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PROGRESS IN ORGANIC COATINGS · 2020 · IF 4.469

Fluorinated diols modified polythiourethane copolymer for marine antifouling coatings

Songbo Xie,Jing Wang,Lida Wang,Wen Sun,Zhaoxia Lu,Guichang Liu,Baorong Hou

The development of environmentally friendly alternatives is a crucial issue, since the prohibition of tributyltin (TBT)-based antifouling coatings. In this work, a series of fluorinated diols modified polythiourethane (HO-FPTU-x) have been synthesized via a simple and convenient polymerization reaction with HDI, PETMP and various of 2,3,5,6-tetrafluoro-1,4-benzenedimethanol (HOCH 2 -FB-Al) at the room temperature, and their antifouling properties are explored as well. The laboratory assays and marine field tests (6 months) show that the HO-FPTU-7.5 (with 7.5 wt% HOCH 2 -FB-Al) coating has shown excellent antifouling/fouling release properties. The side chains of the HO-FPTU polymers simultaneously contain hydrophobic and hydrophilic groups, which construct an “ambiguous’’ surface after immersing into water. The marine organisms may be “confused’’ by the “ambiguous’’ surface and be removed easily during settlement and adhesion. This work provides a facile strategy for designing environment friendly marine antifouling coatings.

研究领域: 材料科学 · 海洋生物学
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Materials · 2023 ·Vol. 16 ·期 11 ·4040 · IF 3.4

Influence of Isocyanate Structure on Recyclable Shape Memory Poly(thiourethane)

Yu Zeng,Jiale Song,Jinfu Li,Chi Yuan

In this study, poly(thiourethane) (PTU) with different structures is synthesized by click chemistry from trimethylolpropane tris(3-mercaptopropionate) (S3) and different diisocyanates (hexamethylene diisocyanate, HDI, isophorone diisocyanate, IPDI and toluene diisocyanate, TDI). Quantitative analysis of the FTIR spectra reveals that the reaction rates between TDI and S3 are the most rapid, resulting from the combined influence of conjugation and spatial site hindrance. Moreover, the homogeneous cross-linked network of the synthesized PTUs facilitates better manageability of the shape memory effect. All three PTUs exhibit excellent shape memory properties (Rrand Rfare over 90%), and an increase in chain rigidity is observed to negatively impact the shape recovery rate and fix rate. Moreover, all three PTUs exhibit satisfactory reprocessability performance, and an increase in chain rigidity is accompanied by a greater decrease in shape memory and a smaller decrease in mechanical performance for recycled PTUs. Contact angle (<90°) and in vitro degradation results (13%/month for HDI-based PTU, 7.5%/month for IPDI-based PTU, and 8.5%/month for TDI-based PTU) indicate that PTUs can be used as long-term or medium-term biodegradable materials. The synthesized PTUs have a high potential for applications in smart response scenarios requiring specific glass transition temperatures, such as artificial muscles, soft robots, and sensors.

研究领域: 材料科学 · 生物学
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JOURNAL OF POLYMER SCIENCE · 2020 ·Vol. 58 ·期 8 ·1092-1104 · IF 0

Design and development of self-repairable and recyclable crosslinked poly(thiourethane-urethane) via enhanced aliphatic disulfide chemistry

Qing Liu,Yibin Liu,Hua Zheng,Chunmei Li,Yi Zhang,Qiuyu Zhang

Thermoset polymer elastomers that are capable of autonomous repairability upon physical damage at ambient temperature are highly desirable because of their thermal and environmental resistance, outstanding mechanical toughness and stability. To aim at this goal, we demonstrated that tris(diethylamino)phosphine was initially proven as an efficient catalyst for the aliphatic disulfide exchange at mild condition. By making use of the aliphatic disulfide bond reshuffling and elasticity of polyurethane elastomers, the inherently cross-linked polysulfide-based poly(thiourethane-urethane) elastomers were prepared and exhibited the ability to mend without extrinsic stimuli in the presence of phosphorus catalyst at room temperature after artificially damaged. The self-healing efficiency via the mechanical recovery approach was investigated to be mainly dependent upon the cross-linking density of polysulfide and hard segments chemistry, which in turns determined the molecular chain diffusion and reshuffling that was corroborated by the stress-relaxation study. The thermoset elastomer based on asymmetric diisocynate showed a maximum self-healing efficiency of 85.6% compared to 71.6% for the elastomer with symmetric monomer building blocks. The self-healable polymer was confirmed to be recyclable and reprocessable through a cut-compression processing cycle under a quite mild pressure and temperature thanks to the disulfide bond reshuffling. Meanwhile, the recycled thermoset elastomer well maintained the mechanical properties to its original material. Graphical In this study, a series of repairable polyurethane elastomers were synthesized utilizing the aliphatic polysulfide chemistry. The feasibility of the enhanced aliphatic disulfide bond exchange in the presence of tris(diethylamino)phosphine as an efficient catalyst was demonstrated. The elastomers exhibit fast self-reparability at room temperature due to the macromolecular network reshuffling of disulfide backbones. Recyclability and reprocessability of polysulfide-based thermoset elastomers through a cut-compression processing cycle at room temperature and mild pressure were also investigated.

研究领域: 材料科学 · 化学工程
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International Journal of Polymer Science · 2019 · IF 1.892

Cure Kinetics of an Optical Polythiourethane with Amine Catalyst by IR Analysis

Weiping Du,Guiming Zhang,Song Wang,Lianjiang Tan,Huifang Chen

An optical polythiourethane based on m-xylylene diisocyanate (XDI) and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (BES) has been studied. Triethylamine was adopted as a catalyst, and the solid-state isothermal cure reaction was carried out using FTIR spectroscopy, in the temperature range of 75°C-105°C. The -NCO absorption band of XDI was used to monitor the conversion of diisocyanate into polythiourethane. The reaction rate enhanced with an increase in the content of the catalyst, and the gel time determined by swelling test was shorter for the system with higher catalyst content. Kinetic parameters were calculated from the infrared spectrum data, and the results showed that the curing reaction of polythiourethane accords with first-order kinetic characteristics. The activation parameters obtained from the evaluation of kinetic data were , , and . The observed negative entropy of activation value supported the formation of a transition state in the cure reaction.

CAS / MDL: 68-12-2 121-44-8
研究领域: 材料科学 · 化学工程
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