A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The su...A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The surface property of the copolymer films was subsequently characterized. The contact angle measurements and energy dispersive analysis of X-ray （EDAX） show that the length and content of perfluoroalkyl side chains in the copolymers are crucial for the preparation of the film with low surface energy. At a given content of fluorinated monomers in the copolymers, the longer the perfluoroalkyl side chain, the larger the water contact angle of the copolymer films will be. On the other hand, the higher the content of fluorinated monomers, the lower the surface energy is. The water contact angle increases with the increase of the fluorinated monomer content and reaches a plateau at 3 wt% of fluorinated monomer content.展开更多
A linear fluorinated benzocyclobutene-type monomer(4F-bis-BCB) was facilely synthesized by a one-step copper-catalyzed etherification reaction and a simple precipitation post-purification method.Moreover,a series of B...A linear fluorinated benzocyclobutene-type monomer(4F-bis-BCB) was facilely synthesized by a one-step copper-catalyzed etherification reaction and a simple precipitation post-purification method.Moreover,a series of BCB-based polymeric low-dielectric(low-k)materials were obtained by the thermal-induced ring-opening copolymerization of 4F-bis-BCB with divinyl tetramethyl disiloxanebisbenzocyclobutene(DVS-BCB) monomer and further simple thermal curing at high temperature(200-300℃).The resultant fully cured materials demonstrated excellent low dielectric properties at high frequency of 10 GHz(dielectric constant(D_(k))<2.6,dielectric loss(D_(f))<1.57×10^(-2)),great hydrophobicity(water contact angle>116°),ultra-low water absorption(<0.19% after soaked in water at room temperature for 60 h) and excellent planarization ability(surface roughness<0.56 nm of 3 μm-thick film).Overall,this new fluorinated BCB-type monomer provides us an alternative for the facile preparation of low-k polymeric materials and exhibits great potential for future applications in high-frequency communication and three-dimensional high-density packaging technologies.展开更多
Cationic fluorinated acrylate latex was prepared via semi-continuous emulsion copolymerization of cationic monomer and other monomers. The resultant latex and its film were characterized with dynamic light scattering ...Cationic fluorinated acrylate latex was prepared via semi-continuous emulsion copolymerization of cationic monomer and other monomers. The resultant latex and its film were characterized with dynamic light scattering detector and contact angle meter. Influences of amount of DMDAAC on the properties of resultant latex and its film were investigated in detail. Results show that the particle size of the latex has the minimum value knd the zeta potential of the latex is increased when the amount of DMDAAC is increased. In addition, the particle size of the latex is unimodal distribution when the amount of DMDAAC is not more than 2.5%. However, the particle size of the latex is bimodal distribution when the amount of DMDAAC is more than 2.5%. The contact angle is varied slightly with the increase of amount of DMDAAC when it is not more than 2.5%. Nevertheless, the contact angle is decreased with the increase of the amount of DMDAAC when it is more than 2.5%.展开更多
Fluorinated liquid crystal monomers(LCMs)are begun to emerge as new persistent organic pollutants.Herein,the structure-reactivity relationships of fluorinated LCMs 1,2,3-trifluoro-5-[3-(3-propylcyclohexyl)cyclohexyl]b...Fluorinated liquid crystal monomers(LCMs)are begun to emerge as new persistent organic pollutants.Herein,the structure-reactivity relationships of fluorinated LCMs 1,2,3-trifluoro-5-[3-(3-propylcyclohexyl)cyclohexyl]benzene(TPrCB),1,2-difluoro-4-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]benzene(DPrCB),4-[(trans,trans)-4'-(3-Buten-1-yl)[1,10-bicyclohexyl]-4-yl]-1,2-difluoro-benzene(BBDB)and 1-[4-(4-ethylcyclohexyl)cyclohexyl]-4(trifluoromethoxy)benzene(ECTB)subject to photocatalysis-generated oxidation species were investigated.The degradation rate constant of BBDB was 3.0,2.6,and 6.8 times higher than DPrCB,TPrCB and ECTB,respectively.The results reveal that BBDB,DPrCB and TPrCB had mainly negative electrostatic potential(ESP)regions which were vulnerable to electrophilic attack by h^(+),·OH and·O_(2)^(-),while ECTB was composed of mainly positive ESP regions which were vulnerable to nucleophilic attack by·OH and·O_(2)^(-).The detoxification processes of BBDB,DPrCB and TPrCB included carbon bond cleavage and benzene ring opening.However,the methoxy group of ECTB reduced the nucleophilic reactivity on the benzene ring,leading to slower detoxification efficiency.These findings may help to develop LCMs treatment technologies based on structure-reactivity relationships。展开更多
Fluorinated polymers exhibit a unique combination of attributes,including chemical inertness,low surface energy,exceptional weather resistance,and intriguing electrical properties.This mini review provides an overview...Fluorinated polymers exhibit a unique combination of attributes,including chemical inertness,low surface energy,exceptional weather resistance,and intriguing electrical properties.This mini review provides an overview of recent advancements in the research of fluorinated polymers,highlighting the development of synthetic strategies for novel fluorinated polymers and their diverse applications in various fields.Traditional fluorinated polyolefins can be modified through chemical methods to produce functional materials.Copolymerization of fluorinated olefins with non-fluorinated monomers effectively addresses synthesis challenges,yielding main-chain fluoro-containing polymers with specific functional groups.Additionally,recent studies have revealed that free radical(co)polymerization of fluorinated(meth)acrylate monomers leads to new fluorinated polymers with enhanced solubility,processability,and structural diversity.Capitalizing on these new synthetic strategies,a range of fluorinated polymer materials has been developed for a multitude of applications,including flexible electrodes,alternating current(AC)electroluminescent devices,energy storage capacitors,triboelectric nanogenerators,and lithium batteries.With their customized structures and excellent properties,fluorinated polymers hold significant promise to uncover more potential applications in the era of flexible and wearable electronics.展开更多
In this paper, we combined high-end cationic UV-curable material with fluorinated chain obtaining a series of new fluorine-containing aromatic oxetane monomers via a mild nucleophilic substitution reaction. The struct...In this paper, we combined high-end cationic UV-curable material with fluorinated chain obtaining a series of new fluorine-containing aromatic oxetane monomers via a mild nucleophilic substitution reaction. The structures and properties of monomers were characterized using ~1 H-NMR, ^（19） F-NMR, dynamic viscosity tests and differential scanning calorimetry（DSC）. It was determined that all of the fluorinated monomers obtained had much lower viscosity and higher thermostability after the introduction of hexafluorobenzene. Then, UV-curable coatings were prepared using four fluorine-containing aromatic oxetane monomers（FOX1-4）; the UV-curing kinetics, with three kinds of initiators, and properties of the cured films were evaluated using real-time Fourier transform infrared（FTIR） spectroscopy, water and diiodomethane contact angle tests, surface energy calculations and scanning electron microscopy（SEM）. The FTIR spectroscopy results showed that the coatings possessed excellent conversion rate（〉 99% with liquid initiator PAG-201 in 150 s）, and as the fluorine content increased, the monomers exhibited decreased mobility with the increasing viscosity and worse solubility with fluorinated monomers, resulting in a lower conversion rate. Moreover, the coatings possessed favorable hydrophobic and oleophobic properties and low surface energies owing to the fluoride chains floating to the membrane-air interface, which was also confirmed by discrete concave structures in SEM images. These new kinds of monomers can replace traditional fluorinated cationic monomers applied to the fingerprint resistant, fouling resistant, scratch resistant and anti-aging coatings, adhesives or printing ink materials.展开更多
基金This work was partly supported by the National Natural Science Foundation of China (No. 50273008)Qingdao Municipal Science and Technology Commission.
文摘A series of copolymers comprising butylmethacrylate, styrene, butylacrylate, hydroxypropyl acrylate and perfluoroalkyl methacrylate were synthesized by the free radical polymerization using BPO as an initiator. The surface property of the copolymer films was subsequently characterized. The contact angle measurements and energy dispersive analysis of X-ray （EDAX） show that the length and content of perfluoroalkyl side chains in the copolymers are crucial for the preparation of the film with low surface energy. At a given content of fluorinated monomers in the copolymers, the longer the perfluoroalkyl side chain, the larger the water contact angle of the copolymer films will be. On the other hand, the higher the content of fluorinated monomers, the lower the surface energy is. The water contact angle increases with the increase of the fluorinated monomer content and reaches a plateau at 3 wt% of fluorinated monomer content.
基金the National Natural Science Foundation of China(No.22075298)the Beijing Municipal Natural Science Foundation(No.2212053)。
文摘A linear fluorinated benzocyclobutene-type monomer(4F-bis-BCB) was facilely synthesized by a one-step copper-catalyzed etherification reaction and a simple precipitation post-purification method.Moreover,a series of BCB-based polymeric low-dielectric(low-k)materials were obtained by the thermal-induced ring-opening copolymerization of 4F-bis-BCB with divinyl tetramethyl disiloxanebisbenzocyclobutene(DVS-BCB) monomer and further simple thermal curing at high temperature(200-300℃).The resultant fully cured materials demonstrated excellent low dielectric properties at high frequency of 10 GHz(dielectric constant(D_(k))<2.6,dielectric loss(D_(f))<1.57×10^(-2)),great hydrophobicity(water contact angle>116°),ultra-low water absorption(<0.19% after soaked in water at room temperature for 60 h) and excellent planarization ability(surface roughness<0.56 nm of 3 μm-thick film).Overall,this new fluorinated BCB-type monomer provides us an alternative for the facile preparation of low-k polymeric materials and exhibits great potential for future applications in high-frequency communication and three-dimensional high-density packaging technologies.
基金supported by the Science and Technology Department of Zhejiang Province under Grant No. 2010C31040the financial support of Zhejiang Provincial Natural Science Foundation of China(No. Y4100152)Zhejiang University of Technology Natural Science Foundation(No.20100202)
文摘Cationic fluorinated acrylate latex was prepared via semi-continuous emulsion copolymerization of cationic monomer and other monomers. The resultant latex and its film were characterized with dynamic light scattering detector and contact angle meter. Influences of amount of DMDAAC on the properties of resultant latex and its film were investigated in detail. Results show that the particle size of the latex has the minimum value knd the zeta potential of the latex is increased when the amount of DMDAAC is increased. In addition, the particle size of the latex is unimodal distribution when the amount of DMDAAC is not more than 2.5%. However, the particle size of the latex is bimodal distribution when the amount of DMDAAC is more than 2.5%. The contact angle is varied slightly with the increase of amount of DMDAAC when it is not more than 2.5%. Nevertheless, the contact angle is decreased with the increase of the amount of DMDAAC when it is more than 2.5%.
基金supported by the Guangdong Basic and Applied Basic Research Foundation(No.2020B1515020038)the Pearl River Talent Recruitment Program of Guangdong Province(2019QN01L148)+3 种基金the National Natural Science Foundation of China(21876063 and 22076064)the Guangdong Special Support Program(2019TX05L129)the Guangdong(China)Innovative and Entrepreneurial Research Team Program(2016ZT06N258)the Special Fund Project for Science and Technology Innovation Strategy of Guangdong Province(2019B121205004).
文摘Fluorinated liquid crystal monomers(LCMs)are begun to emerge as new persistent organic pollutants.Herein,the structure-reactivity relationships of fluorinated LCMs 1,2,3-trifluoro-5-[3-(3-propylcyclohexyl)cyclohexyl]benzene(TPrCB),1,2-difluoro-4-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]benzene(DPrCB),4-[(trans,trans)-4'-(3-Buten-1-yl)[1,10-bicyclohexyl]-4-yl]-1,2-difluoro-benzene(BBDB)and 1-[4-(4-ethylcyclohexyl)cyclohexyl]-4(trifluoromethoxy)benzene(ECTB)subject to photocatalysis-generated oxidation species were investigated.The degradation rate constant of BBDB was 3.0,2.6,and 6.8 times higher than DPrCB,TPrCB and ECTB,respectively.The results reveal that BBDB,DPrCB and TPrCB had mainly negative electrostatic potential(ESP)regions which were vulnerable to electrophilic attack by h^(+),·OH and·O_(2)^(-),while ECTB was composed of mainly positive ESP regions which were vulnerable to nucleophilic attack by·OH and·O_(2)^(-).The detoxification processes of BBDB,DPrCB and TPrCB included carbon bond cleavage and benzene ring opening.However,the methoxy group of ECTB reduced the nucleophilic reactivity on the benzene ring,leading to slower detoxification efficiency.These findings may help to develop LCMs treatment technologies based on structure-reactivity relationships。
基金supported by the National Natural Science Foundation of China (91856128,21774038)Jiangsu Key Laboratory of Advanced Functional Polymers Design and Application (KJS2220)+2 种基金the Fundamental Research Funds for the Central Universities (2022ZYGXZR105)the Pearl River Talents Scheme (2016ZT06C322)the Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices (2019B121203003)。
文摘Fluorinated polymers exhibit a unique combination of attributes,including chemical inertness,low surface energy,exceptional weather resistance,and intriguing electrical properties.This mini review provides an overview of recent advancements in the research of fluorinated polymers,highlighting the development of synthetic strategies for novel fluorinated polymers and their diverse applications in various fields.Traditional fluorinated polyolefins can be modified through chemical methods to produce functional materials.Copolymerization of fluorinated olefins with non-fluorinated monomers effectively addresses synthesis challenges,yielding main-chain fluoro-containing polymers with specific functional groups.Additionally,recent studies have revealed that free radical(co)polymerization of fluorinated(meth)acrylate monomers leads to new fluorinated polymers with enhanced solubility,processability,and structural diversity.Capitalizing on these new synthetic strategies,a range of fluorinated polymer materials has been developed for a multitude of applications,including flexible electrodes,alternating current(AC)electroluminescent devices,energy storage capacitors,triboelectric nanogenerators,and lithium batteries.With their customized structures and excellent properties,fluorinated polymers hold significant promise to uncover more potential applications in the era of flexible and wearable electronics.
基金financially supported by the National Natural Science Foundation of China (No. 21574014)
文摘In this paper, we combined high-end cationic UV-curable material with fluorinated chain obtaining a series of new fluorine-containing aromatic oxetane monomers via a mild nucleophilic substitution reaction. The structures and properties of monomers were characterized using ~1 H-NMR, ^（19） F-NMR, dynamic viscosity tests and differential scanning calorimetry（DSC）. It was determined that all of the fluorinated monomers obtained had much lower viscosity and higher thermostability after the introduction of hexafluorobenzene. Then, UV-curable coatings were prepared using four fluorine-containing aromatic oxetane monomers（FOX1-4）; the UV-curing kinetics, with three kinds of initiators, and properties of the cured films were evaluated using real-time Fourier transform infrared（FTIR） spectroscopy, water and diiodomethane contact angle tests, surface energy calculations and scanning electron microscopy（SEM）. The FTIR spectroscopy results showed that the coatings possessed excellent conversion rate（〉 99% with liquid initiator PAG-201 in 150 s）, and as the fluorine content increased, the monomers exhibited decreased mobility with the increasing viscosity and worse solubility with fluorinated monomers, resulting in a lower conversion rate. Moreover, the coatings possessed favorable hydrophobic and oleophobic properties and low surface energies owing to the fluoride chains floating to the membrane-air interface, which was also confirmed by discrete concave structures in SEM images. These new kinds of monomers can replace traditional fluorinated cationic monomers applied to the fingerprint resistant, fouling resistant, scratch resistant and anti-aging coatings, adhesives or printing ink materials.
