Polythiourethanes(PTU)and polythioesters(PTE)derived from renewable sources are emerging sustainable polymers for their excellent degradability and recyclability.However,P(TU-alt-TE)copolymers have been rare and chall...Polythiourethanes(PTU)and polythioesters(PTE)derived from renewable sources are emerging sustainable polymers for their excellent degradability and recyclability.However,P(TU-alt-TE)copolymers have been rare and challenging to synthesize.Here,we report the efficient synthesis of novel P(TU-alt-TE)copolymers via the alternating copolymerization of N-thiocarboxyanhydrides(NTA)/episufides(ES)and provide mechanistic insight into the alternating chain propagation process via density functional theory(DFT)calculation.The incorporation of ESs into traditional peptide backbone is capable of adjusting the glass transition temperature below thermal decomposition temperature,which confers better thermal processability by regulating the rigidity of the backbone and the hydrogen bond interaction among the polymer chains.Crosslinked PTUs with tailored properties are accessible by altering the feeding ratio of NTAs and(bifunctional)ESs.Moreover,the thiourethane in the backbone can endow interesting underwater adhesion properties to the materials.Considering the broad scope of NTA and ES monomers,this method is expected to provide a promising and general route to a wide range of P(TU-alt-TE)copolymers with diverse properties.展开更多
Enantioselective alternating copolymerization of carbon monoxide with propylene was carried out using palladium catalyst modified by 1,4-3,6-dianhydro-2,5-dideoxy-2,5-bis (diphenylphosphino)-L-iditol (DDPPI). The chir...Enantioselective alternating copolymerization of carbon monoxide with propylene was carried out using palladium catalyst modified by 1,4-3,6-dianhydro-2,5-dideoxy-2,5-bis (diphenylphosphino)-L-iditol (DDPPI). The chiral diphosphine was proved to be effective at enantioselective copolymerization. Optical rotation, elemental analysis, H-1, C-13-NMR and IR spectra showed that the copolymer was optically active, isotactic, alternating poly(1,4-ketone) structure.展开更多
The preparing methods, choice of catalysts and reaction kinetics of one of the monomers, diesteramide(DEA), of polyester-amides were investigated in details. The chemical structure of DEA was analyzed. And the Polyest...The preparing methods, choice of catalysts and reaction kinetics of one of the monomers, diesteramide(DEA), of polyester-amides were investigated in details. The chemical structure of DEA was analyzed. And the Polyester-amides (PEA) were obtained by melt copolymerization with DEA. It is shown that DEA can be synthesized by DMT and hexamethylene diamine with the catalyst EX - 1 or EX - 2. The relationship between reaction rate of synthesizing monomer and concentration of hexamethylene diamine is first order kinetic relation.展开更多
The ring-opening copolymerization of adipic anhydride with propylene oxide was carried out with yttrium triflates as a catalyst. Poly(propylene adipate) could be synthesized by controlling the copolymerization condi...The ring-opening copolymerization of adipic anhydride with propylene oxide was carried out with yttrium triflates as a catalyst. Poly(propylene adipate) could be synthesized by controlling the copolymerization conditions. The copolymerization procedure was tracked by ^1H NMR analyses.展开更多
Cationic ring-opening copolymerization of 1, 4-anhydro-2, 3-O-isopropylidene-α-D-ribo-pyranose (AIRP) with 1,4-anhydro-2,3-di-O-benzyl-α-D-ribopyranose (ADBR) preparedfrom D-ribose was studied. Copolymerization usin...Cationic ring-opening copolymerization of 1, 4-anhydro-2, 3-O-isopropylidene-α-D-ribo-pyranose (AIRP) with 1,4-anhydro-2,3-di-O-benzyl-α-D-ribopyranose (ADBR) preparedfrom D-ribose was studied. Copolymerization using SbCl_5 or BF_3 OEt_2 as catalyst atlow temperature gave stereoregular (1→4)β-D-ribofuranan (C-1 and C-4 ring cleavagesee Scheme 1) or (1→5) α-D-ribofuranan (C-1 and C-5 ring cleavage) respectively. Theeffects of catalysts, reaction time and temperatures on yield and stereoregularity of the ob-tained polymers were studied. Polymers were characterized by molecular weight, ~1HNMR,^(13)CNMR and optical rotation.展开更多
Isothiourea is an important class of sulfur-containing molecules showing unique catalytic and biological activities. As such,polyisothiourea is envisioned to be an interesting type of polymer that potentially exhibits...Isothiourea is an important class of sulfur-containing molecules showing unique catalytic and biological activities. As such,polyisothiourea is envisioned to be an interesting type of polymer that potentially exhibits a number of interesting properties. However, there is no access to synthesizing well-defined polyisothiourea, and currently isothiourea-containing polymers are mainly prepared by immobilizing onto other polymer's side chain. Herein, we report the first facile synthesis of polyisothioureas via alternating copolymerization of aziridines and isothiocayanates. Mediated by the catalytic system of phosphazene superbases/alcohol, a broad scope of aziridines and isothiocayanates could be transformed into polyisothioureas with adjustable substitutions(11 examples). The structures of obtained polyisothioureas were fully characterized with ^(1)H-NMR, ^(13)C-NMR, and ^(1)H-^(13)C HMBC NMR. Moreover, the polyisothioureas show tunable thermal properties depending on substitutions on the isothiourea linkages. The novel structure of these polyisothioureas will enable a powerful platform for the discovery of nextgeneration functional plastics.展开更多
It is highly desirable to develop simple organocatalysts for the controlled ring-opening alternating copolymerization(ROAC)of epoxides and cyclic anhydrides,leading to high molecular weight polyesters.Hence,a phosphaz...It is highly desirable to develop simple organocatalysts for the controlled ring-opening alternating copolymerization(ROAC)of epoxides and cyclic anhydrides,leading to high molecular weight polyesters.Hence,a phosphazenium salt,namely tri[tris(dimethylamino)phosphoranylidenamino]phosphonium chloride(P_(4)^(+)Cl^(-)),is developed as a catalyst for the ROAC of epoxides and cyclic anhydrides.Surprisingly,the combination of P_(4)^(+)Cl^(-)with a protonic initiator,such as 1,4-benzenedimethanol(BDM)exhibited high efficiency in the copolymerization of propylene oxide(PO)and phthalic anhydride(PA).This led to the production of polyester with an exceptional high molecular weight(M_n)of up to 126 k Da,which represented a rare example of poly(PO-alt-PA)with Mnsurpassing 100 k Da.Note that the core P atom is trivalent status and the tris[tris(dimethylamino)]phosphoranyl group will share one proton in the P_(4)^(+)Cl^(-)salt.Once combined with protonic species,the P_(4)^(+)Cl^(-)will not only serve as a proton acceptor but also as a hydrogen bonding donor for the cyclic anhydrides.Therefore,it was assumed that the P_(4)^(+)plus proton served dual role in mimic of base/urea pair to effectively catalyze ROAC,which was supported by density functional theory(DFT)calculations.展开更多
Copolymerization as an efficient strategy can provide an opportunity to create new closed-loop recyclable polymeric materials with tailored properties that are generally inaccessible to the individual homopolymers.In ...Copolymerization as an efficient strategy can provide an opportunity to create new closed-loop recyclable polymeric materials with tailored properties that are generally inaccessible to the individual homopolymers.In this contribution,the bulk ring-opening copolymerization of bio-renewable-caprolactone and trans-hexahydro-(4,5)-benzofuranone was achieved to produce closed-loop recyclable copolyesters by using an organobase/urea binary catalyst at room temperature.The obtained copolyesters exhibited composition-dependent thermal properties.Remarkably,the obtained copolyesters were able to depolymerize back to recover the corresponding monomers under mild conditions.展开更多
In this paper, the fluorescence spectra of model compounds of light-emitting alternating copolymers. M (TPA-PPV) and M (TPA-PAV) (Scheme 1) were studied and the effect of KNO3 on the interaction between model compound...In this paper, the fluorescence spectra of model compounds of light-emitting alternating copolymers. M (TPA-PPV) and M (TPA-PAV) (Scheme 1) were studied and the effect of KNO3 on the interaction between model compounds and ionic micelle-watts interface was also investigated. It is found that (I) The fluorescence changes of M (TPA-PPV) are related to the state of CTAB and SDS solution. (II)Aggregated state can be formed in M (TPA-PAV) solution at low concentration of CTAB. (III) Higher concentration of KNO3 may affect the interaction between model compounds and ionic micelle-water interface.展开更多
Alternating copolymerization of 9,9-dihexyl-2,7-dibromofluorene, N-hexyl-2,7-dibromocarbazole (HCz) with diethynyldimethylsilane, diethynyldiphenylsilane, has been investigated using Sonogashira coupling reaction. Pho...Alternating copolymerization of 9,9-dihexyl-2,7-dibromofluorene, N-hexyl-2,7-dibromocarbazole (HCz) with diethynyldimethylsilane, diethynyldiphenylsilane, has been investigated using Sonogashira coupling reaction. Photophysical properties of the resulting copolymers were investigated with UV-Vis absorption and photoluminescence spectroscopy. All the copolymers in chloro-form solution showed absorption peaks at 270 - 280 nm with shoulder peaks at around 380 nm derived from π-π* transition or intra-molecular charge transfer through σ-π moiety, respectively. The chloroform solutions of the copolymers showed broad emission peaks at 415 - 425 nm. The emission wave lengths of the copolymers in the solid state (cast film) detected at 360 - 385 nm were remarkably blue-shifted in comparison with those in the chloroform solutions. Hydrosilylation reaction of the copolymers with 1,4-bis(dimethylsilyl)benzene yielded networked copolymers soluble in chloroform, indicating formation of branching polymers. The chloroform solutions of the HCz-based networked copolymers showed bimodal emission derived from new highly energy states in the σ-π conjugation.展开更多
Recyclable polymers offer a great opportunity to address the environmental issues of plastics.Herein,functionalization of recyclable polymers,poly((R)-3,4-trans six-membered ring-fused GBL)(P((R)-M)),were reported via...Recyclable polymers offer a great opportunity to address the environmental issues of plastics.Herein,functionalization of recyclable polymers,poly((R)-3,4-trans six-membered ring-fused GBL)(P((R)-M)),were reported via end-group modifications and block/random copolymerizations.Di-n-butylmagnesium was selected to catalyze ring-opening polymerization(ROP)of(R)-M in the presence of a series of functional alcohols as the initiators.Block/random copolymerizations of(R)-M andε-caprolactone(ε-CL),L-lactide(L-LA)and trimethylene carbonate(TMC)were performed to control the onset decomposition temperature(T_(d)),melting temperature(T_(m))and glass transition temperature(T_(g)).These functionalized recyclable polymers would find broad applications as the sustainable plastics.展开更多
A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yie...A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yield of cyclic (arylene phosphonate) oligomers is over 85% by using hexadecyltrimethylammoniun bromide as phase transfer catalyst (PTC) at 0 'C . The structures of the cyclic oligomers were confirmed by a combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and IR analysis. These cyclic oligomers undergo facile ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator to give linear polyphosphonate. Free-radical ring-opening polymerization of cyclic(arylene phosphonate) oligomers containing sulfur linkages was also performed in the melt using 2,2'-dithiobis(benzothiazole) (DTB) as the initiator at 270 °C and the resulting polymer had a Mw, of 8 × 103 with a molecular weight distribution of 4. Ring-opening copolymerization of these cyclic oligomers with cyclic carbonate oligomers was also achieved. The average molecular weight of the resulting copolymer is higher than the corresponding homopolymer and the thermal stability of the copolymer is better than the corresponding homopolymer.展开更多
The copolymerization of styrene (St) with maleic anhydride (MAh) under gamma radiation at room temperature in the presence of benzyl dithiobenzoate (BDTB) was found to display 'living' nature evidenced by cons...The copolymerization of styrene (St) with maleic anhydride (MAh) under gamma radiation at room temperature in the presence of benzyl dithiobenzoate (BDTB) was found to display 'living' nature evidenced by constant concentration of chain radicals during the copolymerization, linear evolution of molecular weights with conversion and narrow molecular weight distribution (M-w/M-n = 1.23-1.35). The compositional analysis and the sequence structural information of the copolymers obtained from DEPT (Distortionless Enhancement by Polarization Transfer) experiments demonstrate that the copolymers obtained also possess strictly alternating structure.展开更多
Synthesis of diverse polythioimidocarbonates via ring-opening copolymerization of epoxides and isothiocyanates catalyzed by organoboron catalyst was reported herein.Both aromatic and aliphatic isothiocyanates underwen...Synthesis of diverse polythioimidocarbonates via ring-opening copolymerization of epoxides and isothiocyanates catalyzed by organoboron catalyst was reported herein.Both aromatic and aliphatic isothiocyanates underwent successful copolymerization with terminal and internal epoxides,allowing for the precise tuning of the performance of the resultant copolymers over a broad range.The wide scope of available isothiocyanates and epoxides enables the direct construction of sulfur-containing functional polymers featuring both high glass transition temperature and refractive index.Additionally,it was observed that aromatic isothiocyanates polymerize much faster than aliphatic ones,and the reactivity difference facilitated the one-step synthesis of block polymers from mixed aromatic isothiocyanates,aliphatic isothiocyanates and epoxides due to the preferential incorporation of aromatic isothiocyanates over the aliphatic analogues during their alternating copolymerization with epoxides.The produced polythioimidocarbonates can be used as positive resists for electron beam lithography(sensitivity of 130μC/cm^(2) and contrast of 1.53 for poly(CHO-alt-EITC)).Coupling with their high refractive index(1.58—1.68),polythioimidocarbonates might find functional applications in optics.These results render ring-opening copolymerization of epoxides and isothiocyanates a facile route to enrich functional polymer library.展开更多
Efficient synthesis of polyester polyols with tunable molecular weight and microstructures from cyclic anhydride/epoxide mixtures by taking advantage of chain transfer reaction remains a great challenge,because most o...Efficient synthesis of polyester polyols with tunable molecular weight and microstructures from cyclic anhydride/epoxide mixtures by taking advantage of chain transfer reaction remains a great challenge,because most of the catalysts exhibit poor tolerance to chain transfer agent(CTA).In this contribution,we demonstrated that potassium acetate(KOAc)and 18-crown-6(18-C-6)combination has great potential in the synthesis of diverse polyester polyols with controllable molecular weight and high-end group fidelity.Com-pared with KOAc,KOAc/18-C-6 pair could induce a much faster chain transfer between the active and dormant chains,and thus produce polyester polyols with narrow and monomodal distribution.In addition,polyester polyols could be efficiently prepared in laboratory by using commercially available cyclic anhydride without further purification(containing about 2%diacid residual as CTA)with an extremely low catalyst loading([catalyst pair]:[anhydride]:[epoxide]=1:50000:250000,[catalyst pair]=0.0004 mol%).KOAc/18-C-6 could also promote the self-switchable copolymerization of cyclic anhydride/epoxide/cyclic ester mixtures.Ring-opening copolymerization of cyclic ester was initiated automatically after the full conversion of cyclic anhydride,finally producing polyester polyols with ABA-type block structure.展开更多
The alternating copolymerization of hydroxyalkyl vinyl ethers and dialkyl maleates is investigated by conventional radical polymerization and reversible addition-fragmentation chain transfer polymerization(RAFT).The i...The alternating copolymerization of hydroxyalkyl vinyl ethers and dialkyl maleates is investigated by conventional radical polymerization and reversible addition-fragmentation chain transfer polymerization(RAFT).The influence of comonomer structure,comonomer feeding ratios,and monomer concentrations on the copolymerization and the copolymer structure have been investigated systematically.With 2-hydroxyethyl vinyl ether(HEVE)and dimethyl maleates(DMM)as comonomers,a well-defined alternating copolymer is prepared with M_(n)=3400 and M_(w)/M_(n)=1.93 up to 71.6% monomer.The alternating sequential chain structure of the copolymers has been proved by both NMR and matrixassisted laser desorption/ionization time-of-flight mass spectrometry(MALDI-TOF MS).The experimental reactivity ratios and theoretical calculated highest occupied molecular orbital and the lowest unoccupied molecular orbital of vinyl ethers and alkyl maleates support that these monomer pairs have tendency to form alternating copolymers.With 2-cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate as the RAFT agent,the molecular weight of HEVE and DMM copolymer increases with the monomer conversion,demonstrating a controlled radical polymerization feature with well-controlled molecular weight and relatively narrower molecular weight distribution.With alternating copolymer of HEVE and DMM as macro-CTA(M_(n)=5200 and M_(w)/M_(n)=1.46),both the chain extension with HEVE and DMM(M_(n)=10400 and M_(w)/M_(n)=1.72)and block copolymerization with vinyl acetate have been successfully achieved(M_(n)=8500 and M_(w)/M_(n)=1.52).展开更多
Amphiphilic copolymer of 5-benzyloxytrimethylene carbonate (BTMC) with poly (vinyl pyrrolidone) (PVP) was successfully synthesized using immobilized porcine pancreas lipase (IPPL) or SnOct2 as catalyst. Hydrox...Amphiphilic copolymer of 5-benzyloxytrimethylene carbonate (BTMC) with poly (vinyl pyrrolidone) (PVP) was successfully synthesized using immobilized porcine pancreas lipase (IPPL) or SnOct2 as catalyst. Hydroxyl terminated PVP, synthesized with 2-mercaptoethanol as a chain transfer reagent, was employed as a rnacroinitiator. The resulting copolymers were characterized by GPC, ^1H NMR and IR. Increasing the BTMC/PVP-OH feed ratio ([B]/[P]) resulted in the increase of Mn of corresponding copolymers and the decrease of Mw/Mn. Immobilized enzyme has comparable catalytic activity to SnOct2 for the copolymerization.展开更多
Styrene-isoprene-styrene(SIS) block copolymer was modified into epoxidized styrene-isoprene-styrene(ESIS) block copolymer with performic acid generated in situ from hydrogen peroxide and formic acid.The structure ...Styrene-isoprene-styrene(SIS) block copolymer was modified into epoxidized styrene-isoprene-styrene(ESIS) block copolymer with performic acid generated in situ from hydrogen peroxide and formic acid.The structure and property of ESIS were characterized by Fourier transform infrared(FT-IR) spectroscopy,gel permeation chromatography(GPC),thermogravimetric/differential thermogravimetric(TG/DTG),melt flow rate(MFR) and dynamic mechanical analysis(DMA),and the reaction mechanism in the process of epoxidation was analyzed.The results showed that C=C double bonds of 1,4-structure were more active than that of 3,4-structure in polyisoprene chains.With epoxidation reaction proceeding,the whole tendency of molecular weight increased and molecular weight distribution widened,and MFR firstly increased and latterly decreased.The heat resistance of ESIS was superior to that of SIS.When SIS was changed into ESIS with 15.3% of mass fraction of epoxide groups,Tg of polyisoprene chains increased from-45.3 ℃ to 10.9 ℃.In the earlier period of epoxidation,some molecular chains ruptured and new substances with low molecular weight formed.However,in the latter period,crosslinking reaction between molecular chains which was initiated by epoxide groups or C=C double bonds occurred and crosslinked insoluble substances came into being.展开更多
A kind of novel triblock copolymers of poly(γ-benzyl L-glutamate)-b-poly(tetrahydrofuran)-b-poly(γ-benzyl L-glutamate)s(PBLG-b-PTHF-b-PBLG)was synthesized by using bis(3-aminopropyl)terminated polytetrahydrofuran to...A kind of novel triblock copolymers of poly(γ-benzyl L-glutamate)-b-poly(tetrahydrofuran)-b-poly(γ-benzyl L-glutamate)s(PBLG-b-PTHF-b-PBLG)was synthesized by using bis(3-aminopropyl)terminated polytetrahydrofuran to initiate the ring-opening polymerization ofγ-benzyl L-glutamate N-carboxyanhydride(BLG-NCA).The corresponding multiblock poly(amino acid-urea)s were prepared in one-pot protocol from the chain extension of PBLG-b-PTHF-b-PBLG with MDI.The resulting triblock and multiblock copolymers were characterized by FTIR,~1H-NMR,^(13)C-NMR and GPC techniques.It is demonstrated that the chain extension has taken place to give rise to the copolymers with the well-defined block composition and narrow molecular weight distribution.A distinct T_g arising from the hard-segments was observed in all the copolymers.Their mechanical properties showed an increasing trend with the molecular weight enhancement of the prepolymers.展开更多
基金supported by the National Natural Science Foundation of China(22125101,22331002 to H.L.,22171037,22101040 to W.R.)。
文摘Polythiourethanes(PTU)and polythioesters(PTE)derived from renewable sources are emerging sustainable polymers for their excellent degradability and recyclability.However,P(TU-alt-TE)copolymers have been rare and challenging to synthesize.Here,we report the efficient synthesis of novel P(TU-alt-TE)copolymers via the alternating copolymerization of N-thiocarboxyanhydrides(NTA)/episufides(ES)and provide mechanistic insight into the alternating chain propagation process via density functional theory(DFT)calculation.The incorporation of ESs into traditional peptide backbone is capable of adjusting the glass transition temperature below thermal decomposition temperature,which confers better thermal processability by regulating the rigidity of the backbone and the hydrogen bond interaction among the polymer chains.Crosslinked PTUs with tailored properties are accessible by altering the feeding ratio of NTAs and(bifunctional)ESs.Moreover,the thiourethane in the backbone can endow interesting underwater adhesion properties to the materials.Considering the broad scope of NTA and ES monomers,this method is expected to provide a promising and general route to a wide range of P(TU-alt-TE)copolymers with diverse properties.
基金the National Natural Science Foundation of China for financial support (No. 29933050).
文摘Enantioselective alternating copolymerization of carbon monoxide with propylene was carried out using palladium catalyst modified by 1,4-3,6-dianhydro-2,5-dideoxy-2,5-bis (diphenylphosphino)-L-iditol (DDPPI). The chiral diphosphine was proved to be effective at enantioselective copolymerization. Optical rotation, elemental analysis, H-1, C-13-NMR and IR spectra showed that the copolymer was optically active, isotactic, alternating poly(1,4-ketone) structure.
文摘The preparing methods, choice of catalysts and reaction kinetics of one of the monomers, diesteramide(DEA), of polyester-amides were investigated in details. The chemical structure of DEA was analyzed. And the Polyester-amides (PEA) were obtained by melt copolymerization with DEA. It is shown that DEA can be synthesized by DMT and hexamethylene diamine with the catalyst EX - 1 or EX - 2. The relationship between reaction rate of synthesizing monomer and concentration of hexamethylene diamine is first order kinetic relation.
基金Supported by the National Natural Science Foundation of China(Nos.20704036, Key Program 20434020)the State Basic Research Projects of China(No.2005CB623802)
文摘The ring-opening copolymerization of adipic anhydride with propylene oxide was carried out with yttrium triflates as a catalyst. Poly(propylene adipate) could be synthesized by controlling the copolymerization conditions. The copolymerization procedure was tracked by ^1H NMR analyses.
文摘Cationic ring-opening copolymerization of 1, 4-anhydro-2, 3-O-isopropylidene-α-D-ribo-pyranose (AIRP) with 1,4-anhydro-2,3-di-O-benzyl-α-D-ribopyranose (ADBR) preparedfrom D-ribose was studied. Copolymerization using SbCl_5 or BF_3 OEt_2 as catalyst atlow temperature gave stereoregular (1→4)β-D-ribofuranan (C-1 and C-4 ring cleavagesee Scheme 1) or (1→5) α-D-ribofuranan (C-1 and C-5 ring cleavage) respectively. Theeffects of catalysts, reaction time and temperatures on yield and stereoregularity of the ob-tained polymers were studied. Polymers were characterized by molecular weight, ~1HNMR,^(13)CNMR and optical rotation.
基金financially supported by the National Key R&D Program of China (No.2021YFA1501700)the Science and Technology Development Plan of Jilin Province (Nos.20230101042JC and 20210201059GX)+1 种基金Basic Science Center Program (No.51988102)the National Natural Science Foundation of China (Nos.52203017 and 52073272)。
文摘Isothiourea is an important class of sulfur-containing molecules showing unique catalytic and biological activities. As such,polyisothiourea is envisioned to be an interesting type of polymer that potentially exhibits a number of interesting properties. However, there is no access to synthesizing well-defined polyisothiourea, and currently isothiourea-containing polymers are mainly prepared by immobilizing onto other polymer's side chain. Herein, we report the first facile synthesis of polyisothioureas via alternating copolymerization of aziridines and isothiocayanates. Mediated by the catalytic system of phosphazene superbases/alcohol, a broad scope of aziridines and isothiocayanates could be transformed into polyisothioureas with adjustable substitutions(11 examples). The structures of obtained polyisothioureas were fully characterized with ^(1)H-NMR, ^(13)C-NMR, and ^(1)H-^(13)C HMBC NMR. Moreover, the polyisothioureas show tunable thermal properties depending on substitutions on the isothiourea linkages. The novel structure of these polyisothioureas will enable a powerful platform for the discovery of nextgeneration functional plastics.
基金supported by the National Key R&D Program of China(2021YFA1501600)National Natural Science Foundation of China(22031005)。
文摘It is highly desirable to develop simple organocatalysts for the controlled ring-opening alternating copolymerization(ROAC)of epoxides and cyclic anhydrides,leading to high molecular weight polyesters.Hence,a phosphazenium salt,namely tri[tris(dimethylamino)phosphoranylidenamino]phosphonium chloride(P_(4)^(+)Cl^(-)),is developed as a catalyst for the ROAC of epoxides and cyclic anhydrides.Surprisingly,the combination of P_(4)^(+)Cl^(-)with a protonic initiator,such as 1,4-benzenedimethanol(BDM)exhibited high efficiency in the copolymerization of propylene oxide(PO)and phthalic anhydride(PA).This led to the production of polyester with an exceptional high molecular weight(M_n)of up to 126 k Da,which represented a rare example of poly(PO-alt-PA)with Mnsurpassing 100 k Da.Note that the core P atom is trivalent status and the tris[tris(dimethylamino)]phosphoranyl group will share one proton in the P_(4)^(+)Cl^(-)salt.Once combined with protonic species,the P_(4)^(+)Cl^(-)will not only serve as a proton acceptor but also as a hydrogen bonding donor for the cyclic anhydrides.Therefore,it was assumed that the P_(4)^(+)plus proton served dual role in mimic of base/urea pair to effectively catalyze ROAC,which was supported by density functional theory(DFT)calculations.
基金support by National Natural Science Foundation of China(Nos.52322304,22075160 and 22031005)Taishan Scholar Foundation of Shandong Province(No.tsqn202103078).
文摘Copolymerization as an efficient strategy can provide an opportunity to create new closed-loop recyclable polymeric materials with tailored properties that are generally inaccessible to the individual homopolymers.In this contribution,the bulk ring-opening copolymerization of bio-renewable-caprolactone and trans-hexahydro-(4,5)-benzofuranone was achieved to produce closed-loop recyclable copolyesters by using an organobase/urea binary catalyst at room temperature.The obtained copolyesters exhibited composition-dependent thermal properties.Remarkably,the obtained copolyesters were able to depolymerize back to recover the corresponding monomers under mild conditions.
基金The authors gratefully thank the NSFC (No. 29992530, 29873060) and CAS for the financial support.
文摘In this paper, the fluorescence spectra of model compounds of light-emitting alternating copolymers. M (TPA-PPV) and M (TPA-PAV) (Scheme 1) were studied and the effect of KNO3 on the interaction between model compounds and ionic micelle-watts interface was also investigated. It is found that (I) The fluorescence changes of M (TPA-PPV) are related to the state of CTAB and SDS solution. (II)Aggregated state can be formed in M (TPA-PAV) solution at low concentration of CTAB. (III) Higher concentration of KNO3 may affect the interaction between model compounds and ionic micelle-water interface.
文摘Alternating copolymerization of 9,9-dihexyl-2,7-dibromofluorene, N-hexyl-2,7-dibromocarbazole (HCz) with diethynyldimethylsilane, diethynyldiphenylsilane, has been investigated using Sonogashira coupling reaction. Photophysical properties of the resulting copolymers were investigated with UV-Vis absorption and photoluminescence spectroscopy. All the copolymers in chloro-form solution showed absorption peaks at 270 - 280 nm with shoulder peaks at around 380 nm derived from π-π* transition or intra-molecular charge transfer through σ-π moiety, respectively. The chloroform solutions of the copolymers showed broad emission peaks at 415 - 425 nm. The emission wave lengths of the copolymers in the solid state (cast film) detected at 360 - 385 nm were remarkably blue-shifted in comparison with those in the chloroform solutions. Hydrosilylation reaction of the copolymers with 1,4-bis(dimethylsilyl)benzene yielded networked copolymers soluble in chloroform, indicating formation of branching polymers. The chloroform solutions of the HCz-based networked copolymers showed bimodal emission derived from new highly energy states in the σ-π conjugation.
基金supported by The National Natural Science Foundation of China(21504039)。
文摘Recyclable polymers offer a great opportunity to address the environmental issues of plastics.Herein,functionalization of recyclable polymers,poly((R)-3,4-trans six-membered ring-fused GBL)(P((R)-M)),were reported via end-group modifications and block/random copolymerizations.Di-n-butylmagnesium was selected to catalyze ring-opening polymerization(ROP)of(R)-M in the presence of a series of functional alcohols as the initiators.Block/random copolymerizations of(R)-M andε-caprolactone(ε-CL),L-lactide(L-LA)and trimethylene carbonate(TMC)were performed to control the onset decomposition temperature(T_(d)),melting temperature(T_(m))and glass transition temperature(T_(g)).These functionalized recyclable polymers would find broad applications as the sustainable plastics.
基金This project was supported by the National Natural Science Foundation of China (No. 20084001).
文摘A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yield of cyclic (arylene phosphonate) oligomers is over 85% by using hexadecyltrimethylammoniun bromide as phase transfer catalyst (PTC) at 0 'C . The structures of the cyclic oligomers were confirmed by a combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and IR analysis. These cyclic oligomers undergo facile ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator to give linear polyphosphonate. Free-radical ring-opening polymerization of cyclic(arylene phosphonate) oligomers containing sulfur linkages was also performed in the melt using 2,2'-dithiobis(benzothiazole) (DTB) as the initiator at 270 °C and the resulting polymer had a Mw, of 8 × 103 with a molecular weight distribution of 4. Ring-opening copolymerization of these cyclic oligomers with cyclic carbonate oligomers was also achieved. The average molecular weight of the resulting copolymer is higher than the corresponding homopolymer and the thermal stability of the copolymer is better than the corresponding homopolymer.
文摘The copolymerization of styrene (St) with maleic anhydride (MAh) under gamma radiation at room temperature in the presence of benzyl dithiobenzoate (BDTB) was found to display 'living' nature evidenced by constant concentration of chain radicals during the copolymerization, linear evolution of molecular weights with conversion and narrow molecular weight distribution (M-w/M-n = 1.23-1.35). The compositional analysis and the sequence structural information of the copolymers obtained from DEPT (Distortionless Enhancement by Polarization Transfer) experiments demonstrate that the copolymers obtained also possess strictly alternating structure.
基金supported by the National Natural Science Foundation of China(Grants 51973186 and 22101253)the National Science Fund for Distinguished Young Scholars(No.T2225004).
文摘Synthesis of diverse polythioimidocarbonates via ring-opening copolymerization of epoxides and isothiocyanates catalyzed by organoboron catalyst was reported herein.Both aromatic and aliphatic isothiocyanates underwent successful copolymerization with terminal and internal epoxides,allowing for the precise tuning of the performance of the resultant copolymers over a broad range.The wide scope of available isothiocyanates and epoxides enables the direct construction of sulfur-containing functional polymers featuring both high glass transition temperature and refractive index.Additionally,it was observed that aromatic isothiocyanates polymerize much faster than aliphatic ones,and the reactivity difference facilitated the one-step synthesis of block polymers from mixed aromatic isothiocyanates,aliphatic isothiocyanates and epoxides due to the preferential incorporation of aromatic isothiocyanates over the aliphatic analogues during their alternating copolymerization with epoxides.The produced polythioimidocarbonates can be used as positive resists for electron beam lithography(sensitivity of 130μC/cm^(2) and contrast of 1.53 for poly(CHO-alt-EITC)).Coupling with their high refractive index(1.58—1.68),polythioimidocarbonates might find functional applications in optics.These results render ring-opening copolymerization of epoxides and isothiocyanates a facile route to enrich functional polymer library.
基金financial support from the National Natural Science Foundation of China(Nos.52222302 and 51973156).
文摘Efficient synthesis of polyester polyols with tunable molecular weight and microstructures from cyclic anhydride/epoxide mixtures by taking advantage of chain transfer reaction remains a great challenge,because most of the catalysts exhibit poor tolerance to chain transfer agent(CTA).In this contribution,we demonstrated that potassium acetate(KOAc)and 18-crown-6(18-C-6)combination has great potential in the synthesis of diverse polyester polyols with controllable molecular weight and high-end group fidelity.Com-pared with KOAc,KOAc/18-C-6 pair could induce a much faster chain transfer between the active and dormant chains,and thus produce polyester polyols with narrow and monomodal distribution.In addition,polyester polyols could be efficiently prepared in laboratory by using commercially available cyclic anhydride without further purification(containing about 2%diacid residual as CTA)with an extremely low catalyst loading([catalyst pair]:[anhydride]:[epoxide]=1:50000:250000,[catalyst pair]=0.0004 mol%).KOAc/18-C-6 could also promote the self-switchable copolymerization of cyclic anhydride/epoxide/cyclic ester mixtures.Ring-opening copolymerization of cyclic ester was initiated automatically after the full conversion of cyclic anhydride,finally producing polyester polyols with ABA-type block structure.
基金financially supported by the National Natural Science Foundation of China(No.22171017).
文摘The alternating copolymerization of hydroxyalkyl vinyl ethers and dialkyl maleates is investigated by conventional radical polymerization and reversible addition-fragmentation chain transfer polymerization(RAFT).The influence of comonomer structure,comonomer feeding ratios,and monomer concentrations on the copolymerization and the copolymer structure have been investigated systematically.With 2-hydroxyethyl vinyl ether(HEVE)and dimethyl maleates(DMM)as comonomers,a well-defined alternating copolymer is prepared with M_(n)=3400 and M_(w)/M_(n)=1.93 up to 71.6% monomer.The alternating sequential chain structure of the copolymers has been proved by both NMR and matrixassisted laser desorption/ionization time-of-flight mass spectrometry(MALDI-TOF MS).The experimental reactivity ratios and theoretical calculated highest occupied molecular orbital and the lowest unoccupied molecular orbital of vinyl ethers and alkyl maleates support that these monomer pairs have tendency to form alternating copolymers.With 2-cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate as the RAFT agent,the molecular weight of HEVE and DMM copolymer increases with the monomer conversion,demonstrating a controlled radical polymerization feature with well-controlled molecular weight and relatively narrower molecular weight distribution.With alternating copolymer of HEVE and DMM as macro-CTA(M_(n)=5200 and M_(w)/M_(n)=1.46),both the chain extension with HEVE and DMM(M_(n)=10400 and M_(w)/M_(n)=1.72)and block copolymerization with vinyl acetate have been successfully achieved(M_(n)=8500 and M_(w)/M_(n)=1.52).
基金the financial support of National Key Fundamental Research Program of China (Grant No. G1999064703) the National Natural Science Foundation of China (Grant No. 20104005).
文摘Amphiphilic copolymer of 5-benzyloxytrimethylene carbonate (BTMC) with poly (vinyl pyrrolidone) (PVP) was successfully synthesized using immobilized porcine pancreas lipase (IPPL) or SnOct2 as catalyst. Hydroxyl terminated PVP, synthesized with 2-mercaptoethanol as a chain transfer reagent, was employed as a rnacroinitiator. The resulting copolymers were characterized by GPC, ^1H NMR and IR. Increasing the BTMC/PVP-OH feed ratio ([B]/[P]) resulted in the increase of Mn of corresponding copolymers and the decrease of Mw/Mn. Immobilized enzyme has comparable catalytic activity to SnOct2 for the copolymerization.
文摘Styrene-isoprene-styrene(SIS) block copolymer was modified into epoxidized styrene-isoprene-styrene(ESIS) block copolymer with performic acid generated in situ from hydrogen peroxide and formic acid.The structure and property of ESIS were characterized by Fourier transform infrared(FT-IR) spectroscopy,gel permeation chromatography(GPC),thermogravimetric/differential thermogravimetric(TG/DTG),melt flow rate(MFR) and dynamic mechanical analysis(DMA),and the reaction mechanism in the process of epoxidation was analyzed.The results showed that C=C double bonds of 1,4-structure were more active than that of 3,4-structure in polyisoprene chains.With epoxidation reaction proceeding,the whole tendency of molecular weight increased and molecular weight distribution widened,and MFR firstly increased and latterly decreased.The heat resistance of ESIS was superior to that of SIS.When SIS was changed into ESIS with 15.3% of mass fraction of epoxide groups,Tg of polyisoprene chains increased from-45.3 ℃ to 10.9 ℃.In the earlier period of epoxidation,some molecular chains ruptured and new substances with low molecular weight formed.However,in the latter period,crosslinking reaction between molecular chains which was initiated by epoxide groups or C=C double bonds occurred and crosslinked insoluble substances came into being.
基金supported by the Ministry Basic Research Found(No.51412010204BQ0161).
文摘A kind of novel triblock copolymers of poly(γ-benzyl L-glutamate)-b-poly(tetrahydrofuran)-b-poly(γ-benzyl L-glutamate)s(PBLG-b-PTHF-b-PBLG)was synthesized by using bis(3-aminopropyl)terminated polytetrahydrofuran to initiate the ring-opening polymerization ofγ-benzyl L-glutamate N-carboxyanhydride(BLG-NCA).The corresponding multiblock poly(amino acid-urea)s were prepared in one-pot protocol from the chain extension of PBLG-b-PTHF-b-PBLG with MDI.The resulting triblock and multiblock copolymers were characterized by FTIR,~1H-NMR,^(13)C-NMR and GPC techniques.It is demonstrated that the chain extension has taken place to give rise to the copolymers with the well-defined block composition and narrow molecular weight distribution.A distinct T_g arising from the hard-segments was observed in all the copolymers.Their mechanical properties showed an increasing trend with the molecular weight enhancement of the prepolymers.