Aliphatic polyesters and polycarbonates are among the promising sustainable polymers,which exhibit unique degradability and chain-chain interactions owing to their heterofunctionality.However,monocomponent aliphatic p...Aliphatic polyesters and polycarbonates are among the promising sustainable polymers,which exhibit unique degradability and chain-chain interactions owing to their heterofunctionality.However,monocomponent aliphatic polyesters and polycarbonates usually suffer from inferior properties and functionalities.By contrast,precisely modulated block copolymers composed of polyesters and polycarbonates give rise to sustainable materials with tailored performance.An efficient approach to synthesize the block copolymers is the ring-opening(co)polymerization of the heterocycle monomers.Herein,this review presents the heterocycle monomer ring-opening(co)polymerization for the formation of sequence-controlled block polyesters and polycarbonates.Available synthetic strategies,different monomers,monomer combinations and the catalyst systems for the formation of different block polyesters and polycarbonates are summarized.展开更多
Polylactide(PLA),methyl methacrylate-butadiene-styrene copolymer(MBS),and poly(propylene carbonate)polyurethane(PPCU)were blended and subjected to blown film process.The rheological,mechanical,morphological,thermal,an...Polylactide(PLA),methyl methacrylate-butadiene-styrene copolymer(MBS),and poly(propylene carbonate)polyurethane(PPCU)were blended and subjected to blown film process.The rheological,mechanical,morphological,thermal,and crystalline properties of the PLA/MBS/PPCU ternary blends and the mechanical properties of the resulting films were studied.Results of mechanical test showed that PPCU and MBS could synergistically toughen PLA.The impact strength of 50/10/40 PLA/MBS/PPCU blend(74.7 k J/m^2)was about 7.5 times higher than that of the neat PLA(10.8 k J/m^2),and the elongation at break of 50/10/40 PLA/MBS/PPCU blend(276.5%)was higher by about 45 times that of PLA(6.2%).The tear strength of PLA/MBS/PPCU films was 20 k N/m higher than that of PLA,and the elongation at break(MD/TD)of 50/10/40 PLA/MBS/PPCU films was 271.1%/222.3%,whereas that of PLA was only 2.7%/3.0%.POM observations displayed that the density of spherulite nucleation increased and the size of crystalline particles decreased with the addition of MBS.With increasing PPCU content from 5%to 20%,the density of spherulite nucleation increased and the size of crystalline particles decreased continuously,but the nucleation density of spherulites was slightly lowered with increasing PPCU content from 30%to 40%.The PLA/MBS/PPCU films exhibited excellent mechanical properties,which expanded the application range of these biodegradable films.展开更多
Aluminum porphyrin complexes are heavy-metal-free and soil-tolerant green catalysts for the copolymerization of CO2 and propylene oxide（PO）, but they suffer from relatively poor poly（propylene carbonate）（PPC） se...Aluminum porphyrin complexes are heavy-metal-free and soil-tolerant green catalysts for the copolymerization of CO2 and propylene oxide（PO）, but they suffer from relatively poor poly（propylene carbonate）（PPC） selectivity. Herein, steric hindrance porphyrin ligand was used to enhance the PPC selectivity. Typically, a bulky anthracene-like group was incorporated into the porphyrin ring to form 5,10,15,20-tetra（1,2,3,4,5,6,7,8-octahydro-1,4：5,8-dimethanoanthracen-9-yl）porphyrin, the aluminum porphyrin complex with this ligand, in combination with bis（triphenylphosphine）iminium chloride as a co-catalyst, produced completely alternate PPC. Additionally, the obtained PPC showed high regioselectivity, with a head-to-tail linkage content（HT） of 92%. Therefore, we demonstrated that introduction of bulky steric ligand into the porphyrin ring could reduce the propylene oxide homopolymerization activity leading to excellent PPC selectivity, and improve regioselectivity for the PO ring-opening during the copolymerization.展开更多
Block copolymer lithography is emerging as one of the leading technologies for patteming nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical a...Block copolymer lithography is emerging as one of the leading technologies for patteming nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical and lamellar domains is required for pattern transfer from the block copolymer film. This review highlights the state-of-art development of brushes to modify the substrates to control the assembly behaviors of block copolymers in films. Selected important contributions to the development of self-assembled monolayers, polymer brushes and mats, and chemically patterned brushes are discussed.展开更多
Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we de...Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we designed a dinuclear Salen-Cr(Ⅲ)complex,which showed higher efficiency for copolymerization of PO/CO_(2)and LA than that of mononuclear Salen-Cr(Ⅲ)complex.Besides,we successfully obtained gradient and random copolymers of PPC-PLA in one pot.Furthermore,by adjusting reaction temperature,block ratios of PPC/PLA in copolymers were controllable(block ratio of PPC/PLA=1.0 at 40℃,while block ratio of PPC/PLA=0.5 at room temperature).While increasing the reaction temperature to 60℃,conversion of LA was much faster than that of PO so that gradient copolymers were obtained.展开更多
Cobalt porphyrin complexes （TPPConIX） （TPP = 5,10,15,20-tetraphenyl-porphyrin; X = halide） in combination with bis（triphenylphosphine） iminium chloride （PPNC1） were used for the eopolymerization of cyelohexene...Cobalt porphyrin complexes （TPPConIX） （TPP = 5,10,15,20-tetraphenyl-porphyrin; X = halide） in combination with bis（triphenylphosphine） iminium chloride （PPNC1） were used for the eopolymerization of cyelohexene oxide and CO2. The highest turnover frequency of 67.2 h^-1 was achieved after 13 h at 20℃, and the obtained poly（1,2-cyclohexylene carbonate） （PCHC） showed number average molecular weight （Mn） of 10 × 10^3. Though the obtained PCHC showed atactie structure, the m-centered tetrads content reached 58.1% at CO2 pressure of 1.0 MPa, and decreased to 51.9% at CO2 pressure of 6.0 MPa, indicating that it was inclined to form atactic polymer at high CO2 pressure.展开更多
A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and e-ca...A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and e-caprolactone, exhibiting notably high activity at ambient temperature, The influence of imine bridge length and substituents of diketone over the course of polymerization was investigated in details. Remarkably, 4a was confirmed to be a rare example of exceedingly active and robust zinc catalysts, achieving major transformation of lactide under extremely low loading （0.025 mol%） within 18 rain. The influence of various monomers as well as the polymerization mechanism have also been discussed.展开更多
Carbon dioxide-based polyols with ultra-low molecular weight(ULMW,Mn<1000 g/mol)are emergent polyurethane precursors with economic and environmental benefits.However,the lack of effective proton-tolerant catalytic ...Carbon dioxide-based polyols with ultra-low molecular weight(ULMW,Mn<1000 g/mol)are emergent polyurethane precursors with economic and environmental benefits.However,the lack of effective proton-tolerant catalytic systems limits the development of this field.In this work,the polymeric aluminum porphyrin catalyst(PAPC)system was applied to the copolymerization of CO_(2)and propylene oxide,where sebacic acid,bisphenol A,poly(ethylene glycol),and water were used as chain transfer agents to achieve the controlled synthesis of CO_(2)-polyols.The molecular weight of the resulting CO_(2)-polyols could be facilely regulated in the range of 400–930 g/mol at low catalyst loadings,fully demonstrating its catalytic advantages of high activity,high product selectivity,and excellent proton tolerance of PAPC.Meanwhile,the catalytic efficiency of PAPC could reach up to 2.1–5.2 kg/g under organic CTA conditions,even reaching 1.9 kg/g using water as the CTA.The cPC content could be controlled within 1.0 wt%under the optimized conditions,indicating the excellent controllability of the PAPC system.ULMW CO_(2)-polyols combines the advantages of low viscosity(∼3000 mPa s at 25°C),low glass transition temperature(∼−73°C),and high carbonate unit content(∼40%),which is important for the development of high-performance polyurethanes.展开更多
Polyion complex （PIC） micelles were spontaneously formed in aqueous solutions through electrostatic interaction between two oppositely charged block copolymers, poly（N-isopropylacrylamide）-b-poly（L-glutamic acid...Polyion complex （PIC） micelles were spontaneously formed in aqueous solutions through electrostatic interaction between two oppositely charged block copolymers, poly（N-isopropylacrylamide）-b-poly（L-glutamic acid） and poly（N-isopropylacrylamide）-b-poly（L-lysine）. Their controlled synthesis was achieved via the ring opening polymerization of N-carboxyanhydrides （NCA）, ε-benzyloxycarbonyl-L-lysine （Lys（Z）-NCA） or γ-benzyl-L-glutamate （BLG-NCA） with amino-terminated poly（N-isopropylacrylamide） macroinitiator and the subsequent deprotection reaction. The formation of PIC micelles was confirmed by dynamic light scattering and transmission electron microscopy. Turbidimetric characterization suggested that the formed PIC micelles had a concentration-dependent thermosensitivity and their phase transition behaviors could be easily adjusted either by the block length of coplymers or the concentration of micelles.展开更多
In this work, a specific polylactide （PLA） 4032D was melt-mixed with a new toughener： butyl acrylate （BA）, ethyl acrylate （EA） and glycidyl methacrylate （GMA） copolymer （BA-EA-GMA）. DMA tests showed that PL...In this work, a specific polylactide （PLA） 4032D was melt-mixed with a new toughener： butyl acrylate （BA）, ethyl acrylate （EA） and glycidyl methacrylate （GMA） copolymer （BA-EA-GMA）. DMA tests showed that PLA/BA-EA-GMA blends were partially miscible. The degree of crystallinity of PLA increased while the cold crystallization temperature shifted to higher temperatures with increasing BA-EA-GMA content. The SEM micrographs showed that PLA/BA-EA-GMA blends had a good dispersion and this phenomenon was in good agreement with their higher impact strength. The result showed that the adding of BA-EA-GMA has enhanced the flexibility of PLA/BA-EA-GMA blends as compared with pure PLA. The impact strength was changed from 3.4 kJ/m2 for pure PLA to 29.6 kJ/m2 for 80/20 PLA/BA-EA-GMA blend.展开更多
The effect of the architecture of poly(ethylene glycol)/poly(L-lactide)(PEG/PLLA) block copolymers on the non-isothermal crystallization behaviors of PLLA blocks was investigated by differential scanning calorimetry(D...The effect of the architecture of poly(ethylene glycol)/poly(L-lactide)(PEG/PLLA) block copolymers on the non-isothermal crystallization behaviors of PLLA blocks was investigated by differential scanning calorimetry(DSC) and wide angle X-ray diffraction(WAXD). 1-Arm MPEG-b-PLLA and 4-arm PEG-b-PLLA(4PEG-b-PLLA) were synthesized by the ring-opening polymerization of Llactide in the presence of poly(ethylene glycol) methyl ether(MPEG) and 4-arm poly(ethylene glycol)(4PEG). 4-Arm PLLA-b-MPEG(4PLLA-b-PEG) was synthesized by coupling 4-arm PLLA and MPEG. The WAXD results indicated that the crystalline structure of PLLA blocks did not alter due to the different chain architectures. The average values of Avrami index(ˉn) were all above 4, which indicated that the nucleation mechanism of PLLA blocks was heterogeneous nucleation, regardless of the architectures. The overall crystallization rates were decreased markedly as following: MPEG-b-PLLA > 4PEG-b-PLLA > 4PLLA-b-PEG, ascribed to the different confinement by PEG blocks and to the steric hindrance of chain architectures. Therefore, the crystallization of PLLA blocks became more difficult and the crystallization activation energy of the PLLA blocks increased due to the confinement of chain architectures.展开更多
The past few decades have witnessed rapid gains in our demands of antifouling membranes such as water purification membranes and hemodialysis membranes.A variety of methodologies have been proposed for improving the a...The past few decades have witnessed rapid gains in our demands of antifouling membranes such as water purification membranes and hemodialysis membranes.A variety of methodologies have been proposed for improving the antifouling performance and the hemocompatibility of the membranes.In this study,a series of copolymers(PSF-PESSB)containing polysulfone(PSF)and poly(arylene ether sulfone)bearing pendant zwitterionic sulfobetaine groups(PESSB)were prepared via one-pot polycondensation.Subsequently,the ultrafiltration(UF)membranes were prepared from different zwitterion-containing copolymers.The prepared membranes showed high thermal stability and mechanical properties.Besides,it also displayed attractive antifouling performance and blood compatibility.Compared with the original PSF membrane,the amount of protein absorption on the modified membrane was reduced;the flux recovery ratio and the resistance to blood cells were significantly improved.The results of this work suggest that PSF-PESSB membranes are expected to be applied in blood purification.The introduction of zwitterion-containing polymers to membranes paves ways for developing advanced hemodialysis technologies for crucial process.展开更多
Antimicrobial peptides(AMPs)have been considered as an alternative to small molecule antibiotics since they are difficult to develop antimicrobial resistance.Hyperbranched polylysine(HPL),an AMP mimics,has gained atte...Antimicrobial peptides(AMPs)have been considered as an alternative to small molecule antibiotics since they are difficult to develop antimicrobial resistance.Hyperbranched polylysine(HPL),an AMP mimics,has gained attention due to its broad-spectrum antibacterial activities,but it also suffers from high toxicity.Here we report a facile strategy to engineer the toxicity of HPL by copolymerizing lysine(K)with a hydrophobic amino acid,e.g.,alanine(A),tryptophan(W)or phenylalanine(F),to afford hyperbranched random copolymers.These copolymers have comparable antibacterial activities to HPL while their cytotoxicities and in vivo toxicities are lowered when the type and content of hydrophobic amino acid and the size of copolymers are optimized.The G.mellonella infection model demonstrates that the copolymers are effective against the S.aureus infection in vivo.The copolymers kill the bacteria through the disruption of cell membranes and the bacteria do not develop resistance to the copolymers.展开更多
The ring-opening polymerization of 5-methyl-1,3-dioxolane-2,4-dione（lactic O-carboxylic anhydride,LacOCA） using organometallic complexes,including Co（Ⅲ） complexes with Schiff base ligands,Tin（Ⅱ） alphatates and...The ring-opening polymerization of 5-methyl-1,3-dioxolane-2,4-dione（lactic O-carboxylic anhydride,LacOCA） using organometallic complexes,including Co（Ⅲ） complexes with Schiff base ligands,Tin（Ⅱ） alphatates and Al（Ⅲ） complexes with Schiff base ligands,was explored.The polymerization was carried out by treatment of the organometallic complexes with LacOCA in toluene under mild conditions.The corresponding poly（lactic acid） was characterized by spectroscopy and thermal analyses,which revealed insight into the structure of the effective catalyst for the polymerization of LacOCA.展开更多
It is of great interest to make a degradable material widely tailorable to replace petroleum-derived products among diverse applications.Here,we report the construction of a new multi-purpose degradable material for t...It is of great interest to make a degradable material widely tailorable to replace petroleum-derived products among diverse applications.Here,we report the construction of a new multi-purpose degradable material for the first time via a simple ternary copolymerization system comprisingε-caprolactone(ε-CL),cyclohexane oxide(CHO)and CO_(2).Under low pressure of 1 bar∼5 bar,the ring-opening polymerization(ROP)ofε-CL and ring-opening copolymerization(ROCOP)of CO_(2) and CHO can simultaneously proceed.The carbonate units are randomly distributed on the polymer chain.These random terpolymers have controllable molar mass(10-106 kDa)and compositions(4-33 mol%CO_(2)).And the obtained materials show large-span tunability from tough plastic to elastomer and even adhesive.展开更多
A new strategy for the metal-free coordination–insertion ring-opening polymerization of tetrahydrofuran by the central metalloid Boron has been first identified.Bis(pentafluorophenyl)(phenoxy)borane was used as a cat...A new strategy for the metal-free coordination–insertion ring-opening polymerization of tetrahydrofuran by the central metalloid Boron has been first identified.Bis(pentafluorophenyl)(phenoxy)borane was used as a catalyst for the polymerization reaction system.And polytetrahydrofuran with high molecular weight and narrow molecular weight distribution could be obtained.The proposed mechanism was studied by MALDI-TOF,ESI-MS and O-18 isotope labeling analyses as a metal-free coordination insertion mechanism.展开更多
Aliphatic polyamides have been considered as eco-friendly materials,useful for a wide range of applications.However,it still presents obstacle to produce sustainable aliphatic polyamides from abundant renewable source...Aliphatic polyamides have been considered as eco-friendly materials,useful for a wide range of applications.However,it still presents obstacle to produce sustainable aliphatic polyamides from abundant renewable sources.Herein,we describe that 4-hydroxyproline(4-HYP),a renewable resource,was readily converted to its corresponding bicyclic bridged lactam monomers bearing pendant Boc-protected secondary amino group,and oligo-ethylene glycol group.Lithium hexamethyldisilazide(LiHMDS)-mediated polymerization of the resulting monomers exhibited a controlled feature,affording sustainable aliphatic polyamides with number-average molecular weight up to 73 kg/mol and a low molecular weight distribution?<1.28.Overall,this work can lead to a novel kind of functional and sustainable polyamides with potential applications,including degradable plastics,and drug delivery.展开更多
Polyester and polyether are two key oxygenated polymers, and completely alternative sequence of poly(ester-alt-ether) could efficiently combine the advantages(including flexibility, degradability, etc.) of both segmen...Polyester and polyether are two key oxygenated polymers, and completely alternative sequence of poly(ester-alt-ether) could efficiently combine the advantages(including flexibility, degradability, etc.) of both segments. Currently, despite their copolymers could be synthesized from one-pot mixture of cyclic esters and epoxides, perfectly alternative microstructure is very challenging to realize and typically restricted to certain monomer pairs. Moving forward, synthesizing poly(ester-alt-ether) from commercially available and largescale monomers would be a significant advance. For example, successfully commercialized poly(glycolic acid)(PGA), which is not easily soluble in polymers due to its high crystallinity and is brittle and difficult to control the degradation cycle, would encounter a new paradigm if engineered into poly(ester-altether). In this work, starting from the design of monomer with hybrid structures, we successfully synthesized a series of 1,4-dioxan-2-one containing different substituents based on glycolide(GA) and epoxides using commercially available Salen-Cr(III) and PPNCl catalytic systems.The new monomers underwent ring-opening polymerization(ROP) to form a series of poly(ester-alt-ether) with perfectly alternating glycolic acid and propylene glycol repeat units under catalytic system of thiourea/base. The poly(ester-alt-ether) have significantly lower glass-transition temperature than PGA. Additionally, the poly(ester-alt-ether) can be chemically recovered to monomer using Sn(Oct)2 or 1,8-diazabicyclo[5.4.0]undecane-7-ene(DBU) as a catalyst in solution, thus establishing a closed-loop life cycle. From monomers derived from GA and epoxides, this work furnishes a novel strategy for the synthesis of poly(ester-alt-ether) with chemical recyclability.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
In this study,the poly(D-lactide)-block-poly(butylene succinate)-block-poly(D-lactide)(PDLA-b-PBS-b-PDLA)triblock copolymers with a fixed length of PBS and various lengths of PDLA are synthesized,and the crystallizati...In this study,the poly(D-lactide)-block-poly(butylene succinate)-block-poly(D-lactide)(PDLA-b-PBS-b-PDLA)triblock copolymers with a fixed length of PBS and various lengths of PDLA are synthesized,and the crystallization behaviors of the PDLA and PBS blocks are investigated.Although both the crystallization behaviors of PBS and PDLA blocks depend on composition,they exhibit different variations.For the PDLA block,its crystallization behaviors are mainly influenced by temperature and block length.The crystallization signals of PDLA block appear in the B-D 2-2 specimen,and these signals get enhanced with PDLA block length.The crystallization rates tend to decrease with increasing PDLA block lendth during crystallizing at 90 and 100°C.Crystallizing at higher temperature,the crystallization rates increase at first and then decrease with block length.The crystallization rates decrease as elevating the crystallization temperature.The melting temperatures of PDLA blocks increase with block lengths and crystallization temperatures.For the PBS block,its crystallization behaviors are mainly controlled by the nucleation and confinement from PDLA block.The crystallization and melting enthalpies as well as the crystallization and melting temperatures of PBS block reduce as a longer PDLA block has been copolymerized,while the crystallization rates of the PBS block exhibit unique component dependence,and the highest rate is observed in the B-D 2-2 specimen.The Avrami exponent of PBS crystallites is reduced as a longer PDLA block is incorporated or the sample is crystallized at higher temperature.This investigation provides a convenient route to tune the crystallization behavior of PBS and PLA.展开更多
基金supported by the National Natural Science Foundation of China,Fund for Distinguished Young Scholars(No.52325301)CAS Project for Young Scientists in Basic Research(YSBR-094)the National Natural Science Foundation of China,Basic Science Center Program(No.51988102).
文摘Aliphatic polyesters and polycarbonates are among the promising sustainable polymers,which exhibit unique degradability and chain-chain interactions owing to their heterofunctionality.However,monocomponent aliphatic polyesters and polycarbonates usually suffer from inferior properties and functionalities.By contrast,precisely modulated block copolymers composed of polyesters and polycarbonates give rise to sustainable materials with tailored performance.An efficient approach to synthesize the block copolymers is the ring-opening(co)polymerization of the heterocycle monomers.Herein,this review presents the heterocycle monomer ring-opening(co)polymerization for the formation of sequence-controlled block polyesters and polycarbonates.Available synthetic strategies,different monomers,monomer combinations and the catalyst systems for the formation of different block polyesters and polycarbonates are summarized.
基金financially supported by the National Science Foundation of Zhejiang Province of China (No. LQY19B040001)the fund of Science and Technology Bureau of Jilin Province of China (No. 20170204012SF)+1 种基金the Program of Changchun Science and Technology Bureau (No. 16CX23)National Key Research and Development Program of China (No. 2016YFC0501402-5)
文摘Polylactide(PLA),methyl methacrylate-butadiene-styrene copolymer(MBS),and poly(propylene carbonate)polyurethane(PPCU)were blended and subjected to blown film process.The rheological,mechanical,morphological,thermal,and crystalline properties of the PLA/MBS/PPCU ternary blends and the mechanical properties of the resulting films were studied.Results of mechanical test showed that PPCU and MBS could synergistically toughen PLA.The impact strength of 50/10/40 PLA/MBS/PPCU blend(74.7 k J/m^2)was about 7.5 times higher than that of the neat PLA(10.8 k J/m^2),and the elongation at break of 50/10/40 PLA/MBS/PPCU blend(276.5%)was higher by about 45 times that of PLA(6.2%).The tear strength of PLA/MBS/PPCU films was 20 k N/m higher than that of PLA,and the elongation at break(MD/TD)of 50/10/40 PLA/MBS/PPCU films was 271.1%/222.3%,whereas that of PLA was only 2.7%/3.0%.POM observations displayed that the density of spherulite nucleation increased and the size of crystalline particles decreased with the addition of MBS.With increasing PPCU content from 5%to 20%,the density of spherulite nucleation increased and the size of crystalline particles decreased continuously,but the nucleation density of spherulites was slightly lowered with increasing PPCU content from 30%to 40%.The PLA/MBS/PPCU films exhibited excellent mechanical properties,which expanded the application range of these biodegradable films.
基金financially supported by the National Natural Science Foundation of China(No.51673193)Key Project for Frontier Research(2016)Youth Innovation Promotion Association Chinese Academy of Sciences
文摘Aluminum porphyrin complexes are heavy-metal-free and soil-tolerant green catalysts for the copolymerization of CO2 and propylene oxide（PO）, but they suffer from relatively poor poly（propylene carbonate）（PPC） selectivity. Herein, steric hindrance porphyrin ligand was used to enhance the PPC selectivity. Typically, a bulky anthracene-like group was incorporated into the porphyrin ring to form 5,10,15,20-tetra（1,2,3,4,5,6,7,8-octahydro-1,4：5,8-dimethanoanthracen-9-yl）porphyrin, the aluminum porphyrin complex with this ligand, in combination with bis（triphenylphosphine）iminium chloride as a co-catalyst, produced completely alternate PPC. Additionally, the obtained PPC showed high regioselectivity, with a head-to-tail linkage content（HT） of 92%. Therefore, we demonstrated that introduction of bulky steric ligand into the porphyrin ring could reduce the propylene oxide homopolymerization activity leading to excellent PPC selectivity, and improve regioselectivity for the PO ring-opening during the copolymerization.
基金financially supported by the National Natural Science Foundation of China(Nos.51173181 and 51373166)“The Hundred Talents Program”from the Chinese Academy of Sciences and the International S&T Cooperation Program from Department of Science and Technology of Jilin Province(No.20160414032GH)
文摘Block copolymer lithography is emerging as one of the leading technologies for patteming nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical and lamellar domains is required for pattern transfer from the block copolymer film. This review highlights the state-of-art development of brushes to modify the substrates to control the assembly behaviors of block copolymers in films. Selected important contributions to the development of self-assembled monolayers, polymer brushes and mats, and chemically patterned brushes are discussed.
基金financially supported by the National Key R&D Program of China (No. 2021YFA1501700)the National Natural Science Foundation of China+1 种基金Basic Science Center Program (No.51988102)the National Natural Science Foundation of China (No. 52073272)
文摘Copolymerization of propylene oxide(PO)/carbon dioxide(CO_(2))and lactide(LA)is achievable to form new copolymers,combining the advantages of both poly(propylene carbonate)(PPC)and polylactide(PLA).In this study,we designed a dinuclear Salen-Cr(Ⅲ)complex,which showed higher efficiency for copolymerization of PO/CO_(2)and LA than that of mononuclear Salen-Cr(Ⅲ)complex.Besides,we successfully obtained gradient and random copolymers of PPC-PLA in one pot.Furthermore,by adjusting reaction temperature,block ratios of PPC/PLA in copolymers were controllable(block ratio of PPC/PLA=1.0 at 40℃,while block ratio of PPC/PLA=0.5 at room temperature).While increasing the reaction temperature to 60℃,conversion of LA was much faster than that of PO so that gradient copolymers were obtained.
基金financially supported by the National Natural Science Foundation of China(Nos.20634040 and 50903084)
文摘Cobalt porphyrin complexes （TPPConIX） （TPP = 5,10,15,20-tetraphenyl-porphyrin; X = halide） in combination with bis（triphenylphosphine） iminium chloride （PPNC1） were used for the eopolymerization of cyelohexene oxide and CO2. The highest turnover frequency of 67.2 h^-1 was achieved after 13 h at 20℃, and the obtained poly（1,2-cyclohexylene carbonate） （PCHC） showed number average molecular weight （Mn） of 10 × 10^3. Though the obtained PCHC showed atactie structure, the m-centered tetrads content reached 58.1% at CO2 pressure of 1.0 MPa, and decreased to 51.9% at CO2 pressure of 6.0 MPa, indicating that it was inclined to form atactic polymer at high CO2 pressure.
基金financially supported by the National Natural Science Foundation of China(Nos.21574124,51503203 and51233004)
文摘A series of zinc silylamido complexes based upon NNO tridentate enolic Schiff base framework have been synthesized and characterized. These complexes were tested for the ring opening polymerization of lactide and e-caprolactone, exhibiting notably high activity at ambient temperature, The influence of imine bridge length and substituents of diketone over the course of polymerization was investigated in details. Remarkably, 4a was confirmed to be a rare example of exceedingly active and robust zinc catalysts, achieving major transformation of lactide under extremely low loading （0.025 mol%） within 18 rain. The influence of various monomers as well as the polymerization mechanism have also been discussed.
基金The authors greatly appreciated the financial support from National Natural Science Foundation of China(Nos.22101277,51988102,22271275,22201280).
文摘Carbon dioxide-based polyols with ultra-low molecular weight(ULMW,Mn<1000 g/mol)are emergent polyurethane precursors with economic and environmental benefits.However,the lack of effective proton-tolerant catalytic systems limits the development of this field.In this work,the polymeric aluminum porphyrin catalyst(PAPC)system was applied to the copolymerization of CO_(2)and propylene oxide,where sebacic acid,bisphenol A,poly(ethylene glycol),and water were used as chain transfer agents to achieve the controlled synthesis of CO_(2)-polyols.The molecular weight of the resulting CO_(2)-polyols could be facilely regulated in the range of 400–930 g/mol at low catalyst loadings,fully demonstrating its catalytic advantages of high activity,high product selectivity,and excellent proton tolerance of PAPC.Meanwhile,the catalytic efficiency of PAPC could reach up to 2.1–5.2 kg/g under organic CTA conditions,even reaching 1.9 kg/g using water as the CTA.The cPC content could be controlled within 1.0 wt%under the optimized conditions,indicating the excellent controllability of the PAPC system.ULMW CO_(2)-polyols combines the advantages of low viscosity(∼3000 mPa s at 25°C),low glass transition temperature(∼−73°C),and high carbonate unit content(∼40%),which is important for the development of high-performance polyurethanes.
基金financially supported by the National Natural Science Foundation of China (Nos. 20904053, 51021003,51173184)the Ministry of Science and Technology of China (International cooperation program 2011RI0001)the Program of the Science and Technology of Changchun (No. 2010061)
文摘Polyion complex （PIC） micelles were spontaneously formed in aqueous solutions through electrostatic interaction between two oppositely charged block copolymers, poly（N-isopropylacrylamide）-b-poly（L-glutamic acid） and poly（N-isopropylacrylamide）-b-poly（L-lysine）. Their controlled synthesis was achieved via the ring opening polymerization of N-carboxyanhydrides （NCA）, ε-benzyloxycarbonyl-L-lysine （Lys（Z）-NCA） or γ-benzyl-L-glutamate （BLG-NCA） with amino-terminated poly（N-isopropylacrylamide） macroinitiator and the subsequent deprotection reaction. The formation of PIC micelles was confirmed by dynamic light scattering and transmission electron microscopy. Turbidimetric characterization suggested that the formed PIC micelles had a concentration-dependent thermosensitivity and their phase transition behaviors could be easily adjusted either by the block length of coplymers or the concentration of micelles.
基金financially supported by the Science&Technology Bureau of Jilin Province of China(No.20126023)
文摘In this work, a specific polylactide （PLA） 4032D was melt-mixed with a new toughener： butyl acrylate （BA）, ethyl acrylate （EA） and glycidyl methacrylate （GMA） copolymer （BA-EA-GMA）. DMA tests showed that PLA/BA-EA-GMA blends were partially miscible. The degree of crystallinity of PLA increased while the cold crystallization temperature shifted to higher temperatures with increasing BA-EA-GMA content. The SEM micrographs showed that PLA/BA-EA-GMA blends had a good dispersion and this phenomenon was in good agreement with their higher impact strength. The result showed that the adding of BA-EA-GMA has enhanced the flexibility of PLA/BA-EA-GMA blends as compared with pure PLA. The impact strength was changed from 3.4 kJ/m2 for pure PLA to 29.6 kJ/m2 for 80/20 PLA/BA-EA-GMA blend.
基金financially supported by the National Natural Science Foundation of China(Nos.51303176,51873209,51573178,and 51773194)the National Key Research and Development Program of China(No.2016YFB0302500)
文摘The effect of the architecture of poly(ethylene glycol)/poly(L-lactide)(PEG/PLLA) block copolymers on the non-isothermal crystallization behaviors of PLLA blocks was investigated by differential scanning calorimetry(DSC) and wide angle X-ray diffraction(WAXD). 1-Arm MPEG-b-PLLA and 4-arm PEG-b-PLLA(4PEG-b-PLLA) were synthesized by the ring-opening polymerization of Llactide in the presence of poly(ethylene glycol) methyl ether(MPEG) and 4-arm poly(ethylene glycol)(4PEG). 4-Arm PLLA-b-MPEG(4PLLA-b-PEG) was synthesized by coupling 4-arm PLLA and MPEG. The WAXD results indicated that the crystalline structure of PLLA blocks did not alter due to the different chain architectures. The average values of Avrami index(ˉn) were all above 4, which indicated that the nucleation mechanism of PLLA blocks was heterogeneous nucleation, regardless of the architectures. The overall crystallization rates were decreased markedly as following: MPEG-b-PLLA > 4PEG-b-PLLA > 4PLLA-b-PEG, ascribed to the different confinement by PEG blocks and to the steric hindrance of chain architectures. Therefore, the crystallization of PLLA blocks became more difficult and the crystallization activation energy of the PLLA blocks increased due to the confinement of chain architectures.
基金financially supported by the National Natural Science Foundation of China(52003266,21961160739)the Development of Scientific and Technological Project of the Jilin Province(YDZJ202101ZYTS162,20200801051GH)Chinese Academy of Sciences-Wego Group High-tech Research&Development。
文摘The past few decades have witnessed rapid gains in our demands of antifouling membranes such as water purification membranes and hemodialysis membranes.A variety of methodologies have been proposed for improving the antifouling performance and the hemocompatibility of the membranes.In this study,a series of copolymers(PSF-PESSB)containing polysulfone(PSF)and poly(arylene ether sulfone)bearing pendant zwitterionic sulfobetaine groups(PESSB)were prepared via one-pot polycondensation.Subsequently,the ultrafiltration(UF)membranes were prepared from different zwitterion-containing copolymers.The prepared membranes showed high thermal stability and mechanical properties.Besides,it also displayed attractive antifouling performance and blood compatibility.Compared with the original PSF membrane,the amount of protein absorption on the modified membrane was reduced;the flux recovery ratio and the resistance to blood cells were significantly improved.The results of this work suggest that PSF-PESSB membranes are expected to be applied in blood purification.The introduction of zwitterion-containing polymers to membranes paves ways for developing advanced hemodialysis technologies for crucial process.
基金financially supported by the National Natural Science Foundation of China(No.51973212)Department of Science and Technology of Jilin Province(Nos.20210203119SF and 20210203173SF)。
文摘Antimicrobial peptides(AMPs)have been considered as an alternative to small molecule antibiotics since they are difficult to develop antimicrobial resistance.Hyperbranched polylysine(HPL),an AMP mimics,has gained attention due to its broad-spectrum antibacterial activities,but it also suffers from high toxicity.Here we report a facile strategy to engineer the toxicity of HPL by copolymerizing lysine(K)with a hydrophobic amino acid,e.g.,alanine(A),tryptophan(W)or phenylalanine(F),to afford hyperbranched random copolymers.These copolymers have comparable antibacterial activities to HPL while their cytotoxicities and in vivo toxicities are lowered when the type and content of hydrophobic amino acid and the size of copolymers are optimized.The G.mellonella infection model demonstrates that the copolymers are effective against the S.aureus infection in vivo.The copolymers kill the bacteria through the disruption of cell membranes and the bacteria do not develop resistance to the copolymers.
基金supported by the National Natural Science Foundation of China(No.50973108) and the G-CO program,Waseda University
文摘The ring-opening polymerization of 5-methyl-1,3-dioxolane-2,4-dione（lactic O-carboxylic anhydride,LacOCA） using organometallic complexes,including Co（Ⅲ） complexes with Schiff base ligands,Tin（Ⅱ） alphatates and Al（Ⅲ） complexes with Schiff base ligands,was explored.The polymerization was carried out by treatment of the organometallic complexes with LacOCA in toluene under mild conditions.The corresponding poly（lactic acid） was characterized by spectroscopy and thermal analyses,which revealed insight into the structure of the effective catalyst for the polymerization of LacOCA.
基金funded by the National Key R&D Program of China(No.2021YFA1501700)the Science and Technology Development Plan of Jilin Province(Nos.20230101042JC,20210201059GX)+2 种基金the National Natural Science Foundation of China,Basic Science Center Program(No.51988102)the National Natural Science Foundation of China(Nos.52203017,52073272 and 22293062)Bureau of International Cooperation Chinese Academy of Sciences(No.029GJHZ2023017MI).
文摘It is of great interest to make a degradable material widely tailorable to replace petroleum-derived products among diverse applications.Here,we report the construction of a new multi-purpose degradable material for the first time via a simple ternary copolymerization system comprisingε-caprolactone(ε-CL),cyclohexane oxide(CHO)and CO_(2).Under low pressure of 1 bar∼5 bar,the ring-opening polymerization(ROP)ofε-CL and ring-opening copolymerization(ROCOP)of CO_(2) and CHO can simultaneously proceed.The carbonate units are randomly distributed on the polymer chain.These random terpolymers have controllable molar mass(10-106 kDa)and compositions(4-33 mol%CO_(2)).And the obtained materials show large-span tunability from tough plastic to elastomer and even adhesive.
基金funded by the National Key R&D Program of China(No.2021YFA1501700)the Science and Technology Development Plan of Jilin Province(Nos.20230101042JC,20210201059GX)+2 种基金the National Natural Science Foundation of China,Basic Science Center Program(No.51988102)the National Natural Science Foundation of China(Nos.52203017,52073272 and 22293062)Bureau of International Cooperation Chinese Academy of Sciences(No.029GJHZ2023017MI)。
文摘A new strategy for the metal-free coordination–insertion ring-opening polymerization of tetrahydrofuran by the central metalloid Boron has been first identified.Bis(pentafluorophenyl)(phenoxy)borane was used as a catalyst for the polymerization reaction system.And polytetrahydrofuran with high molecular weight and narrow molecular weight distribution could be obtained.The proposed mechanism was studied by MALDI-TOF,ESI-MS and O-18 isotope labeling analyses as a metal-free coordination insertion mechanism.
基金financially supported by the National Natural Science Foundation of China(Nos.U21A2089 and 51873211)。
文摘Aliphatic polyamides have been considered as eco-friendly materials,useful for a wide range of applications.However,it still presents obstacle to produce sustainable aliphatic polyamides from abundant renewable sources.Herein,we describe that 4-hydroxyproline(4-HYP),a renewable resource,was readily converted to its corresponding bicyclic bridged lactam monomers bearing pendant Boc-protected secondary amino group,and oligo-ethylene glycol group.Lithium hexamethyldisilazide(LiHMDS)-mediated polymerization of the resulting monomers exhibited a controlled feature,affording sustainable aliphatic polyamides with number-average molecular weight up to 73 kg/mol and a low molecular weight distribution?<1.28.Overall,this work can lead to a novel kind of functional and sustainable polyamides with potential applications,including degradable plastics,and drug delivery.
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)+2 种基金the National Natural Science Foundation of ChinaBasic Science Center Program (No.51988102)the National Natural Science Foundation of China (Nos. 52203017 and 52073272)。
文摘Polyester and polyether are two key oxygenated polymers, and completely alternative sequence of poly(ester-alt-ether) could efficiently combine the advantages(including flexibility, degradability, etc.) of both segments. Currently, despite their copolymers could be synthesized from one-pot mixture of cyclic esters and epoxides, perfectly alternative microstructure is very challenging to realize and typically restricted to certain monomer pairs. Moving forward, synthesizing poly(ester-alt-ether) from commercially available and largescale monomers would be a significant advance. For example, successfully commercialized poly(glycolic acid)(PGA), which is not easily soluble in polymers due to its high crystallinity and is brittle and difficult to control the degradation cycle, would encounter a new paradigm if engineered into poly(ester-altether). In this work, starting from the design of monomer with hybrid structures, we successfully synthesized a series of 1,4-dioxan-2-one containing different substituents based on glycolide(GA) and epoxides using commercially available Salen-Cr(III) and PPNCl catalytic systems.The new monomers underwent ring-opening polymerization(ROP) to form a series of poly(ester-alt-ether) with perfectly alternating glycolic acid and propylene glycol repeat units under catalytic system of thiourea/base. The poly(ester-alt-ether) have significantly lower glass-transition temperature than PGA. Additionally, the poly(ester-alt-ether) can be chemically recovered to monomer using Sn(Oct)2 or 1,8-diazabicyclo[5.4.0]undecane-7-ene(DBU) as a catalyst in solution, thus establishing a closed-loop life cycle. From monomers derived from GA and epoxides, this work furnishes a novel strategy for the synthesis of poly(ester-alt-ether) with chemical recyclability.
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financially supported by the National Natural Science Foundation of China (Nos. 51403089, 51373169, 21574060, and 21374044)the Major Special Projects of Jiangxi Provincial Department of Science and Technology (No. 20114ABF05100)+3 种基金the Project of Jiangxi Provincial Department of Education (No. GJJ170229)the Technology Plan Landing Project of Jiangxi Provincial Department of Education (No. GCJ2011-243)the Outstanding Youth Foundation of Jiangxi Normal University, China Postdoctoral Science Foundation (No. 2019M652282)Postdoctoral Science Foundation of Jiangxi Province (No. 2018KY37)
文摘In this study,the poly(D-lactide)-block-poly(butylene succinate)-block-poly(D-lactide)(PDLA-b-PBS-b-PDLA)triblock copolymers with a fixed length of PBS and various lengths of PDLA are synthesized,and the crystallization behaviors of the PDLA and PBS blocks are investigated.Although both the crystallization behaviors of PBS and PDLA blocks depend on composition,they exhibit different variations.For the PDLA block,its crystallization behaviors are mainly influenced by temperature and block length.The crystallization signals of PDLA block appear in the B-D 2-2 specimen,and these signals get enhanced with PDLA block length.The crystallization rates tend to decrease with increasing PDLA block lendth during crystallizing at 90 and 100°C.Crystallizing at higher temperature,the crystallization rates increase at first and then decrease with block length.The crystallization rates decrease as elevating the crystallization temperature.The melting temperatures of PDLA blocks increase with block lengths and crystallization temperatures.For the PBS block,its crystallization behaviors are mainly controlled by the nucleation and confinement from PDLA block.The crystallization and melting enthalpies as well as the crystallization and melting temperatures of PBS block reduce as a longer PDLA block has been copolymerized,while the crystallization rates of the PBS block exhibit unique component dependence,and the highest rate is observed in the B-D 2-2 specimen.The Avrami exponent of PBS crystallites is reduced as a longer PDLA block is incorporated or the sample is crystallized at higher temperature.This investigation provides a convenient route to tune the crystallization behavior of PBS and PLA.
