The Experts below are selected from a list of 2901 Experts worldwide ranked by ideXlab platform
Jerome P. Claverie - One of the best experts on this subject based on the ideXlab platform.
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Ultrahigh Tg Epoxy Thermosets Based on Insertion Polynorbornenes
Macromolecules, 2016Co-Authors: Basile Commarieu, Jonathan Potier, Moubarak Compaore, Sylvain Dessureault, Brian L. Goodall, Xu Li, Jerome P. ClaverieAbstract:Thermosetting materials (thermosets) are widely used organic materials derived from 3D-network forming monomers. Achieving high glass transition temperature (Tg) thermosets is often a challenging task due to the complexity of designing efficiently and cheaply monomers which are rigid enough to prevent molecular motions within the thermoset. We report here a very simple route to prepare epoxy thermosets with Tg as high as 350 °C, based on insertion Polynorbornenes. The epoxy monomer (PNBE(epoxy)) is prepared by the epoxidation of poly(5-vinylnorbornene) obtained by catalytic insertion polymerization of 5-vinylnorbornene. PNBE(epoxy) can be cross-linked with simple biosourced compounds. Alternatively, polar insertion Polynorbornene can also be used as cross-linker in the formulation of an epoxy resin, once again resulting in epoxy resins with Tg higher than 300 °C and devoid of degradation at this temperature. Thus, this study clearly demonstrates the viability of catalytic polymerization to access epoxy th...
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Ultrahigh Tg Epoxy Thermosets Based on Insertion Polynorbornenes
2016Co-Authors: Basile Commarieu, Jonathan Potier, Moubarak Compaore, Sylvain Dessureault, Brian L. Goodall, Jerome P. ClaverieAbstract:Thermosetting materials (thermosets) are widely used organic materials derived from 3D-network forming monomers. Achieving high glass transition temperature (Tg) thermosets is often a challenging task due to the complexity of designing efficiently and cheaply monomers which are rigid enough to prevent molecular motions within the thermoset. We report here a very simple route to prepare epoxy thermosets with Tg as high as 350 °C, based on insertion Polynorbornenes. The epoxy monomer (PNBE(epoxy)) is prepared by the epoxidation of poly(5-vinylnorbornene) obtained by catalytic insertion polymerization of 5-vinylnorbornene. PNBE(epoxy) can be cross-linked with simple biosourced compounds. Alternatively, polar insertion Polynorbornene can also be used as cross-linker in the formulation of an epoxy resin, once again resulting in epoxy resins with Tg higher than 300 °C and devoid of degradation at this temperature. Thus, this study clearly demonstrates the viability of catalytic polymerization to access epoxy thermosets with ultrahigh Tg
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High Tg sulfonated insertion Polynorbornene ionomers prepared by catalytic insertion polymerization
Polymer, 2016Co-Authors: Florian Pierre, Basile Commarieu, Ana C. Tavares, Jerome P. ClaverieAbstract:Abstract A simple method to synthesize high Tg sulfonated ionomers based on catalytic insertion Polynorbornene is reported. Copolymers of norbornene and 5-methyl alcohol norbornene (endo:exo = 82:18) or 5-methyl bromide norbornene (endo:exo = 86:14) as well as terpolymers of norbornene, 5-methyl alcohol norbornene and 5-hexyl norbornene are prepared using a cationic Pd catalyst. These copolymers are then thioacetylated. Using hydrogen peroxide as oxidant, a sulfonated Polynorbornene is obtained. Ionomers containing as much as 30 mol% SO3H and with Tgs above 200 °C are obtained in a four-step procedure of overall 40–75% yield.
Erqiang Chen - One of the best experts on this subject based on the ideXlab platform.
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homopolymer and random copolymer of polyhedral oligomeric silsesquioxane poss based side chain Polynorbornenes flexible spacer effect and composition dependence
Macromolecules, 2018Co-Authors: Xiaohui Zheng, Jianfeng Zhao, Tipeng Zhao, Tao Yang, Xiangkui Ren, Chenyang Liu, Shuang Yang, Erqiang ChenAbstract:A series of homopolymers and random copolymers of polyhedral oligomeric silsesquioxane (POSS)-based side-chain Polynorbornenes were prepared using ring-opening metathesis polymerization. For the homopolymer P-z-POSS (z represents the spacer length, z = 5, 12, and 17), the POSS groups tethered to the side chain are linked to the Polynorbornene backbone through the flexible spacer with different lengths. For the random copolymer P-6-co-17(X/Y) (X/Y = 1/1, 3/1, 6/1, and 9/1), the composition was regulated by adjusting the molar feed ratio X/Y of the norbornene monomer with butyl ester side group (M-6) to the POSS containing monomer with the longest spacer (M-17-POSS). Using various techniques, we studied the spacer length effect on POSS crystallization of the homopolymers and the composition dependence of physical properties of the copolymers. It is found that P-5-POSS is amorphous. On the contrary, POSS crystallization is observed in P-12-POSS and P-17-POSS, and the longer the spacer is, the higher the POSS...
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Homopolymer and Random Copolymer of Polyhedral Oligomeric Silsesquioxane (POSS)-Based Side-Chain Polynorbornenes: Flexible Spacer Effect and Composition Dependence
2018Co-Authors: Xiaohui Zheng, Jianfeng Zhao, Tipeng Zhao, Tao Yang, Xiangkui Ren, Chenyang Liu, Shuang Yang, Erqiang ChenAbstract:A series of homopolymers and random copolymers of polyhedral oligomeric silsesquioxane (POSS)-based side-chain Polynorbornenes were prepared using ring-opening metathesis polymerization. For the homopolymer P-z-POSS (z represents the spacer length, z = 5, 12, and 17), the POSS groups tethered to the side chain are linked to the Polynorbornene backbone through the flexible spacer with different lengths. For the random copolymer P-6-co-17(X/Y) (X/Y = 1/1, 3/1, 6/1, and 9/1), the composition was regulated by adjusting the molar feed ratio X/Y of the norbornene monomer with butyl ester side group (M-6) to the POSS containing monomer with the longest spacer (M-17-POSS). Using various techniques, we studied the spacer length effect on POSS crystallization of the homopolymers and the composition dependence of physical properties of the copolymers. It is found that P-5-POSS is amorphous. On the contrary, POSS crystallization is observed in P-12-POSS and P-17-POSS, and the longer the spacer is, the higher the POSS crystallization ability is. With the comonomer of M-17-POSS, all the P-6-co-17(X/Y) samples can have the POSS group to crystallize, resulting in a nanosegregation similar to the lamellar morphology. The lamellar period is inversely proportional to the POSS volume fraction. The POSS crystallites are raft-like, containing two layers of POSS groups stacked together. Uniaxial stretching can well align the POSS crystallites in the copolymers to be parallel to the stretching direction, and the lamellar period is decreased with increasing the strain. Varying X/Y from 1/1 to 9/1 changes the copolymer from plastic to thermoplastic elastomer, wherein the latter takes the POSS crystallites as the physical cross-links
Basile Commarieu - One of the best experts on this subject based on the ideXlab platform.
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Ultrahigh Tg Epoxy Thermosets Based on Insertion Polynorbornenes
Macromolecules, 2016Co-Authors: Basile Commarieu, Jonathan Potier, Moubarak Compaore, Sylvain Dessureault, Brian L. Goodall, Xu Li, Jerome P. ClaverieAbstract:Thermosetting materials (thermosets) are widely used organic materials derived from 3D-network forming monomers. Achieving high glass transition temperature (Tg) thermosets is often a challenging task due to the complexity of designing efficiently and cheaply monomers which are rigid enough to prevent molecular motions within the thermoset. We report here a very simple route to prepare epoxy thermosets with Tg as high as 350 °C, based on insertion Polynorbornenes. The epoxy monomer (PNBE(epoxy)) is prepared by the epoxidation of poly(5-vinylnorbornene) obtained by catalytic insertion polymerization of 5-vinylnorbornene. PNBE(epoxy) can be cross-linked with simple biosourced compounds. Alternatively, polar insertion Polynorbornene can also be used as cross-linker in the formulation of an epoxy resin, once again resulting in epoxy resins with Tg higher than 300 °C and devoid of degradation at this temperature. Thus, this study clearly demonstrates the viability of catalytic polymerization to access epoxy th...
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Ultrahigh Tg Epoxy Thermosets Based on Insertion Polynorbornenes
2016Co-Authors: Basile Commarieu, Jonathan Potier, Moubarak Compaore, Sylvain Dessureault, Brian L. Goodall, Jerome P. ClaverieAbstract:Thermosetting materials (thermosets) are widely used organic materials derived from 3D-network forming monomers. Achieving high glass transition temperature (Tg) thermosets is often a challenging task due to the complexity of designing efficiently and cheaply monomers which are rigid enough to prevent molecular motions within the thermoset. We report here a very simple route to prepare epoxy thermosets with Tg as high as 350 °C, based on insertion Polynorbornenes. The epoxy monomer (PNBE(epoxy)) is prepared by the epoxidation of poly(5-vinylnorbornene) obtained by catalytic insertion polymerization of 5-vinylnorbornene. PNBE(epoxy) can be cross-linked with simple biosourced compounds. Alternatively, polar insertion Polynorbornene can also be used as cross-linker in the formulation of an epoxy resin, once again resulting in epoxy resins with Tg higher than 300 °C and devoid of degradation at this temperature. Thus, this study clearly demonstrates the viability of catalytic polymerization to access epoxy thermosets with ultrahigh Tg
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High Tg sulfonated insertion Polynorbornene ionomers prepared by catalytic insertion polymerization
Polymer, 2016Co-Authors: Florian Pierre, Basile Commarieu, Ana C. Tavares, Jerome P. ClaverieAbstract:Abstract A simple method to synthesize high Tg sulfonated ionomers based on catalytic insertion Polynorbornene is reported. Copolymers of norbornene and 5-methyl alcohol norbornene (endo:exo = 82:18) or 5-methyl bromide norbornene (endo:exo = 86:14) as well as terpolymers of norbornene, 5-methyl alcohol norbornene and 5-hexyl norbornene are prepared using a cationic Pd catalyst. These copolymers are then thioacetylated. Using hydrogen peroxide as oxidant, a sulfonated Polynorbornene is obtained. Ionomers containing as much as 30 mol% SO3H and with Tgs above 200 °C are obtained in a four-step procedure of overall 40–75% yield.
Xiaohui Zheng - One of the best experts on this subject based on the ideXlab platform.
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homopolymer and random copolymer of polyhedral oligomeric silsesquioxane poss based side chain Polynorbornenes flexible spacer effect and composition dependence
Macromolecules, 2018Co-Authors: Xiaohui Zheng, Jianfeng Zhao, Tipeng Zhao, Tao Yang, Xiangkui Ren, Chenyang Liu, Shuang Yang, Erqiang ChenAbstract:A series of homopolymers and random copolymers of polyhedral oligomeric silsesquioxane (POSS)-based side-chain Polynorbornenes were prepared using ring-opening metathesis polymerization. For the homopolymer P-z-POSS (z represents the spacer length, z = 5, 12, and 17), the POSS groups tethered to the side chain are linked to the Polynorbornene backbone through the flexible spacer with different lengths. For the random copolymer P-6-co-17(X/Y) (X/Y = 1/1, 3/1, 6/1, and 9/1), the composition was regulated by adjusting the molar feed ratio X/Y of the norbornene monomer with butyl ester side group (M-6) to the POSS containing monomer with the longest spacer (M-17-POSS). Using various techniques, we studied the spacer length effect on POSS crystallization of the homopolymers and the composition dependence of physical properties of the copolymers. It is found that P-5-POSS is amorphous. On the contrary, POSS crystallization is observed in P-12-POSS and P-17-POSS, and the longer the spacer is, the higher the POSS...
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Homopolymer and Random Copolymer of Polyhedral Oligomeric Silsesquioxane (POSS)-Based Side-Chain Polynorbornenes: Flexible Spacer Effect and Composition Dependence
2018Co-Authors: Xiaohui Zheng, Jianfeng Zhao, Tipeng Zhao, Tao Yang, Xiangkui Ren, Chenyang Liu, Shuang Yang, Erqiang ChenAbstract:A series of homopolymers and random copolymers of polyhedral oligomeric silsesquioxane (POSS)-based side-chain Polynorbornenes were prepared using ring-opening metathesis polymerization. For the homopolymer P-z-POSS (z represents the spacer length, z = 5, 12, and 17), the POSS groups tethered to the side chain are linked to the Polynorbornene backbone through the flexible spacer with different lengths. For the random copolymer P-6-co-17(X/Y) (X/Y = 1/1, 3/1, 6/1, and 9/1), the composition was regulated by adjusting the molar feed ratio X/Y of the norbornene monomer with butyl ester side group (M-6) to the POSS containing monomer with the longest spacer (M-17-POSS). Using various techniques, we studied the spacer length effect on POSS crystallization of the homopolymers and the composition dependence of physical properties of the copolymers. It is found that P-5-POSS is amorphous. On the contrary, POSS crystallization is observed in P-12-POSS and P-17-POSS, and the longer the spacer is, the higher the POSS crystallization ability is. With the comonomer of M-17-POSS, all the P-6-co-17(X/Y) samples can have the POSS group to crystallize, resulting in a nanosegregation similar to the lamellar morphology. The lamellar period is inversely proportional to the POSS volume fraction. The POSS crystallites are raft-like, containing two layers of POSS groups stacked together. Uniaxial stretching can well align the POSS crystallites in the copolymers to be parallel to the stretching direction, and the lamellar period is decreased with increasing the strain. Varying X/Y from 1/1 to 9/1 changes the copolymer from plastic to thermoplastic elastomer, wherein the latter takes the POSS crystallites as the physical cross-links
Maxim V. Bermeshev - One of the best experts on this subject based on the ideXlab platform.
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Synthesis and Gas Transport Properties of Addition Polynorbornene with Perfluorophenyl Side Groups.
Polymers, 2020Co-Authors: G. O. Karpov, Eugene Sh Finkelshtein, Ilya L. Borisov, Alexey Volkov, Maxim V. BermeshevAbstract:Polynorbornenes represent a fruitful class of polymers for structure–property study. Recently, vinyl-addition Polynorbornenes bearing side groups of different natures were observed to exhibit excellent gas permeation ability, along with attractive C4H10/CH4 and CO2/N2 separation selectivities. However, to date, the gas transport properties of fluorinated addition Polynorbornenes have not been reported. Herein, we synthesized addition Polynorbornene with fluoroorganic substituents and executed a study on the gas transport properties of the polymer for the first time. A norbornene-type monomer with a C6F5 group, 3-pentafluorophenyl-exo-tricyclononene-7, was successfully involved in addition polymerization, resulting in soluble, high-molecular-weight products obtained in good or high yields. By varying the monomer concentration and monomer/catalyst ratio, it was possible to reach Mw values of (2.93–4.35) × 105. The molecular structure was confirmed by NMR and FTIR analysis. The contact angle with distilled water revealed the hydrophobic nature of the synthesized polymer as expected due to the presence of fluoroorganic side groups. A study of the permeability of various gases (He, H2, O2, N2, CO2, and CH4) through the prepared polymer disclosed a synergetic effect, which was achieved by the presence of both bulky perfluorinated side groups and rigid saturated main chains. Addition poly(3-pentafluorophenyl-exo-tricyclononene-7) was more permeable than its metathesis analogue by a factor of 7–21, or the similar polymer with flexible main chains, poly(pentafluorostyrene), in relation to the gases tested. Therefore, this investigation opens the door to fluorinated addition Polynorbornenes as new potential polymeric materials for membrane gas separation.
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Dielectric properties of addition and metathesis Polynorbornenes with bulky side-substituents
Polymer, 2020Co-Authors: G. O. Karpov, Dmitry A. Alentiev, Alyona I. Wozniak, Evgeniya V. Bermesheva, I. V. Lounev, Yuri A. Gusev, Victor P. Shantarovich, Maxim V. BermeshevAbstract:Abstract Structure-property study of Polynorbornenes for low dielectric permittivity materials was performed. Dielectric properties of various Polynorbornenes bearing F-, Si- and alkenyl-side groups were investigated. The incorporation of both fluoroorganic- and Me3Si-groups as side substituents was found to be a fruitful tool to tune dielectric properties and to obtain polymeric materials with low values of dielectric relative permittivity (hereinafter dielectric permittivity) and the dissipation factors. Addition Polynorbornenes with Me3Si- or alkenyl-side groups disclosed dielectric permittivity in the range of 2.07–2.34. Polynorbornenes containing fluouroorganic groups exhibited dielectric permittivity as low as 1.94–2.78. To the best of our knowledge, the achieved values of dielectric permittivity are the lowest ones among published for Polynorbornenes. The investigated polymers also exhibited low or moderate values of the dissipation factor. The obtained results are considered and discussed along with the data of wide-angle X-ray diffraction, positron annihilating lifetime spectroscopy, low temperature nitrogen adsorption/desorption investigations.
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Porous polymers from norbornene derivatives
PROCEEDINGS OF THE INTERNATIONAL CONFERENCE ON ADVANCED MATERIALS: ICAM 2019, 2019Co-Authors: Dmitry A. Alentiev, Maxim V. BermeshevAbstract:In the paper porous polymeric materials recently obtained from norbornene derivatives are presented. Up to now three groups of Polynorbornenes exhibited the presence of micro-either mesopores and large surface area are considered. The first one is the group of Me3Si-containing addition Polynorbornenes. These polymers are microporous and possess Brunauer-Emmett-Teller (BET) surface area up to 800 m2/g. The second group includes Polynorbornenes with carbocycles in the side polymer chains. Up to now, only polydicyclopentadiene is reported as porous material from this group. The third group includes polymers based on bifunctional norbornenes. These polymers have demonstrated tunable porous properties and large BET surface area up to 1000 m2/g.In the paper porous polymeric materials recently obtained from norbornene derivatives are presented. Up to now three groups of Polynorbornenes exhibited the presence of micro-either mesopores and large surface area are considered. The first one is the group of Me3Si-containing addition Polynorbornenes. These polymers are microporous and possess Brunauer-Emmett-Teller (BET) surface area up to 800 m2/g. The second group includes Polynorbornenes with carbocycles in the side polymer chains. Up to now, only polydicyclopentadiene is reported as porous material from this group. The third group includes polymers based on bifunctional norbornenes. These polymers have demonstrated tunable porous properties and large BET surface area up to 1000 m2/g.
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Glassy Polynorbornenes with Si–O–Si Containing Side Groups. Novel Materials for Hydrocarbon Membrane Separation
Macromolecules, 2013Co-Authors: Maxim V. Bermeshev, Alexandr V Syromolotov, Ludmila Starannikova, V G Lakhtin, Yuri Yampolskii, Maria L. Gringolts, Eugene Sh FinkelshteinAbstract:Polymers of a new class of glassy materials that demonstrate unusual solubility controlled permeability—metathesis Si–O–Si containing Polynorbornenes—are synthesized. The introduction of bulky Si(OSiMe3)3 substituents into the Polynorbornene backbone is shown to provide the polymers with increased gas permeability, higher than all other known metathesis Polynorbornenes. The prepared glassy polymers reveal behavior similar to that known for rubbers and, in particular, siloxanes: permeability coefficients increase for the penetrants of larger size. That is, these polymers are capable to remove higher hydrocarbons from natural and associated petroleum gases.
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Highly permeable polymer materials based on silicon-substituted norbornenes
Petroleum Chemistry, 2010Co-Authors: Maria L. Gringolts, Maxim V. Bermeshev, K. L. Makovetskii, L. E. Starannikova, A. V. Syromolotov, M. F. Filatova, E. Sh. Finkel'shteinAbstract:An approach to the manufacture of highly permeable polymers based on the synthesis and polymerization of norbornenes, norbornadienes, and tricyclononenes with different numbers and different positions of silicon-containing substituents has been developed. It has been found that these monomers are readily involved in metathesis polymerization yielding high-molecular-mass polymers possessing good filmforming properties. The addition (vinyl) polymerization of norbornenes is a more complex process; however, the product silylated Polynorbornenes exhibit a higher gas permeability than the corresponding metathesis Polynorbornenes. By the level of the gas-transport parameters, the silylated addition Polynorbornenes obtained in the study are grouped with the most advanced high-permeability polymers. It has been shown that the presence of Me3Si substituent groups, their amount, and the main-chain structure are responsible for the enhancement of the gas permeability of Polynorbornenes. Thus, a series of polymers with a regularly changing structure has been obtained, a result that makes it possible to reveal the polymer structure-property relations.