without adding an opening agent or a compatibilizer, thereby ensuring the product quality and having the product quality. Good processing performance.
  • the static friction coefficient of the membrane is too large and tends to be self-adhesive; the static friction coefficient is too small, and the product is too slippery to be processed and wound.
  • the content of the carboxyl group in the polyterephthalate-co-sebacate resin is 30 mol/ton or less.
  • the carboxyl group content is increased, the water resistance of the polyester resin is deteriorated during storage or processing, and the product quality tends to be deteriorated.
  • the carboxyl group content is too low, the process route becomes complicated, and the equipment investment is excessively high, which is economically disadvantageous.
  • the polyethylene terephthalate-co-succinate resin has a melt index of 190 ° C and a condition of 2.16 Kg weight of 3.0 g/10 min to 20.0 g/10 min.
  • the water content in the polyterephthalate-co-sebacate resin is from 50 ppm to 800 ppm based on the total mass of the entire polyethylene terephthalate-co-sebacate resin. .
  • the process route becomes complicated, the drying time is too long, economically unfavorable, and may have a negative impact on color and other varieties.
  • the water content is too high, the polyethylene terephthalate-co-succinate resin is hydrolyzed during storage, and the quality of the product tends to be deteriorated.
  • the invention also provides a preparation method of the above polyterephthalate-co-sebacate resin, comprising the following steps:
  • the metered terephthalic acid, 1,4-butanediol and tetrakis(2-ethylhexyl) titanate are put into the reaction kettle and the temperature is raised to 240-250 ° C under pressure.
  • the reaction is carried out at 0.15-0.3 MPa for 2 hours, and then the temperature of the azelaic acid is added to be controlled at 240-250 ° C, and the reaction is carried out under a vacuum of 10-30 KPa for 1-2 hours;
  • the pressure in the reaction vessel is further reduced to 100 Pa or less, and the reaction is carried out at 230-260 ° C for 2-4 hours, the stirring is stopped, the reactor is filled with high-purity nitrogen gas, and the resin is extruded from the reaction vessel for granulation, that is, The resin was obtained.
  • the invention has the following beneficial effects:
  • T crystal peak half width / (T melting point - T crystallization temperature) 0.05 - 0.26, due to effective control of the crystallization rate of the resin, the polyethylene terephthalate - co-succinate resin in the preparation of 25 ⁇
  • the film has a thickness of 1 ⁇ m, its static friction coefficient is 0.2-0.3, and its light transmittance is 90% or more, which balances the light transmittance and static friction coefficient of the film, and maintains high light transmission performance.
  • the low static friction coefficient can be smoothly processed without adding an opening agent or a compatibilizing agent, so that the prepared polyethylene terephthalate-co-sebacate resin exhibits good transparency and processability.
  • the metered terephthalic acid, 1,4-butanediol and tetrakis(2-ethylhexyl) titanate were put into the reaction vessel and heated to 240-250 ° C at a pressure of 0.15-
  • the reaction was carried out at 0.3 MPa for 2 hours, and then the temperature of the azelaic acid was added to be 240- React at 250 ° C under a vacuum of 10-30 KPa for 1-2 hours; then reduce the pressure in the reactor to below 100 Pa, and react at 230-260 ° C for 2-4 hours, stop stirring, and fill the reactor with high purity nitrogen.
  • the resin is extruded from the reactor to be granulated to obtain a polyethylene terephthalate-co-succinate resin.
  • Table 1 The performance results are shown in Table 1.
  • Example 1 The mass of sebacic acid was 2616.5 g, the mass of 1,4-butanediol was 3395.8 g, the mass of terephthalic acid was 2024.0 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • Example 2 The mass of sebacic acid was 2625.9 g, the mass of 1,4-butanediol was 3394.7 g, the mass of terephthalic acid was 2015.1 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • Example 3 The mass of sebacic acid was 2639.9 g, the mass of 1,4-butanediol was 3393.2 g, the mass of terephthalic acid was 2001.6 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • Example 4 The mass of sebacic acid was 2611.8 g, the mass of 1,4-butanediol was 3396.3 g, the mass of terephthalic acid was 2028.5 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • Example 5 The mass of sebacic acid was 2779.6 g, the mass of 1,4-butanediol was 3377.9 g, the mass of terephthalic acid was 1868.1 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • Example 6 The mass of sebacic acid was 2309.0 g, the mass of 1,4-butanediol was 3429.5 g, the mass of terephthalic acid was 2318.1 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • Example 7 The mass of sebacic acid was 2607.1 g, the mass of 1,4-butanediol was 3396.8 g, the mass of terephthalic acid was 2033.0 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • Example 8 The mass of sebacic acid was 2602.4 g, the mass of 1,4-butanediol was 3397.3 g, the mass of terephthalic acid was 2037.4 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • Example 9 The mass of sebacic acid was 2356.7 g, the mass of 1,4-butanediol was 3424.3 g, the mass of terephthalic acid was 2272.5 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • Example 10 The mass of sebacic acid was 2361.4 g, the mass of 1,4-butanediol was 3423.7 g, the mass of terephthalic acid was 2267.9 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • Comparative Example 1 Under the protection of high purity nitrogen, the metered sebacic acid, terephthalic acid and 1,4-butanediol were put into the reaction vessel, and tetrakis(2-ethylhexyl) titanate was added thereto, and the temperature was raised to 200-230 ° C reaction 1-3 hours, vacuum, reduce the pressure inside the reactor to below 100 Pa within 2 hours, react at 230-260 ° C for 2-4 hours, stop stirring, fill the reactor with high purity nitrogen The resin was extruded from the reaction vessel to form a resin.
  • the mass of sebacic acid is 2616.5 g
  • the mass of 1,4-butanediol is 3395.8 g
  • the mass of terephthalic acid is 2024.0 g
  • the mass of tetrakis(2-ethylhexyl) titanate is 6.0 g. .
  • Comparative Example 2 the mass of sebacic acid was 2356.7 g, the mass of 1,4-butanediol was 3424.3 g, the mass of terephthalic acid was 2272.5 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • the preparation process was the same as in Comparative Example 1.
  • Comparative Example 3 the mass of sebacic acid was 2756.4 g, the mass of 1,4-butanediol was 3380.4 g, the mass of terephthalic acid was 1890.2 g, and the mass of tetrakis(2-ethylhexyl) titanate was 6.0g.
  • the preparation process was the same as in Example 1.
  • Test method for carboxyl content Test according to the method A of GB/T14190-2008.
  • Test method for water content Test according to the method B of GB/T12006.2-2009.
  • DSC test method the instrument is Germany NETZSCH 204F1, scanning temperature 0-200 ° C, temperature rise and fall rate 10 °C / min, two cycles of temperature rise and fall, the melting point and crystallization temperature are the data on the second cycle curve.
  • Transmittance test method The instrument is Shanghai Shenguang Instrument Co., Ltd. WGT-S transmittance/haze tester, the synthetic resin is made into a film with a thickness of 25 ⁇ 1 ⁇ m, and tested by GB/T2410-2008 method.
  • Static friction coefficient test method The synthetic resin was made into a film having a thickness of 25 ⁇ 1 ⁇ m, and tested by the method of GB 10006-88.
  • T-peak peak half-width / (T-melting-T crystallization temperature) 0.05-0.26
  • the polyethylene terephthalate-co-succinate resin has a static friction coefficient of 0.2-0.3 when it is made into a film having a thickness of 25 ⁇ 1 ⁇ m, and its light transmission is The rate is more than 90%, and the light transmittance and static friction coefficient of the film are balanced, and good transparency and processability are exhibited.
  • Comparative Example 1-2 when the T-peak peak half-width/(T-melting-T crystallization temperature) is higher than 0.26, although the film exhibits a high light transmittance, the static friction coefficient is high, which is disadvantageous for The processing proceeded smoothly; in Comparative Example 3, when the T-peak peak half-width/(T-melting-T crystallization temperature) was less than 0.05, the film exhibited a lower static friction coefficient, but its transparency was poor.

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Abstract

本发明公开了一种聚对苯二甲酸酯-共-癸二酸酯树脂及其制备方法，由二元酸和二元醇聚合而成，按摩尔百分比计，所述二元酸由45mol％-55mol％的对苯二甲酸和45mol％-55mol％的癸二酸组成；所述二元醇为1,4-丁二醇，所述聚对苯二甲酸酯-共-癸二酸酯树脂的热性能参数满足如下关系式： T结晶峰半峰宽/(T熔点-T结晶温度)＝0.05-0.26；由该聚对苯二甲酸酯-共-癸二酸酯树脂在制成25±1μm厚度的薄膜时，其静摩擦系数为0.2-0.3，且其透光率为90％以上，平衡了膜材的透光率与静摩擦系数，在维持了较高的透光性能的同时也具有较低的静摩擦系数，无需添加开口剂或相容剂也能顺利加工，使制备得到的聚对苯二甲酸酯-共-癸二酸酯树脂表现出良好的透明性和加工性能。

Description

一种聚对苯二甲酸酯-共-癸二酸酯树脂及其制备方法 技术领域
本发明属于高分子合成领域，具体涉及一种聚对苯二甲酸酯-共-癸二酸酯树脂及其制备方法。
背景技术
聚对苯二甲酸酯-共-癸二酸酯树脂是由癸二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物，聚对苯二甲酸酯-共-癸二酸酯树脂中含柔性的脂肪链和刚性的芳香链因而具有高韧性和耐高温性,而由于酯键的存在，促使其同时具有生物可降解性，是目前生物降解塑料研究中非常活跃和市场应用最好降解材料之一。
但实际使用时发现聚对苯二甲酸酯-共-癸二酸酯树脂的结晶速度在影响膜材的透明性的同时也会影响膜的加工。结晶速率过慢，刚吹出的膜被卷到卷轴上时它们趋于自粘，而销售和运输大部分环节需要卷到卷轴上，不利于大批量加工；结晶速度过快，膜材的透明性会有所下降。
现有技术通常添加开口剂和爽滑剂来改善上述问题，如专利CN 103627151 B中添加了0.5-1％爽滑剂和0.5-3％的开口剂。爽滑剂通常为硬脂酸盐类、有机羧酸酰胺类或蜡类中的一种或多种，其中硬脂酸盐类为：硬脂酸钙、硬脂酸镁、硬脂酸锌、硬脂酸钡，有机羧酸酰胺类为：芥酸酰胺、油酸酰胺、N,N-乙撑双硬脂酰胺，蜡类为：聚乙烯蜡、氧化聚乙烯蜡、石蜡；开口剂通常使用：二氧化硅、滑石粉、碳酸钙、晶须硅、氧化镁、氢氧化铝或氢氧化镁。上述爽滑剂和开口剂均为非食品添加剂，对于开发食品包装膜材不利。
差示扫描量热分析(DSC)是最常用的热分析仪器之一，用于表征聚合物熔融结晶过程，反应了分子链结构与结晶之间的关系，分子链结构的变化，直接决定了DSC在升温或降温的过程中熔融或结晶行为。本发明经研究发现，当聚对苯二甲酸酯-共-癸二酸酯树脂聚对苯二甲酸酯-共-癸二酸酯树脂的热性能参数满足特定关系式时，由于具有特定的分子链的结构及结晶状态，从而展现出了良好的产品品质，又具有良好的加工性能。
发明内容
本发明的目的在于提供一种聚对苯二甲酸酯-共-癸二酸酯树脂，该树脂的热性能参数满足特定的关系式，具有较高的透光性能且具有较低的静摩擦系数。
本发明是通过以下技术方案实现的：
一种聚对苯二甲酸酯-共-癸二酸酯树脂，由二元酸和二元醇聚合而成，按摩尔百分比计，所述二元酸由45mol％-55mol％的对苯二甲酸和45mol％-55mol％的癸二酸组成；所述二元醇为1,4-丁二醇，其特征在于，所述聚对苯二甲酸酯-共-癸二酸酯树脂的热性能参数满足如下关系式：
T结晶峰半峰宽/(T熔点-T结晶温度)＝0.05-0.26；
其中，T结晶峰半峰宽为DSC测试第二次降温曲线上结晶峰的半峰宽，T熔点为DSC测试第二次升温曲线上熔融峰的峰值，T结晶温度为DSC测试第二次降温曲线上结晶峰的峰值。
T结晶峰半峰宽/(T熔点-T结晶温度)实际反映的是聚对苯二甲酸酯-共-癸二酸酯树脂的结晶行为。结晶行为与晶体熔融行为和分子链的结构特征具有密切联系。影响T结晶峰半峰宽、T熔点、T结晶温度的因素有很多，比如由于原料单体比例的不同，单体自聚程度的大小，分子量和分子链序列结构的变化，分子链段是否均匀及分子链是否规整，分子链 的缠结或支化程度的高低，分子链内旋转能力的高低，分子链的运动能力，制备工艺过程等诸多因素的影响，从而影响了最终制备得到的聚对苯二甲酸酯-共-癸二酸酯树脂的分子链结构存在较大区别，从而导致其宏观的透光率和静摩擦系数产生变化。
本发明通过研究发现，当聚对苯二甲酸酯-共-癸二酸酯树脂的热性能参数满足：T结晶峰半峰宽/(T熔点-T结晶温度)＝0.05-0.26时，树脂吹膜时可以平衡透光率与膜材的静摩擦系数，表现出较高的透光率且具有较低的静摩擦系数，无需添加开口剂或相容剂也能顺利加工，保证了产品品质又具有良好的加工性能。膜材的静摩擦系数太大，趋于自粘；静摩擦系数太小，产品过滑不宜加工收卷。当T结晶峰半峰宽/(T熔点-T结晶温度)低于0.05时，由于分子链结构的变化，结晶速率过快，导致其透光率较低，影响产品的品质；当T结晶峰半峰宽/(T熔点-T结晶温度)高于0.26时，由于分子链结构的变化，结晶速率过慢，导致其静摩擦系数较大，不利于加工的顺利进行。优选的，本发明聚对苯二甲酸酯-共-癸二酸酯树脂的热性能参数满足：T结晶峰半峰宽/(T熔点-T结晶温度)＝0.1-0.21。
优选的，所述聚对苯二甲酸酯-共-癸二酸酯树脂中的羧基含量为30摩尔/吨以下。该羧基含量变多时，聚酯树脂保存或加工时耐水性变差，使产品质量有变差的倾向，羧基含量过低时工艺路线变得复杂，设备投入过高，在经济上不利。
优选的，所述聚对苯二甲酸酯-共-癸二酸酯树脂的熔融指数在190℃，2.16Kg砝码的条件测试为3.0g/10min-20.0g/10min。
优选的，基于整个聚对苯二甲酸酯-共-癸二酸酯树脂的总质量，所述聚对苯二甲酸酯-共-癸二酸酯树脂中的水含量为为50ppm-800ppm。水含量过少时，工艺路线变得复杂，烘干时间也过长，在经济上不利，且可能对颜色及其它品种产生负面影响。另一方面，水含量过高时，聚对苯二甲酸酯-共-癸二酸酯树脂保存时水解，使产品质量有变差的倾向。
本发明还提供了上述的一种聚对苯二甲酸酯-共-癸二酸酯树脂的制备方法，包括如下步骤：
(1)在高纯氮气保护下，将计量的对苯二甲酸、1,4-丁二醇、四(2-乙基己基)钛酸酯投入反应釜中升温至240-250℃，在压力为0.15-0.3MPa下反应2小时，再加入癸二酸控制温度为240-250℃，在10-30KPa的真空下反应1-2小时；
(2)再将反应釜内压力降至100Pa以下，于230-260℃反应2-4小时，停止搅拌，向反应釜内充入高纯氮气，将树脂从反应釜中压出造粒，即得到树脂。
本发明与现有技术相比，具有如下有益效果：
本发明通过研究发现，本发明的聚对苯二甲酸酯-共-癸二酸酯树脂热性能参数满足关系式：
T结晶峰半峰宽/(T熔点-T结晶温度)＝0.05-0.26，由于有效控制了树脂的结晶速率，将聚对苯二甲酸酯-共-癸二酸酯树脂在制成25±1μm厚度的薄膜时，其静摩擦系数为0.2-0.3，且其透光率为90％以上，平衡了膜材的透光率与静摩擦系数，在维持了较高的透光性能的同时也具有较低的静摩擦系数，无需添加开口剂或相容剂也能顺利加工，使制备得到的聚对苯二甲酸酯-共-癸二酸酯树脂表现出良好的透明性和加工性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
聚对苯二甲酸酯-共-癸二酸酯树脂(PBSeT)的合成：
在高纯氮气保护下，将计量的对苯二甲酸、1,4-丁二醇、四(2-乙基己基)钛酸酯投入反应釜中升温至240-250℃，在压力为0.15-0.3MPa下反应2小时，再加入癸二酸控制温为240- 250℃，在10-30KPa的真空下反应1-2小时；再将反应釜内压力降至100Pa以下，于230-260℃反应2-4小时，停止搅拌，向反应釜内充入高纯氮气，将树脂从反应釜中压出造粒，即得到聚对苯二甲酸酯-共-癸二酸酯树脂。，性能结果如表1所示。
实施例1：癸二酸的质量为2616.5g、1,4-丁二醇的质量为3395.8g、对苯二甲酸的质量为2024.0g、四(2-乙基己基)钛酸酯的质量为6.0g。
实施例2：癸二酸的质量为2625.9g、1,4-丁二醇的质量为3394.7g、对苯二甲酸的质量为2015.1g、四(2-乙基己基)钛酸酯的质量为6.0g。
实施例3：癸二酸的质量为2639.9g、1,4-丁二醇的质量为3393.2g、对苯二甲酸的质量为2001.6g、四(2-乙基己基)钛酸酯的质量为6.0g。
实施例4：癸二酸的质量为2611.8g、1,4-丁二醇的质量为3396.3g、对苯二甲酸的质量为2028.5g、四(2-乙基己基)钛酸酯的质量为6.0g。
实施例5：癸二酸的质量为2779.6g、1,4-丁二醇的质量为3377.9g、对苯二甲酸的质量为1868.1g、四(2-乙基己基)钛酸酯的质量为6.0g。
实施例6：癸二酸的质量为2309.0g、1,4-丁二醇的质量为3429.5g、对苯二甲酸的质量为2318.1g、四(2-乙基己基)钛酸酯的质量为6.0g。
实施例7：癸二酸的质量为2607.1g、1,4-丁二醇的质量为3396.8g、对苯二甲酸的质量为2033.0g、四(2-乙基己基)钛酸酯的质量为6.0g。
实施例8：癸二酸的质量为2602.4g、1,4-丁二醇的质量为3397.3g、对苯二甲酸的质量为2037.4g、四(2-乙基己基)钛酸酯的质量为6.0g。
实施例9：癸二酸的质量为2356.7g、1,4-丁二醇的质量为3424.3g、对苯二甲酸的质量为2272.5g、四(2-乙基己基)钛酸酯的质量为6.0g。
实施例10：癸二酸的质量为2361.4g、1,4-丁二醇的质量为3423.7g、对苯二甲酸的质量为2267.9g、四(2-乙基己基)钛酸酯的质量为6.0g。
对比例1：在高纯氮气保护下，将计量的癸二酸、对苯二甲酸、1,4-丁二醇投入反应釜中，加入四(2-乙基己基)钛酸酯，升温至200-230℃反应1-3小时，抽真空，在2小时内将反应釜内压力降至100Pa以下，于230-260℃反应2-4小时，停止搅拌，向反应釜内充入高纯氮气，将树脂从反应釜中压出造粒，即得到树脂。
其中，癸二酸的质量为2616.5g、1,4-丁二醇的质量为3395.8g、对苯二甲酸的质量为2024.0g、四(2-乙基己基)钛酸酯的质量为6.0g。
对比例2：癸二酸的质量为2356.7g、1,4-丁二醇的质量为3424.3g、对苯二甲酸的质量为2272.5g、四(2-乙基己基)钛酸酯的质量为6.0g。制备工艺同对比例1。
对比例3：癸二酸的质量为2756.4g、1,4-丁二醇的质量为3380.4g、对苯二甲酸的质量为1890.2g、四(2-乙基己基)钛酸酯的质量为6.0g。制备工艺同实施例1。
性能评价方法：
羧基含量的测试方法：按GB/T14190-2008中方法A规定进行测试。
水含量的测试方法：按GB/T12006.2-2009中方法B规定进行测试。
熔融指数测试方法：在190℃，2.16Kg砝码的条件测试。
DSC测试方法：仪器为德国NETZSCH 204F1，扫描温度0-200℃，升降温速率10 ℃/分钟，升降温两个循环，熔点和结晶温度均采用第二个循环曲线上的数据。
透过率测试方法：仪器为上海申光仪器仪表有限公司WGT-S透光率/雾度测定仪，将合成树脂制成25±1μm厚度的薄膜，采用GB/T2410-2008方法进行测试。
静摩擦系数测试方法：将合成树脂制成25±1μm厚度的薄膜，采用GB 10006-88方法进行测试。
表1
Figure PCTCN2017113754-appb-000001
Figure PCTCN2017113754-appb-000002
由表1结果可以看出，聚对苯二甲酸酯-共-癸二酸酯树脂的热性能参数满足关系式：T结晶峰半峰宽/(T熔点-T结晶温度)＝0.05-0.26时，由于有效控制了树脂的结晶速率，将聚对苯二甲酸酯-共-癸二酸酯树脂在制成25±1μm厚度的薄膜时，其静摩擦系数为0.2-0.3，且其透光率为90％以上，平衡了膜材的透光率与静摩擦系数，表现出良好的透明性和加工性能。对比例1-2中，当T结晶峰半峰宽/(T熔点-T结晶温度)高于0.26时，虽然膜材表现出较高的透光率，但其静摩擦系数却较高，不利于加工的顺利进行；对比例3中，当T结晶峰半峰宽/(T熔点-T结晶温度)低于0.05时，膜材表现出较低的静摩擦系数，但其透明性能较差。

Claims (7)

  1. 一种聚对苯二甲酸酯-共-癸二酸酯树脂，由二元酸和二元醇聚合而成，按摩尔百分比计，所述二元酸由45mol％-55mol％的对苯二甲酸和45mol％-55mol％的癸二酸组成；所述二元醇为1,4-丁二醇，其特征在于，所述聚对苯二甲酸酯-共-癸二酸酯树脂的热性能参数满足如下关系式：
    T结晶峰半峰宽/(T熔点-T结晶温度)＝0.05-0.26；
    其中，T结晶峰半峰宽为DSC测试第二次降温曲线上结晶峰的半峰宽，T熔点为DSC测试第二次升温曲线上熔融峰的峰值，T结晶温度为DSC测试第二次降温曲线上结晶峰的峰值。
  2. 根据权利要求1所述的聚对苯二甲酸酯-共-癸二酸酯树脂，其特征在于，DSC测试的方法为：仪器为德国NETZSCH 204 F1，扫描温度0-200℃，升降温速率10℃/分钟，升降温两个循环，熔点和结晶温度均采用第二个循环曲线上的数据。
  3. 根据权利要求1所述的聚对苯二甲酸酯-共-癸二酸酯树脂，其特征在于，所述聚对苯二甲酸酯-共-癸二酸酯树脂的热性能参数满足如下关系式：
    T结晶峰半峰宽/(T熔点-T结晶温度)＝0.1-0.21；
    其中，T结晶峰半峰宽为DSC测试第二次降温曲线上结晶峰的半峰宽，T熔点为DSC测试第二次升温曲线上熔融峰的峰值，T结晶温度为DSC测试第二次降温曲线上结晶峰的峰值。
  4. 根据权利要求1所述的聚对苯二甲酸酯-共-癸二酸酯树脂，其特征在于，所述聚对苯二甲酸酯-共-癸二酸酯中的羧基含量为30摩尔/吨以下，羧基含量的测试方法GB/T14190-2008中方法A规定进行测试。
  5. 根据权利要求1所述的聚对苯二甲酸酯-共-癸二酸酯树脂组合物，其特征在于，所述聚对苯二甲酸酯-共-癸二酸酯树脂的熔融指数在190℃，2.16Kg砝码的条件测试为3.0g/10min-20.0g/10min。
  6. 根据权利要求1所述的一种聚对苯二甲酸酯-共-癸二酸酯树脂，其特征在于，基于整个聚对苯二甲酸酯-共-癸二酸酯树脂的总质量，聚对苯二甲酸酯-共-癸二酸酯中的水含量为50ppm～800ppm，水含量的测试方法按GB/T12006.2-2009中方法B规定进行测试。
  7. 根据权利要求1-5任一项所述的一种聚对苯二甲酸酯-共-癸二酸酯树脂的制备方法，其特征在于，包括如下步骤：
    (1)在高纯氮气保护下，将计量的对苯二甲酸、1,4-丁二醇、四(2-乙基己基)钛酸酯投入反应釜中升温至240-250℃，在压力为0.15-0.3MPa下反应2小时，再加入癸二酸控制温为240-250℃，在10-30KPa的真空下反应1-2小时；
    (2)再将反应釜内压力降至100Pa以下，于230-260℃反应2-4小时，停止搅拌，向反应釜 内充入高纯氮气，将树脂从反应釜中压出造粒，即得到树脂。
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