Synthesis, structure and properties of high refrective index polythiourethane

doi:10.11949/0438-1157.20240654

Abstract

Abstract:

Polythiourethane, as a high refractive index optical resin, has excellent optical, thermal and mechanical properties and is widely used in the optoelectronic field. The effect of different monomer structures and monomer functional group ratios on the comprehensive performance of polythiourethane was studied. The results showed that the refractive index and dispersion degree of polythiourethane were closely related to their sulfur content and aromatic ring structure content. Adjusting the functional group ratio can increase the refractive index of high refractive index polythiourethane from 1.6848 to 1.6900. The thermal and mechanical properties of polythiourethane are influenced by various factors such as the rigidity of the monomer structure, the degree of functional groups, the uniformity of the cross-linking network, and the degree of reaction. Most of the prepared polythiourethane can be well applied in fields such as optical lenses and optical binders.

Key words: polythiourethane, high refractive index, optical resin, reaction, synthesis, polymers

摘要：

聚硫氨酯作为一种高折射率光学树脂，具有优异的光学、热学和力学性能，被广泛应用于光电领域。研究了不同单体结构和单体官能团比对聚硫氨酯综合性能的影响，结果表明，聚硫氨酯的折射率和色散程度与其含硫量和芳环结构含量有较大的关系，调整官能团比可使高折射率聚硫氨酯的折射率从1.6848上升至1.6900。聚硫氨酯的热学性能和力学性能受到单体结构刚性、官能团度、交联网络均匀程度和反应程度多个方面影响。制备的大部分聚硫氨酯都可以很好地满足光学透镜、光学黏结剂等领域的要求。

关键词: 聚硫氨酯, 高折射率, 光学树脂, 反应, 合成, 聚合物

CLC Number:

TQ 317.3

Xin YING, Miao DU, Pengju PAN, Guorong SHAN. Synthesis, structure and properties of high refrective index polythiourethane[J]. CIESC Journal, 2025, 76(2): 858-867.

应昕, 杜淼, 潘鹏举, 单国荣. 高折射率聚硫氨酯的合成、结构与性能[J]. 化工学报, 2025, 76(2): 858-867.

Figures/Tables 10

References 33

1	Zhou Y T, Zhu Z C, Zhang K, et al. Molecular structure and properties of sulfur-containing high refractive index polymer optical materials[J]. Macromolecular Rapid Communications, 2023, 44(23): e2300411.
2	Jang W, Choi K, Choi J S, et al. Transparent, ultrahigh-refractive index polymer film (n ∼1.97) with minimal birefringence (Δn <0.0010) [J]. ACS Applied Materials & Interfaces, 2021, 13(51): 61629-61637.
3	Zhang J, Bai T W, Liu W X, et al. All-organic polymeric materials with high refractive index and excellent transparency[J]. Nature Communications, 2023, 14(1): 3524.
4	Shim H, Monticone F, Miller O D. Fundamental limits to the refractive index of transparent optical materials[J]. Advanced Materials, 2021, 33(43): e2103946.
5	Huo N, Tenhaeff W E. High refractive index polymer thin films by charge-transfer complexation[J]. Macromolecules, 2023, 56(5): 2113-2122.
6	Xue S Y, Lei X F, Xiao Y Y, et al. Rapid, mild synthesis of transparent polyimides with high refractive index via thiol-Michael click reaction[J]. ACS Applied Polymer Materials, 2024, 6(4): 2315-2326.
7	Dan S M, Gu H M, Tan J J, et al. Transparent epoxy/TiO₂ optical hybrid films with tunable refractive index prepared via a simple and efficient way[J]. Progress in Organic Coatings, 2018, 120: 252-259.
8	Zhang Q Y, Goh E S M, Beuerman R, et al. Development of optically transparent ZnS/poly(vinylpyrrolidone) nanocomposite films with high refractive indices and high Abbe numbers[J]. Journal of Applied Polymer Science, 2013, 129(4): 1793-1798.
9	Xia Y, Zhang C, Wang J X, et al. Synthesis of transparent aqueous ZrO₂ nanodispersion with a controllable crystalline phase without modification for a high-refractive-index nanocomposite film[J]. Langmuir, 2018, 34(23): 6806-6813.
10	Mazumder K, Voit B, Banerjee S. Recent progress in sulfur-containing high refractive index polymers for optical applications[J]. ACS Omega, 2024, 9(6): 6253-6279.
11	Fang L X, Sun J, Chen X Y, et al. Phosphorus- and sulfur-containing high-refractive-index polymers with high T_g and transparency derived from a bio-based aldehyde[J]. Macromolecules, 2020, 53(1): 125-131.
12	Scheiger J M, Theato P. High Refractive Index Sulfur‐Containing Polymers (HRISPs)[M]. Germany: Wiley, 2021: 305-338.
13	Tang Y H, Pina-Hernandez C, Niu Q J, et al. A novel high-refractive index episulfide-thiol polymer for nanoimprinting optical elements[J]. Journal of Materials Chemistry C, 2018, 6(32): 8823-8831.
14	Su Y, Filho E B D S, Peek N, et al. High refractive index polymers (n > 1.7), based on thiol-ene cross-linking of polarizable P S and P Se organic/inorganic monomers[J]. Macromolecules, 2019, 52(22): 9012-9022.
15	Matsumura Y, Horikoshi H, Furukawa K, et al. Synthesis of bismuth-containing polymer films with high refractive index and X-ray shielding property by radical polymerization of styrylbismuthine derivatives[J]. ACS Macro Letters, 2022, 11(6): 723-726.
16	Badur T, Dams C, Hampp N. High refractive index polymers by design[J]. Macromolecules, 2018, 51(11): 4220-4228.
17	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.
18	Xue S Y, Lei X F, Xiao Y Y, et al. Highly refractive polyimides derived from efficient catalyst-free thiol-yne click polymerization[J]. Macromolecules, 2021, 54(24): 11256-11268.
19	Qu T F, Nan G M, Ouyang Y, et al. Structure-property relationship, glass transition, and crystallization behaviors of conjugated polymers[J]. Polymers, 2023, 15(21): 4268.
20	Gamardella F, De la Flor S, Ramis X, et al. Recyclable poly(thiourethane) vitrimers with high T_g. Influence of the isocyanate structure[J]. Reactive and Functional Polymers, 2020, 151: 104574.
21	Jia Y Y, Shi B J, Jin J S, et al. High refractive index polythiourethane networks with high mechanical property via thiol-isocyanate click reaction[J]. Polymer, 2019, 180: 121746.
22	Zhang Y W, Wang Y S, Chen Y Y, et al. High-refractive index polythiourethane resin based on 2,3-bis((2-mercaptoethyl) thio)-1-propanethiol and 1,3-bis(isocyanantomethyl) cyclohexane using tertiary amine catalyst[J]. Journal of Applied Polymer Science, 2021, 138(17): e50278.
23	Liu J, Shi Y J, Li J J, et al. Closed-loop recyclable vinylogous carbamothioate-based covalent adaptable networks[J]. Macromolecules, 2023, 56(17): 6644-6654.
24	Kultys A, Puszka A. Transparent poly(thiourethane-urethane)s based on dithiol chain extender[J]. Journal of Thermal Analysis and Calorimetry, 2014, 117(3): 1427-1439.
25	Jeong J E, Lee J W, Bae M J, et al. NIR-triggered high-efficiency self-healable protective optical coating for vision systems[J]. ACS Applied Materials & Interfaces, 2023, 15(6): 8510-8520.
26	Chen Y Y, Qin Z Y, Tang G F, et al. Balancing optical property and enhancing stability for high-refractive index polythiourethane with assistance of cubic thiol-functionalized silsesquioxanes[J]. ACS Applied Polymer Materials, 2021, 3(1): 153-161.
27	Erice A, Ruiz de Luzuriaga A, Azcune I, et al. New injectable and self-healable thermoset polythiourethane based on S-aromatic thiourethane dissociative exchange mechanism[J]. Polymer, 2020, 196: 122461.
28	Zeng Y L, Fan L, Deng M, et al. Development of high refractive and high water content polythiourethane/AA hydrogels for potential artificial cornea implants[J]. International Journal of Polymeric Materials and Polymeric Biomaterials, 2020, 69(9): 580-591.
29	慎政焕, 明正焕, 沈钟珉, 等. 聚硫氨酯类塑料镜: 111566518A[P]. 2020-08-21.
	Shen Z H, Ming Z H, Shen Z M, et al. Polythiourethane plastic lens: 111566518A[P]. 2020-08-21.
30	刘洋, 张建林, 曹帅, 等. 一种高折射率超韧光学树脂材料及其制备方法: 113444247A[P]. 2021-09-28.
	Liu Y, Zhang J L, Cao S, et al. A high refractive index ultra tough optical resin material and its preparation method: 113444247A[P]. 2021-09-28.
31	张建林, 曹飞羽, 易先君, 等. 光学树脂单体及其制备方法、光学树脂及其制备方法: 111763320B[P]. 2021-09-10.
	Zhang J L, Cao F Y, Yi X J, et al. Optical resin monomer and its preparation method, optical resin and its preparation method: 111763320B[P]. 2021-09-10.
32	孔凡波, 梁万根, 张建林, 等. 一种高折射率光学树脂材料、其制备方法及应用: 117362565A[P]. 2024-01-09.
	Kong F B, Liang W G, Zhang J L, et al. A high refractive index optical resin material, its preparation method and application: 117362565A[P]. 2024-01-09.
33	尚永华, 朱付林, 张文强, 等. 一种环己烷二亚甲基二异氰酸酯组合物、改性组合物及聚氨酯树脂和光学树脂: 117801222A[P]. 2024-04-02.
	Shang Y H, Zhu F L, Zhang W Q, et al. A cyclohexane dimethyl diisocyanate composition, modified composition, polyurethane resin, and optical resin: 117801222A[P]. 2024-04-02.

Property	PTU1	PTU2	PTU3	PTU4	PTU5	PTU6
composition	BES-XDI	BES-TDI	BES-MDI	PETMP-XDI	PETMP-MDI	BMMD-XDI
sulf content/%(mass)	29.48	30.66	25.16	14.80	12.94	25.87
refractive index（589 nm）	1.6560	1.6785	1.6862	1.5912	1.6261	1.6596
Abbe’s number	31.31	25.53	23.90	34.44	24.81	32.25
total transmittance/%	87.67±0.64	86.81±0.77	86.48±0.75	89.20±0.58	84.42±0.86	87.11±0.73
haze/%	0.22±0.08	4.1±0.13	0.06±0.02	2.07±0.09	18.78±0.20	0.71±0.11
λ_UV/nm	290	320	313	285	317	282
T_g(DSC)/℃	69.6	122.5	125.3	70.9	124.3	98.4
T_g(DMA)/℃	96.6	122.4	140.7	99.1	80.7/134.7	—
FWHM/℃	14.4	31.8	23.2	11.6	46.4/29.3	—
T_d5%/℃	280	262.1	268.6	290.6	279.6	282.9
T_dmax/℃	301.7	283.9	295.4	303.4	350.8	312.3
tensile strength/MPa	104.74±9.32	50.31±4.01	79.57±4.12	94.46±9.52	79.74±1.58	—
tensile strength at break/MPa	104.74±9.32	50.31±4.01	79.57±4.12	63.80±3.38	69.50±3.94	—
tensile strain at break/%	10.04±1.54	4.78±1.37	13.07+2.91	16.55±2.27	27.86±3.29	—
tensile yield strength/MPa	—	—	—	94.46±9.52	79.74±1.58	—
tensile strain at yield/%	—	—	—	9.92±0.49	11.61±0.45	—
pencil hardness	2H	2H	2H	2H	2H	3H
density/(g/cm³)	1.3633	1.3783	1.3417	1.3958	1.3846	1.4230
contact angle/(°)	94.87±2.28	94.02±5.34	92.35±3.47	94.52±1.18	77.24±1.69	83.95±0.69

Property	PTU1	PTU2	PTU3	PTU4	PTU5	PTU6
composition	BES-XDI	BES-TDI	BES-MDI	PETMP-XDI	PETMP-MDI	BMMD-XDI
sulf content/%(mass)	29.48	30.66	25.16	14.80	12.94	25.87
refractive index（589 nm）	1.6560	1.6785	1.6862	1.5912	1.6261	1.6596
Abbe’s number	31.31	25.53	23.90	34.44	24.81	32.25
total transmittance/%	87.67±0.64	86.81±0.77	86.48±0.75	89.20±0.58	84.42±0.86	87.11±0.73
haze/%	0.22±0.08	4.1±0.13	0.06±0.02	2.07±0.09	18.78±0.20	0.71±0.11
λ_UV/nm	290	320	313	285	317	282
T_g(DSC)/℃	69.6	122.5	125.3	70.9	124.3	98.4
T_g(DMA)/℃	96.6	122.4	140.7	99.1	80.7/134.7	—
FWHM/℃	14.4	31.8	23.2	11.6	46.4/29.3	—
T_d5%/℃	280	262.1	268.6	290.6	279.6	282.9
T_dmax/℃	301.7	283.9	295.4	303.4	350.8	312.3
tensile strength/MPa	104.74±9.32	50.31±4.01	79.57±4.12	94.46±9.52	79.74±1.58	—
tensile strength at break/MPa	104.74±9.32	50.31±4.01	79.57±4.12	63.80±3.38	69.50±3.94	—
tensile strain at break/%	10.04±1.54	4.78±1.37	13.07+2.91	16.55±2.27	27.86±3.29	—
tensile yield strength/MPa	—	—	—	94.46±9.52	79.74±1.58	—
tensile strain at yield/%	—	—	—	9.92±0.49	11.61±0.45	—
pencil hardness	2H	2H	2H	2H	2H	3H
density/(g/cm³)	1.3633	1.3783	1.3417	1.3958	1.3846	1.4230
contact angle/(°)	94.87±2.28	94.02±5.34	92.35±3.47	94.52±1.18	77.24±1.69	83.95±0.69

Property	1	2	3	4	5	6	7	8	9
—SH/—NCO	0.90	0.95	1.00	1.05	1.10	1.20	1.30	1.40	1.50
refractive index（589 nm）	1.6848	1.6859	1.6862	1.6871	1.6880	1.6886	1.6895	1.6898	1.6900
Abbe’s number	23.48	23.48	23.90	23.95	24.00	24.35	24.05	24.41	24.46
total transmittance/%	86.62±0.83	86.50±0.69	86.48±0.75	86.48±0.62	86.35±0.87	86.34±0.93	86.50±0.76	86.20±0.68	86.36±0.91
Haze/%	0.09±0.02	0.17±0.04	0.06±0.04	0.04±0.03	0.16±0.05	0.50±0.08	0.59±0.06	0.47±0.09	1.57±0.10
λ_UV/nm	313	313	313	312	312	311	311	311	311
T_g(DSC)/℃	131.3	127.8	125.3	119.9	119.4	101.1	98.0	89.7	69.4
T_g(DMA)/℃	153.3	147.2	139.5	131.9	129.1	116.6	107.2	102.3	89.7
FWHM/℃	33.5	38.7	36.0	30.0	28.5	23.3	19.7	17.5	19.1
T_d5%/℃	266.3	268.6	268.6	268.0	271.8	270.5	269.2	269.0	266.2
T_dmax/℃	290.1	292.5	295.4	293.6	297.1	290.1	290.9	287.6	286.0
tensile strength/MPa	60.31±3.25	72.06±3.42	79.57±4.12	77.73±5.18	73.28±4.72	72.12±2.21	68.69±3.35	67.48±3.72	37.48±3.80
tensile strain at break/%	7.45±1.66	8.37±1.58	13.07±2.91	15.7±3.13	17.42±2.68	16.84±3.89	11.58±1.73	6.89±1.76	4.02±1.30
pencil hardness	2H	2H	2H	2H	2H	2H	H	H	HB
density/(g/cm³)	1.3356	1.3392	1.3417	1.3463	1.3497	1.3573	1.3625	1.3686	1.3715
contact angle/(°)	91.60±2.15	100.03±1.76	92.35±3.47	95.34±1.38	98.17±1.24	93.94±2.91	90.95±1.79	101.39±1.21	97.30±1.41

Property	1	2	3	4	5	6	7	8	9
—SH/—NCO	0.90	0.95	1.00	1.05	1.10	1.20	1.30	1.40	1.50
refractive index（589 nm）	1.6848	1.6859	1.6862	1.6871	1.6880	1.6886	1.6895	1.6898	1.6900
Abbe’s number	23.48	23.48	23.90	23.95	24.00	24.35	24.05	24.41	24.46
total transmittance/%	86.62±0.83	86.50±0.69	86.48±0.75	86.48±0.62	86.35±0.87	86.34±0.93	86.50±0.76	86.20±0.68	86.36±0.91
Haze/%	0.09±0.02	0.17±0.04	0.06±0.04	0.04±0.03	0.16±0.05	0.50±0.08	0.59±0.06	0.47±0.09	1.57±0.10
λ_UV/nm	313	313	313	312	312	311	311	311	311
T_g(DSC)/℃	131.3	127.8	125.3	119.9	119.4	101.1	98.0	89.7	69.4
T_g(DMA)/℃	153.3	147.2	139.5	131.9	129.1	116.6	107.2	102.3	89.7
FWHM/℃	33.5	38.7	36.0	30.0	28.5	23.3	19.7	17.5	19.1
T_d5%/℃	266.3	268.6	268.6	268.0	271.8	270.5	269.2	269.0	266.2
T_dmax/℃	290.1	292.5	295.4	293.6	297.1	290.1	290.9	287.6	286.0
tensile strength/MPa	60.31±3.25	72.06±3.42	79.57±4.12	77.73±5.18	73.28±4.72	72.12±2.21	68.69±3.35	67.48±3.72	37.48±3.80
tensile strain at break/%	7.45±1.66	8.37±1.58	13.07±2.91	15.7±3.13	17.42±2.68	16.84±3.89	11.58±1.73	6.89±1.76	4.02±1.30
pencil hardness	2H	2H	2H	2H	2H	2H	H	H	HB
density/(g/cm³)	1.3356	1.3392	1.3417	1.3463	1.3497	1.3573	1.3625	1.3686	1.3715
contact angle/(°)	91.60±2.15	100.03±1.76	92.35±3.47	95.34±1.38	98.17±1.24	93.94±2.91	90.95±1.79	101.39±1.21	97.30±1.41

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