高稳定性钛系聚酯催化剂TiOC@SiO2的制备及应用

doi:10.16085/j.issn.1000-6613.2023-0349

摘要/Abstract

摘要：

钛系聚酯催化剂因催化活性高、环境友好等优点，是传统锑系聚酯催化剂的理想替代品。为了制备出耐水解性好、分散性好、催化性能稳定的钛系聚酯催化剂，采用反相微乳液法，制备得到核壳结构催化剂TiOC@SiO₂。在钛有机化合物的表面包覆一层硅氧烷，以此稳定钛有机化合物的催化活性。利用多种现代表征方法对TiOC@SiO₂的形貌、结构和性能进行了表征分析，并探究其在合成聚对苯二甲酸乙二醇酯（PET）中的催化性能。研究结果表明，TiOC@SiO₂催化剂为粒径约200nm的核壳球形结构，无Ti—O—Si键，钛含量为6.95%。TiOC@SiO₂催化剂在90℃下水浴2h后，其结构和催化活性保持不变，复合结构显著提高了钛有机化合物的耐水解性和分散性。在聚酯合成实验中，仅添加5μg/g TiOC@SiO₂，在270℃下缩聚反应92min，即可制备出特性黏度为0.677dL/g、端羧基含量为14.4mol/t、b值为2.16的PET。

关键词: 催化剂, 聚合, 纳米粒子, 聚酯, 催化性能

Abstract:

Titanium-based polyester catalysts are ideal substitutes for traditional antimony-based catalysts due to their high catalytic activity and environmental friendliness. In order to prepare titanium polyester catalyst with hydrolysis resistance, good dispersibility and stable catalytic performance, TiOC@SiO₂ catalyst was prepared by reverse microemulsion method. A layer of siloxane was coated on the surface of titanium containing organic compound to stabilize the catalytic activity. The morphology, structure and properties of TiOC@SiO₂ were characterized by various modern characterization methods, and its catalytic performance in the synthesis of polyethylene terephthalate (PET) was evaluated. The results showed that the TiOC@SiO₂ catalyst had a core-shell spherical structure with a particle size of about 200nm, but no Ti—O—Si bond, and a Ti content of 6.95%. The structure and catalytic activity of TiOC@SiO₂ catalyst remained unchanged at 90℃ for 2h. The composite structure significantly improved the hydrolysis resistance of the titanium organic compounds and dispersibility. In the polyethylene terephthalate synthesis experiment, with only 5μg/g TiOC@SiO₂ added and polycondensation at 270℃ for 92min, polyester with intrinsic viscosity of 0.677dL/g, terminal carboxyl content of 14.4mol/t and b value of 2.16 was prepared.

Key words: catalyst, polymerization, nanoparticles, polyester, catalytic performance

中图分类号:

TS15

刘斌, 王勇军, 吕汪洋, 陈文兴. 高稳定性钛系聚酯催化剂TiOC@SiO₂的制备及应用[J]. 化工进展, 2024, 43(3): 1395-1402.

LIU Bin, WANG Yongjun, LYU Wangyang, CHEN Wenxing. Preparation and application of high stability titanium polyester catalyst TiOC@SiO₂[J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1395-1402.

图/表 10

参考文献 17

1	孙宾, 王鸣义. 钛系催化剂在聚酯合成领域的应用进展及趋势(上)[J]. 纺织导报, 2019(9): 38-49.
	SUN Bin, WANG Mingyi. Application and prospect of titanium-based catalysts in the polyester synthesis(Ⅰ)[J]. China Textile Leader, 2019(9): 38-49.
2	陈锡荣, 张伟, 闫一凡, 等. 钛系聚酯催化剂的研究进展[J]. 化工进展, 2005, 24(5): 480-482, 488.
	CHEN Xirong, ZHANG Wei, YAN Yifan, et al. Progress of study on titanium system catalyst for polyester[J]. Chemical Industry and Engineering Progress, 2005, 24(5): 480-482, 488.
3	MICHEAL Martl, THOMAS Mezger, GERRIET Oberlein, et al. Titanium dioxide/silicon dioxide coprecipitates and titanium dioxide/zirconium dioxide coprecipiates as polycondensation catalysts for polyesters and copolyesters: US5684116[P]. 1997-11-04.
4	YIN Ming, LI Chuncheng, GUAN Guohu, et al. Novel catalysts based on titanium dioxide/silicon dioxide for poly(ethylene terephthalate)[J]. Journal of Applied Polymer Science, 2010, 115(4): 2470-2478.
5	ASHUTOSH Thakur, TAKUYA Hamamoto, TOMOHIRO Ikeda, et al. Microwave-assisted polycondensation for screening of organically-modified TiO₂/SiO₂ catalysts[J]. Applied Catalysis A: General, 2020, 595: 117508.
6	WOLFGANG Schmidt, ULRICH Thiele, Griebler WOLF-DIETER, et al. Titanium-containing catalyst and process for the production of polyester: US5656716[P]. 1997-08-12.
7	STEVEN Raymondlustig, ROBERT Rayburch, EUGENE Mccarron, et al. Catalysis with titanium oxides: US6034203[P]. 2000-03-07.
8	LIN Qisong, GAO Feng, WANG Yongjun, et al. Ethylene glycol-soluble Ti/Mg-citrate complex catalyst for synthesis of high intrinsic viscosity poly(ethylene terephthalate)[J]. Polymer, 2022, 246: 124741.
9	LI Xingui, SONG Ge, HUANG Meirong. Cost-effective sustainable synthesis of high-performance high-molecular-weight poly(trimethylene terephthalate) by eco-friendly and highly active Ti/Mg catalysts[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(3): 2181-2195.
10	LE Roux Erwan. Recent advances on tailor-made titanium catalysts for biopolymer synthesis[J]. Coordination Chemistry Reviews, 2016, 306: 65-85.
11	HALA Assi, GEORGES Mouchaham, NATHALIE Steunou, et al. Titanium coordination compounds: From discrete metal complexes to metal-organic frameworks[J]. Chemical Society Reviews, 2017, 46(11): 3431-3452.
12	LAURENCE Rozes, Sanchez CLE´MENT. Titanium oxo-clusters: Precursors for a Lego-like construction of nanostructured hybrid materials[J]. Chemical Society Reviews, 2011, 40(2): 1006-1030.
13	LI Ziwei, LI Min, BIAN Zhoufeng, et al. Design of highly stable and selective core/yolk-shell nanocatalysts—A review[J]. Applied Catalysis B: Environmental, 2016(188): 324-341.
14	高睿, 韩美玲, 黄丽丽, 等. 空心纳米Ni@SiO₂复合材料的制备及其催化性能[J]. 精细化工, 2022, 39(1): 74-79.
	GAO Rui, HAN Meiling, HUANG Lili, et al. Synthesis and catalytic activity of hollow nano Ni@SiO₂ composites[J]. Fine Chemicals, 2022, 39(1): 74-79.
15	李金辉, 李冰, 彭丹, 等. 有机硅浸渍漆用包覆型铂催化剂的制备[J]. 化工进展, 2019, 38(7): 3170-3175.
	LI Jinhui, LI Bing, PENG Dan, et al. Preparation of microencapsulated platinum catalysts for additive liquid silicone impregnating varnish[J]. Chemical Industry and Engineering Progress, 2019, 38(7): 3170-3175.
16	TANG Rongzhi, CHEN Tong, CHEN Yong, et al. Core-shell TiO₂@SiO₂ catalyst for transesterification of dimethyl carbonate and phenol to diphenyl carbonate[J]. Chinese Journal of Catalysis, 2014, 35(4): 457-461.
17	WANG Dian, YIN Tongtong, ZHANG Yanhua, et al. Titania coated silica core-shell spheres with dual grain size as efficient photocatalysts[J]. Microporous and Mesoporous Materials, 2022, 338: 111966.

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PET合成条件			酯化时间/min	缩聚时间/min	特性黏度/dL·g^-1	端羧基含量/mol·t^-1	b值
催化剂种类	催化剂含量/μg·g^-1	缩聚温度/℃	酯化时间/min	缩聚时间/min	特性黏度/dL·g^-1	端羧基含量/mol·t^-1	b值
TiOC@SiO₂	3	268	88	128	0.667	27.1	5.21
		270	87	120	0.673	25.3	4.25
		272	88	114	0.672	28.4	4.77
	5	268	84	100	0.675	18.3	3.43
		270	81	92	0.677	15.4	2.16
		272	83	86	0.683	17.3	3.20
	7	268	79	84	0.678	23.7	3.73
		270	80	77	0.682	18.4	3.17
		272	78	74	0.675	22.7	3.64
Sb₂O₃	200	270	120	118	0.676	20.4	1.28

PET合成条件			酯化时间/min	缩聚时间/min	特性黏度/dL·g^-1	端羧基含量/mol·t^-1	b值
催化剂种类	催化剂含量/μg·g^-1	缩聚温度/℃	酯化时间/min	缩聚时间/min	特性黏度/dL·g^-1	端羧基含量/mol·t^-1	b值
TiOC@SiO₂	3	268	88	128	0.667	27.1	5.21
		270	87	120	0.673	25.3	4.25
		272	88	114	0.672	28.4	4.77
	5	268	84	100	0.675	18.3	3.43
		270	81	92	0.677	15.4	2.16
		272	83	86	0.683	17.3	3.20
	7	268	79	84	0.678	23.7	3.73
		270	80	77	0.682	18.4	3.17
		272	78	74	0.675	22.7	3.64
Sb₂O₃	200	270	120	118	0.676	20.4	1.28

缩聚条件		T_g/℃	T_mc/℃	T_m/℃	ΔT^①/℃
催化剂	缩聚温度/℃	T_g/℃	T_mc/℃	T_m/℃	ΔT^①/℃
TiOC@SiO₂	268	77.11	174.98	249.50	74.52
	270	77.74	182.17	249.30	67.13
	272	78.25	180.05	248.71	68.46
Sb₂O₃	270	76.22	186.06	244.45	58.39

缩聚条件		T_g/℃	T_mc/℃	T_m/℃	ΔT^①/℃
催化剂	缩聚温度/℃	T_g/℃	T_mc/℃	T_m/℃	ΔT^①/℃
TiOC@SiO₂	268	77.11	174.98	249.50	74.52
	270	77.74	182.17	249.30	67.13
	272	78.25	180.05	248.71	68.46
Sb₂O₃	270	76.22	186.06	244.45	58.39

高稳定性钛系聚酯催化剂TiOC@SiO₂的制备及应用

Preparation and application of high stability titanium polyester catalyst TiOC@SiO₂

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