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用于合成聚对苯二甲酸乙二醇酯的KF/Al2O3催化剂研究
Study of KF/Al2O3 Catalyst in Synthesis of Poly(ethylene terephthalate) by Esterification
- 高分子学报 2018年0卷第9期 页码：1184-1193
- 作者机构：
3.中国科学院大学 北京 100049
- 作者简介：
E-mail: syliu@cioc.ac.cn Shao-ying Liu, E-mail: syliu@cioc.ac.cn
E-mail: gywang@cioc.ac.cn Gong-ying Wang, E-mail: gywang@cioc.ac.cn
- 基金信息：国家重点研发计划项目(项目号 2016YFB0301900)和四川省科技支撑计划项目(项目号 2015GZ0065)资助()
DOI：10.11777/j.issn1000-3304.2018.18014
中图分类号：纸质出版日期：2018-9，
收稿日期：2018-1-15，
修回日期：2018-3-8，
扫 描 看 全 文
蔡志锋, 王庆印, 刘绍英, 王公应. 用于合成聚对苯二甲酸乙二醇酯的KF/Al2O3催化剂研究[J]. 高分子学报, 2018,0(9):1184-1193.
Zhi-feng Cai, Qing-yin Wang, Shao-ying Liu, Gong-ying Wang. Study of KF/Al2O3 Catalyst in Synthesis of Poly(ethylene terephthalate) by Esterification[J]. Acta Polymerica Sinica, 2018,0(9):1184-1193.
蔡志锋, 王庆印, 刘绍英, 王公应. 用于合成聚对苯二甲酸乙二醇酯的KF/Al2O3催化剂研究[J]. 高分子学报, 2018,0(9):1184-1193. DOI： 10.11777/j.issn1000-3304.2018.18014.
Zhi-feng Cai, Qing-yin Wang, Shao-ying Liu, Gong-ying Wang. Study of KF/Al2O3 Catalyst in Synthesis of Poly(ethylene terephthalate) by Esterification[J]. Acta Polymerica Sinica, 2018,0(9):1184-1193. DOI： 10.11777/j.issn1000-3304.2018.18014.
摘要
采用浸渍法制备了KF/Al
2
O
3
催化剂，研究了KF含量和焙烧温度对KF/Al
2
O
3
催化剂结构、活性和性能的影响，采用X射线衍射(XRD)、扫描电子显微镜(SEM)和N
2
低温物理吸附对KF/Al
2
O
3
催化剂的结构进行表征，也用Hammett indicator测定了KF/Al
2
O
3
催化剂的碱度和碱量. 探讨了KF含量、焙烧温度与KF/Al
2
O
3
催化剂结构、碱度和碱量的关系以及KF/Al
2
O
3
催化剂结构、碱度和碱量与其用于酯化法合成聚对苯二甲酸乙二醇酯(PET)催化活性的关系. 研究结果表明，KF/Al
2
O
3
催化剂中出现了K
3
AlF
6
、 KAlO
2
和K
2
CO
3
等新的物相，催化剂中的中等强度的碱性有利于PET的聚合反应、强碱性会促进PET的降解反应. KF含量为25%，在400 °C焙烧的25-KF/Al
2
O
3
-400催化剂中含
γ
-Al
2
O
3
、K
3
AlF
6
和少量K
2
CO
3
，碱性和碱量适中，催化活性最好，制备的PET的特性黏数为1.07 dL/g、端羧基值为20.29 mol/t、二甘醇含量为2.85%、聚酯黄度(
L
)值为86.6和聚酯白度(
b
)值为4.6.
Abstract
A series of KF/Al
2
O
3
solid base catalysts were prepared by a wet impregnation method and applied to the synthesis of poly(ethylene terephthalate) (PET) from 1
4-dicarboxybenzene and ethylene glycol. The effect of KF content and calcination temperature on the structure
active components and properties of the catalysts were investigated. The structure of KF/Al
2
O
3
catalysts was characterized by X-ray diffraction (XRD)
scanning electron microscopy (SEM) and BET. The basic strength and basicity of KF/Al
2
O
3
catalysts were measured by Hammett indicator. The relationship between KF content
calcination temperature and the structure
basic strength and basicity of KF/Al
2
O
3
catalyst was investigated. The relationship between the structure
basic strength and basicity of KF/Al
2
O
3
catalysts and the catalytic activity in PET synthesis was also studied. The results showed that KF/Al
2
O
3
catalysts could be used to synthesize high-molecular-weight PET. It was found that several types of basic centers such as K
3
AlF
6
KAlO
2
K
2
O and K
2
CO
3
existed in the catalyst. The specific surface area of KF/Al
2
O
3
was reduced with increasing KF content. The particle size of KF/Al
2
O
3
increased with increasing KF content. The basic strength and basicity of KF/Al
2
O
3
increased with increasing KF content and calcination temperature. The activity of KF/Al
2
O
3
was related to the basic strength and basicity and was not really influenced by the specific surface area and particle size. Medium strength basic sites were responsible for the higher intrinsic viscosity
and strong basic sites could cause decomposition of the obtained polymer. Strong basic sites were mainly due to potassium carbonate
potassium aluminate and potassium oxide. The catalytic effect of 25-KF/Al
2
O
3
-400 was better than that of Sb
2
O
3
. It contained
γ
-Al
2
O
3
K
3
AlF
6
and a small amount of K
2
CO
3
. It had moderate basic strength
basicity and high activity. Based on the obtained results
the possible active site was K
3
AlF
6
. The intrinsic viscosity of 1.07 dL/g
with carboxyl end group content of 20.29 mol/t
DEG content of 2.85%
L
value of 86.6 and
b
value of 4.6
was obtained with 0.1 wt% of catalyst concentration.
关键词
KF/Al2O3碱度与碱量构效关系聚对苯二甲酸乙二醇酯
Keywords
KF/Al2O3Basic strength and basicityStructure-activity relationshipPoly(ethylene terephthalate)
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