以去氢枞胺为结构导向剂合成磷酸铝

doi:10.3969/j.issn.0253-2417.2020.03.009

摘要/Abstract

摘要：

以去氢枞胺为结构导向剂、蒎烯为溶剂，通过微波辅助溶剂热法合成了磷酸铝，采用X射线衍射、氮气吸附-脱附、扫描电镜、透射电镜、热重和程序升温红外等方法对样品进行了表征。结果表明：去氢枞胺存在于磷酸铝原粉中起到了结构导向作用，反应温度与反应时间对样品的物相和孔结构有较大的影响，在170℃下反应4 h后，得到了孔结构优良的"绵状"无定形磷酸铝，比表面积272 m²/g，具有多级孔结构，平均孔径3.01 nm，孔容0.69 cm³/g。

关键词: 去氢枞胺, 溶剂热, 磷酸铝

Abstract:

Aluminum phosphate was synthesized through microwave-assisted solvothermal method with dehydroabietylamine as the structure directing agent and pinene as the solvent. The products were characterized by X-ray diffraction, nitrogen adsorption-desorption, scanning electron microscope, transmission electron microscope, thermal gravimetric analysis and temperature-programmed infrared. The results indicated that the reaction temperature and duration showed significant effect on the phase and porosity of the aluminum phosphate, and the product with good porosity was obtained under the conditions of temperature 170℃ and duration 4 h or more. The typical sample possessed "sticky" morphology with amorphous structure, and micro- and meso-porous with the BET specific surface area of 272.00 m²/g, average pore size of 3.01 nm and huge pore volume of 0.69 cm³/g. The results also confirmed the existence of dehydroabietylamine in the as-synthesized aluminum phosphate, which confirmed the structure-directing property of the dehydroabietylamine.

Key words: dehydroabietylamine, solvothermal, aluminum phosphate

中图分类号:

TQ35
O611.4

杨晨,朱桂华,王亚明,刘志华,蒋丽红,何沛. 以去氢枞胺为结构导向剂合成磷酸铝[J]. 林产化学与工业, 2020, 40(3): 69-75.

Chen YANG,Guihua ZHU,Yaming WANG,Zhihua LIU,Lihong JIANG,Pei HE. Synthesis of Aluminum Phosphate with Dehydroabietylamine as Structure Directing Agent[J]. Chemistry and Industry of Forest Products, 2020, 40(3): 69-75.

图/表 7

图1

图2

表1

图3

图4

图5

表2

参考文献 32

1	徐如人, 庞文琴, 于吉红. 分子筛与多孔材料化学[M]. 北京: 科学出版社, 2004.
	XU R R , PANG W Q , YU J H . Zeolites and Porous Materials[M]. Beijing: Science Press, 2004.
2	WILSON S T , LOK B M , MESSINA C A , et al. Alu minophosphate molecular sieves:A new class of microporous crystalline inorganic solids[J]. Journal of the American Chemical Society, 1982, 104 (4): 1146- 1147.
3	LIU Z H , YANG C , ZHENG Q Y , et al. Adsorption of phenol from cigarette smoke using CoAPO-11[J]. Reaction Kinetics, Mechanisms and Catalysis, 2019, 127 (2): 1005- 1023.
4	WANG P , WANG C X , LYU G , et al. Synthesis of regularly shaped AlPO₄-11 molecular sieve through a solid transformation approach[J]. Microporous and Mesoporous Materials, 2020, 295, 109962.
5	LEE J H , KIM E J , LÓPEZ-ARBELOA F , et al. Microporous aluminophosphates synthesized with 1, 2, 3-trimethylimidazolium and fluoride[J]. Dalton Transactions, 2016, 45 (18): 7616- 7626.
6	LEE S , JO C , PARK H , et al. Sulfonium-based organic structure-directing agents for microporous aluminophosphate synthesis[J]. Microporous and Mesoporous Materials, 2019, 280, 75- 81.
7	AZIM M M , STARK A . Ionothermal synthesis and characterisation of Mn-, Co-, Fe- and Ni-containing aluminophosphates[J]. Microporous and Mesoporous Materials, 2018, 272, 251- 259.
8	XU R S , SHI X C , ZHANG W P , et al. Cooperative structure-directing effect in the synthesis of aluminophosphate molecular sieves in ionic liquids[J]. Physical Chemistry Chemical Physics, 2010, 12 (10): 2443- 2449.
9	PEI R Y , TIAN Z J , WEI Y , et al. Ionothermal synthesis of AlPO₄-34 molecular sieves using heterocyclic aromatic a mine as the structure directing agent[J]. Materials Letters, 2010, 64 (21): 2384- 2387.
10	MARTÍNEZ-FRANCO R , CANTÍN Á , VIDAL-MOYA A , et al. Self-assembled aromatic molecules as efficient organic structure directing agents to synthesize the silicoaluminophosphate SAPO-42 with isolated Si species[J]. Chemistry of Materials, 2015, 27 (8): 2981- 2989.
11	饶小平, 宋湛谦, 高宏. 脱氢枞胺及其衍生物的研究与应用进展[J]. 化学通报, 2006, 69 (3): 168- 172.
	RAO X P , SONG Z Q , GAO H . Research and application progress on dehydroabietylamine and its derivatives[J]. Chemistry, 2006, 69 (3): 168- 172.
12	WIEMANN J , LOESCHE A , CSUK R . Novel dehydroabietylamine derivatives as potent inhibitors of acetylcholinesterase[J]. Bioorganic Chemistry, 2017, 74, 145- 157.
13	ZHAO F Y , WANG W F , LU W , et al. High anticancer potency on tumor cells of dehydroabietylamine Schiff-base derivatives and a copper(Ⅱ) complex[J]. European Journal of Medicinal Chemistry, 2018, 146, 451- 459.
14	PARAMESHA M , RAMESH C K , KRISHNA V , et al. Effect of dehydroabietylamine in angiogenesis and GSK3-β inhibition during wound healing activity in rats[J]. Medicinal Chemistry Research, 2015, 24 (1): 295- 303.
15	ASLAM A , HASHMI I A , AHMED V U , et al. Synthesis of supramolecular organogels derived from urea and bisurea derivatives of dehydroabietylamine[J]. Synthetic Communications, 2013, 43 (20): 2824- 2831.
16	LAAKSONEN T , HEIKKINEN S , WÄHLÄ K . Synthesis and applications of secondary a mine derivatives of (+)-dehydroabietylamine in chiral molecular recognition[J]. Organic & Biomolecular Chemistry, 2015, 13 (42): 10548- 10555.
17	WANG P , ZHAO Z D , BI L W , et al. Synthesis of mesoporous γ-Al₂O₃ templated with rosin-based quaternary ammonium salt by ammonia precipitation[J]. Asian Journal of Chemistry, 2012, 24 (8): 3439- 3444.
18	WANG P , CHEN S X , ZHAO Z D , et al. Synthesis of ordered porous SiO₂ with pores on the border between the micropore and mesopore regions using rosin-based quaternary ammonium salt[J]. RSC Advances, 2015, 5 (15): 11223- 11228.
19	WANG P , ZHAO Z D , BI L W , et al. Synthesis of mesoporous γ-Al₂O₃ using rosin-based quaternary ammonium salt as template agent[J]. Chemistry and Industry of Forest Products, 2012, 32 (2): 87- 91.
20	王鹏, 赵振东, 徐丽锋, 等. 松香基季铵盐引导合成高分散纤维状介孔γ-Al₂O₃[J]. 林产化学与工业, 2014, 34 (2): 29- 32.
	WANG P , ZHAO Z D , XU L F , et al. Synthesis of highly dispersed fibrous mesoporous γ-Al₂O₃ with rosin-based quaternary ammonium salt[J]. Chemistry and Industry of Forest Products, 2014, 34 (2): 29- 32.
21	YANG C , JIANG L H , ZHENG Y , et al. Use of pinene as a solvent for the synthesis of aluminophosphate and its application in the hydrogenation of pinene[J]. Microporous and Mesoporous Materials, 2020, 294, 109856.
22	YANG C , JIANG L H , WANG H B , et al. Process optimization for selective hydrogenation of α-pinene over Ni/AlPO₄[J]. Korean Journal of Chemical Engineering, 2018, 35 (2): 409- 420.
23	徐桦, 邵俊. 正磷酸铝高压下相变的分子动力学模拟[J]. 物理化学学报, 2000, 16 (6): 512- 516.
	XU H , SHAO J . Molecular dynamics simulation of the phase transition of α-berlinite under high pressure[J]. Acta Physico-Chimica Sinica, 2000, 16 (6): 512- 516.
24	李宝宗, 徐文国, 裘式纶, 等. 磷酸铝分子筛骨架结构及其稳定性的模拟计算(Ⅱ)——骨架结构中各类键长、键角的取值及其分布[J]. 高等学校化学学报, 1997, 18 (7): 1576- 1579.
	LI B Z , XU W G , QIU S L , et al. Simulated calculation of aluminophosphate molecular sieves structure and stability (Ⅱ):Bond lengths, bond angles and distribution of framework structure[J]. Chemical Journal of Chinese Universities, 1997, 18 (7): 1576- 1579.
25	LIU G , JIA M J , ZHOU Z , et al. Synthesis and pore formation study of amorphous mesoporous aluminophosphates in the presence of citric acid[J]. Journal of Colloid & Interface Science, 2006, 302 (1): 278- 286.
26	LIU G , JIA M J , ZHOU Z , et al. Synthesis of amorphous mesoporous aluminophosphate materials with high thermal stability using a citric acid route[J]. Chemical Communications, 2004, 10 (14): 1660- 1661.
27	LIU S G , DING Y Q , LI P F , et al. Adsorption of the anionic dye Congo red from aqueous solution onto natural zeolites modified with N, N-dimethyl dehydroabietyla mine oxide[J]. Chemical Engineering Journal, 2014, 248, 135- 144.
28	LIU B Y , LIU Z , HAN G C , et al. Synthesis, spectroscopic properties, crystal structure and density functional studies of Cu (Ⅱ) complex with 2-((dehydroabietyla mine) methyl)-6-methoxyphenol[J]. Journal of Molecular Structure, 2010, 975 (1): 194- 199.
29	SMIDT E , MEISSL K . The applicability of Fourier transform infrared (FT-IR) spectroscopy in waste management[J]. Waste Management, 2007, 27 (2): 268- 276.
30	WILSON H W . The infrared and Raman spectra of α- and β-pinenes[J]. Applied Spectroscopy, 1976, 30 (2): 209- 212.
31	AENUGU H P R , KUMAR D S , SRISUDHARSON , et al. Near infra red spectroscopy:An overview[J]. International Journal of Chemtech Research, 2011, 3 (2): 825- 836.
32	MAHMUD H N M E , KASSIM A , ZAINAL Z , et al. Fourier transform infrared study of polypyrrole-poly(vinyl alcohol) conducting polymer composite films:Evidence of film formation and characterization[J]. Journal of Applied Polymer Science, 2006, 100 (5): 4107- 4113.

样品 samples	时间/h duration	温度/℃ temperature	比表面积/(m²·g^-1) S_BET	平均孔径/nm average pore size	孔容/(cm³·g^-1) pore volume
a	4	160	19.18	5.24	0.05
c	4	180	260.80	3.23	0.58
d	4	190	158.38	3.03	0.37
e	4	200	113.33	3.88	0.26
f	4	210	73.84	3.92	0.17
g	1	170	35.77	6.13	0.07
h	2	170	79.21	5.44	0.10
i	3	170	253.69	3.12	0.64
j(b)	4	170	272.00	3.01	0.69
k	5	170	275.41	3.02	0.69

结构导向剂 SDA	溶剂 solvent	晶型 phase	形貌 morphology	比表面积/ (m²·g^-1) S_BET	孔容/ (cm³·g^-1) pore volume	平均孔径/nm pore size	文献 reference
去氢枞胺 dehydroabietyla mine	蒎烯 pinene	无定形/鳞石英 amorphous/tridymite	绵状聚集 sticky morphology	272	0.7	3.01	本研究 present
杂环芳胺 heterocyclic aromatic a mine	离子液体 [BMIm]Br	无定形/CHA amorphous/CHA	棒状聚集 stick-like shape				^[9]
芳香分子 aromatic molecule	水 H₂O	无定形/LTA amorphous/LTA	菱形 rhombohedral	600			^[10]
三乙胺 triethyla mine	蒎烯 pinene	AFI型 AFI topology	棱柱状 prism shape	297	0.3	3.3	^[21]
三乙醇胺 triethanola mine	蒎烯 pinene	鳞石英 tridymite	片状 flaky morphology	129	0.1	2.5	^[22]

[1]	李顺利,刘玉,黄飞,刘凯,陈洪雷. 基于木质纤维原料预水解过程同步合成碳纳米点[J]. 林产化学与工业, 2020, 40(3): 61-68.
[2]	伍锦秀,董勇,夏剑雨,陈妍,曹云峰,刘祝兰. 高吸液性木质纤维气凝胶的制备及表征[J]. 林产化学与工业, 2020, 40(3): 52-60.
[3]	南静娅,张盖同,王利军,储富祥,王春鹏. 大豆蛋白/聚丙烯酰胺复合水凝胶的制备及压缩回弹性能研究[J]. 林产化学与工业, 2020, 40(3): 45-51.
[4]	孙昊,赵大力,金彦任,刘艳艳,蒋剑春,邢浩洋. 活性炭孔隙结构对炭基金属氧化物催化剂HCN防护性能的影响[J]. 林产化学与工业, 2020, 40(3): 39-44.
[5]	张倩男,徐方敏,连之娜,李鑫,勇强. 柱前衍生反相高效液相色谱法测定田菁种子水解液中的单糖[J]. 林产化学与工业, 2020, 40(3): 31-38.
[6]	胡雨萌,侯敏杰,许苗军,李斌. 纤维素基一体化三明治结构超级电容器的制备及性能[J]. 林产化学与工业, 2020, 40(3): 23-30.
[7]	钟磊,王超,吕高金,吉兴香,杨桂花,陈嘉川. 低共熔溶剂在木质素分离方面的研究进展[J]. 林产化学与工业, 2020, 40(3): 12-22.
[8]	许倩,张晨,吴嘉维,欧阳嘉. 花青素的生物合成研究进展[J]. 林产化学与工业, 2020, 40(3): 1-11.
[9]	何云, 段文贵, 林桂汕, 岑波, 卜俊文, 雷福厚. 柠檬醛基缩氨基硫脲化合物的合成及除草活性[J]. 林产化学与工业, 2020, 40(3): 76-84.
[10]	邱金丹, 李璐, 魏敏平, 谢云飞, 于航, 姚卫蓉. 无患子果皮提取物化学成分及其对白色念珠菌的抑制作用[J]. 林产化学与工业, 2020, 40(3): 85-91.
[11]	杨小华, 丁海阳, 李守海, 许利娜, 林雅玫, 李梅. 桐油基非离子型自乳化水性环氧固化剂的制备及性能[J]. 林产化学与工业, 2020, 40(3): 92-98.
[12]	王鑫纯, 徐伟, 蒋建新, 朱莉伟. 野皂荚多糖氧化降解产物的体外代谢过程研究[J]. 林产化学与工业, 2020, 40(3): 99-107.
[13]	董爱文, 李维新, 王欢, 邹亚珂. 超临界CO₂萃取红麸杨果实中黄颜木素及其体外抗氧化活性研究[J]. 林产化学与工业, 2020, 40(3): 108-114.
[14]	侯兴隆, 郭奇, 建晓朋, 吴迪超, 许伟, 刘军利. 响应面法优化设计木质素基活性炭的制备[J]. 林产化学与工业, 2020, 40(3): 115-122.
[15]	齐志文, 周昊, 薛兴颖, 颜洋洋, 王成章. 三甲氧基没食子酸1,2,4-噻二唑-3,5-二酮衍生物的合成及其对HL60细胞增殖的抑制作用[J]. 林产化学与工业, 2020, 40(3): 123-129.