Study on molecular weight-refractive index model of polymethylphenylsiloxane

doi:10.11949/0438-1157.20230735

Abstract

Abstract:

Polysiloxane is a special silicone material that is widely used. The refractive index is an important indicator for measuring the performance of polysiloxane. A molecular weight-refractive index model suitable for polymethylphenylsiloxanes has been established by using the group contribution method and optimized based on the free volume theory. The optimized model can effectively predict the refractive index of polymethylphenylsiloxanes from molecular weight and temperature, with a relative error within ±0.2%. The influence of molecular weight and temperature on refractive index has been explained by the optimized model: the refractive index increases with the increase of molecular weight and eventually tends to a certain value; the refractive index decreases significantly with the increase of temperature. The relevant results are significant for the design and synthesis of polysiloxanes with high refractive index.

Key words: group contribution, refractive index, model, polymethylphenylsiloxane, molecular weight

摘要：

聚硅氧烷是应用广泛的一种特种有机硅材料，折射率是衡量聚硅氧烷性能的重要指标。应用基团贡献法建立了适用于聚苯基甲基硅氧烷体系的分子量-折射率模型，结合自由体积理论对模型进行了修正。修正后的模型能够根据分子量和温度有效地预测聚苯基甲基硅氧烷的折射率，相对误差在±0.2%范围内。根据修正后的模型阐述了分子量、温度对折射率的影响：折射率随着分子量的增大而升高，最终趋于一定值；折射率随着温度的升高明显下降。研究结果可为高折射率聚硅氧烷的设计与合成提供参考。

关键词: 基团贡献, 折射率, 模型, 聚苯基甲基硅氧烷, 分子量

CLC Number:

TQ 314.2

Donglin ZHONG, Suyun JIE, Miao DU, Pengju PAN, Guorong SHAN. Study on molecular weight-refractive index model of polymethylphenylsiloxane[J]. CIESC Journal, 2024, 75(1): 190-196.

钟东霖, 介素云, 杜淼, 潘鹏举, 单国荣. 聚苯基甲基硅氧烷分子量-折射率模型研究[J]. 化工学报, 2024, 75(1): 190-196.

Figures/Tables 9

References 34

1	Shi J F, Zhao N, Xia S, et al. Phosphazene superbase catalyzed ring-opening polymerization of cyclotetrasiloxane toward copolysiloxanes with high diphenyl siloxane content[J]. Polymer Chemistry, 2019, 10(17): 2126-2133.
2	Wolf M P, Salieb-Beugelaar G B, Hunziker P. PDMS with designer functionalities—properties, modifications strategies and applications[J]. Progress in Polymer Science, 2018, 83: 97-134.
3	Maiti A, Small W, Kroonblawd M P, et al. Constitutive model of radiation aging effects in filled silicone elastomers under strain[J]. The Journal of Physical Chemistry B, 2021, 125(35): 10047-10057.
4	Razavi M, Primavera R, Vykunta A, et al. Silicone-based bioscaffolds for cellular therapies[J]. Materials Science and Engineering: C, 2021, 119: 111615.
5	Zhang X S, Chen Y J, Hu J L. Recent advances in the development of aerospace materials[J]. Progress in Aerospace Sciences, 2018, 97: 22-34.
6	Zalewski K, Chyłek Z, Trzciński W A. A review of polysiloxanes in terms of their application in explosives[J]. Polymers, 2021, 13(7): 1080.
7	Tian H Y, Tang Z H, Zhuang X L, et al. Biodegradable synthetic polymers: preparation, functionalization and biomedical application[J]. Progress in Polymer Science, 2012, 37(2): 237-280.
8	Pan Z Q, Cheng Y, Zhang Z. Synthesis of high refractive index silicone LED encapsulation with ultra-high hardness[J]. Silicon, 2022, 14(13): 7863-7870.
9	Muthamil S T, Mondal T. Radiation curable polysiloxane: synthesis to applications[J]. Soft Matter, 2021, 17(26): 6284-6297.
10	Meier D, Huch V, Kickelbick G. Aryl-group substituted polysiloxanes with high-optical transmission, thermal stability, and refractive index[J]. Journal of Polymer Science, 2021, 59(20): 2265-2283.
11	Lay M, Ramli M R, Ramli R, et al. Crosslink network and phenyl content on the optical, hardness,and thermal aging of PDMS LED encapsulant[J]. Journal of Applied Polymer Science, 2019, 136(34): 47895.
12	Tan C Z. Dependence of the refractive index on density, temperature and the wavelength of the incident light[J]. The European Physical Journal B, 2021, 94(7): 139.
13	Tao Z. Effect of magnetic field of light on refractive index[J]. Chinese Physics, 2004, 13(8): 1358-1364.
14	Gharagheizi F, Ilani-Kashkouli P, Kamari A, et al. A chemical structure based model for the estimation of refractive indices of organic compounds[J]. Fluid Phase Equilibria, 2014, 384: 1-13.
15	Xu J, Chen B, Zhang Q J, et al. Prediction of refractive indices of linear polymers by a four-descriptor QSPR model[J]. Polymer, 2004, 45: 8651-8659.
16	Khan P M, Rasulev B, Roy K. QSPR modeling of the refractive index for diverse polymers using 2D descriptors[J]. ACS Omega, 2018, 3(10): 13374-13386.
17	Hamadanian M, Keshavarz M H, Shahrousvand E. The reliable predicting refractive index for diverse polymers only from structural moieties in repeating unit structures[J]. Materials Today Communications, 2023, 35: 105823.
18	Jabeen F, Chen M, Rasulev B, et al. Refractive indices of diverse data set of polymers: a computational QSPR based study[J]. Computational Materials Science, 2017, 137: 215-224.
19	Yang C J, Jenekhe S A. Group contribution to molar refraction and refractive index of conjugated polymers[J]. Chemistry of Materials, 1995, 7(7): 1276-1285.
20	Cai C, Marsh A, Zhang Y H, et al. Group contribution approach to predict the refractive index of pure organic components in ambient organic aerosol[J]. Environmental Science & Technology, 2017, 51(17): 9683-9690.
21	Gharagheizi F, Ilani-Kashkouli P, Kamari A, et al. Group contribution model for the prediction of refractive indices of organic compounds[J]. Journal of Chemical & Engineering Data, 2014, 59(6): 1930-1943.
22	程大海, 伍川, 董红, 等. 原子贡献法估算硅烷及硅氧烷的摩尔折射度[J]. 杭州师范大学学报(自然科学版), 2013, 12(5): 395-403.
	Cheng D H, Wu C, Dong H, et al. The molar refraction estimation of silanes and siloxanes by atom contribution method[J]. Journal of Hangzhou Normal University(Natural Science Edition), 2013, 12(5): 395-403.
23	程大海, 伍川, 董红, 等. 基团贡献法预测硅烷及硅氧烷的折射率[J]. 杭州师范大学学报(自然科学版), 2014, 13(2): 113-122.
	Cheng D H, Wu C, Dong H, et al. Prediction for the refractive index of silane and siloxane by group contribution method[J]. Journal of Hangzhou Normal University (Natural Science Edition), 2014, 13(2): 113-122.
24	Katritzky A R, Sild S, Karelson M. General quantitative structure-property relationship treatment of the refractive index of organic compounds[J]. Journal of Chemical Information and Computer Sciences, 1998, 38(5): 840-844.
25	Kragh H. The Lorenz-Lorentz formula: origin and early history[J]. Substantia. An International Journal of the History of Chemistry, 2018, 2(2): 7-18.
26	蒋立纯, 方仕江. 具有高折光率的苯基乙烯基硅油的合成与表征[J]. 化工新型材料, 2014, 42(2): 136-138, 148.
	Jiang L C, Fang S J. Synthesis and characterization of methyl phenyl vinyl silicone oil with high refractive index[J]. New Chemical Materials, 2014, 42(2): 136-138, 148.
27	李谷, 符若文, 冯开才. 高分子物理[M]. 北京: 化学工业出版社, 2005.
	Li G, Fu R W, Feng K C. Polymer Physics[M]. Beijing: Chemical Industry Press, 2005.
28	Ihmels E C, Gmehling J. Extension and revision of the group contribution method GCVOL for the prediction of pure compound liquid densities[J]. Industrial & Engineering Chemistry Research, 2003, 42(2): 408-412.
29	Wang Y M, Cao R W, Wang M H, et al. Design and synthesis of phenyl silicone rubber with functional epoxy groups through anionic copolymerization and subsequent epoxidation[J]. Polymer, 2020, 186: 122077.
30	Fuchise K, Igarashi M, Sato K, et al. Organocatalytic controlled/living ring-opening polymerization of cyclotrisiloxanes initiated by water with strong organic base catalysts[J]. Chemical Science, 2018, 9(11): 2879-2891.
31	周安安, 单国荣, 黄志明, 等. 羟基聚硅氧烷一步合成的速率研究[J]. 化学反应工程与工艺, 2004, 20(1): 53-58.
	Zhou A A, Shan G R, Huang Z M, et al. Study on the rate for preparing hydroxy terminated polydimethylsiloxane in one-step process in the presence of water[J]. Chemical Reaction Engineering and Technology, 2004, 20(1): 53-58.
32	夏爽, 刘小兵, 赵娜, 等. 环硅氧烷阴离子开环均聚及共聚研究进展[J]. 高分子学报, 2018(12): 1482-1492.
	Xia S, Liu X B, Zhao N, et al. Progress in anionic ring-opening homo/co-polymerization of cyclosiloxanes[J]. Acta Polymerica Sinica, 2018(12): 1482-1492.
33	Doolittle A K. Studies in Newtonian flow(Ⅱ): The dependence of the viscosity of liquids on free-space[J]. Journal of Applied Physics, 1951, 22(8): 1471-1475.
34	郑强, 林宇, 叶一兰, 等. 《高分子物理》教学中WLF方程的系数求解与分析[J]. 高分子通报, 2010(6): 99-105.
	Zheng Q, Lin Y, Ye Y L, et al. The solution and analysis on parameters of WLF equation in teaching the course Polymer Physics[J]. Polymer Bulletin, 2010(6): 99-105.

Molecular weight	Refractive index
Molecular weight	30℃	40℃	50℃	60℃
3058	1.5202	1.5168	1.5136	1.5098
5552	1.5336	1.5298	1.5269	1.5236
8264	1.5401	1.5361	1.5324	1.5286
10075	1.5415	1.5376	1.5340	1.5301
13794	1.5441	1.5409	1.5383	1.5347
18843	1.5460	1.5417	1.538	1.5345
20999	1.5464	1.5433	1.5408	1.5370
28253	1.5475	1.5437	1.5405	1.5366
46634	1.5495	1.5459	1.5418	1.5387

Molecular weight	Refractive index
Molecular weight	30℃	40℃	50℃	60℃
3058	1.5202	1.5168	1.5136	1.5098
5552	1.5336	1.5298	1.5269	1.5236
8264	1.5401	1.5361	1.5324	1.5286
10075	1.5415	1.5376	1.5340	1.5301
13794	1.5441	1.5409	1.5383	1.5347
18843	1.5460	1.5417	1.538	1.5345
20999	1.5464	1.5433	1.5408	1.5370
28253	1.5475	1.5437	1.5405	1.5366
46634	1.5495	1.5459	1.5418	1.5387

Temperature/℃	f
30	0.019
40	0.022
50	0.024
60	0.026

Temperature/℃	f
30	0.019
40	0.022
50	0.024
60	0.026

Molecular weight	Refractive index
	30℃		40℃		50℃		60℃
	Exp.	Pred.	Exp.	Pred.	Exp.	Pred.	Exp.	Pred.
6575	1.5377	1.5376	1.5346	1.5349	1.5311	1.5313	1.5283	1.5268
10163	1.5409	1.5410	1.5371	1.5384	1.5335	1.5349	1.5299	1.5303
12097	1.5428	1.5420	1.5394	1.5395	1.5359	1.5359	1.5321	1.5314
14907	1.5439	1.5430	1.5402	1.5405	1.5360	1.5369	1.5328	1.5324
26201	1.5470	1.5449	1.5431	1.5424	1.5392	1.5389	1.5359	1.5344