Polymer Chemistry
·
2016
·Vol. 7
·期 40
·6202-6210
·
IF 5.687
Yaochen Zheng,Shengying Cai,Li Peng,Yu Jin,Han Xu,Zhulin Weng,Zhengguo Gao,Bo Zhao,Chao Gao
We have coined a new term, group interval-controlled polymers (GICPs), to describe the unique structure of macromolecules with a tunable functional group interval. The precise control of a polymer main chain structure itself is still a big challenge, let alone the purposeful control of group interval simultaneously. Here, we successfully synthesized a series of epoxy GICPs via one-step UV-triggered thiol–yne polymerization of commercial glycidyl propargyl ether and dithiols at 0 °C. Subsequently, α,ω-thiols of each epoxy GICP were capped by two allyl glycidyl ethers via a thiol–ene click reaction, affording a stable product. Their unique group interval-controlled chemical structures were confirmed by a combination of nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and pyrene-fluorescent probe tests. Moreover, the epoxy groups within the GICPs were highly reactive and could be further functionalized and turned into a diverse range of customized groups such as azide, tertiary amino, thioester, and hydroxyl, etc. Therefore, a series of GICPs with designed functional groups are readily achieved on a large scale. Our work presents a reliable synthetic methodology for GICPs, paving a new way for the precise structure control of artificial macromolecules.
研究领域:
高分子化学
·
材料科学
✓ 已验证
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-11
·
IF 15.7
Xia Yanni,Shao Tong,Sun Yue,Wang Jianuo,Gu Chaoyuan,Zhang Chengjian,Zhang Xinghong
The precise placement of thioester bonds into sequence-controlled polymers remains a grand challenge. Here, we demonstrate the versatile synthesis of sequence-controlled polymers from the step polymerization of cyclic thioanhydrides ( A ), diacrylates ( B ), and diols/diamines ( C ). In addition to easily accessible diverse monomers, the method is metal-free/catalyst-free, atom-economical, and wide in monomer scope, yielding 107 polymers with >90% yields and weight-average molecular weights of up to 175.4 kDa. The obtained polymers contain ABAC -type repeating units and precisely distributed in-chain thioester and ester (and amide) groups. The chemoselectivity of the polymerization is revealed by density functional theory calculations. The polymer library exhibits considerably tunable performance: glass-transition temperatures of −36–72 °C, melting temperatures of 43–133 °C, degradability, thermoplastics/elastomers, and thioester-based functions. This study furnishes a facile method to precisely incorporate thioester bonds into sequence-controlled polymers.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
·
2018
·Vol. 34
·期 5
·828-832
·
IF 1.248
Qiao Yaping,Yuan Xiaoyan,Zhao Yunhui,Ren Lixia
Controlled preparation of brush polymers is important in the design of functional materials. In this study, poly( tert -butyl acrylate) macromonomers functionalized with norbornenyl end group(NB-P t BA) were synthesized via atom transfer radical polymerization in three different molecular weights, 2000(NB-P t BA-2k), 3000(NB-P t BA-3k), and 8000(NB-P t BA-8k). Additionally, brush polymers with P t BA as side chains were synthesized via ring-opening metathesis polymerization(ROMP). Kinetic studies on ROMP of NB-P t BA showed that there was a ceiling degree of polymerization(CDP) for the brush polymers, beyond which the polymerization of NB-P t BA was out of control. For brush polymers of P[NB-P t BA-2k] and P[NB-P t BA-3k], CDPs were estimated to be ca . 400, but the value of P[NB-P t BA-8k] was ca . 100. Therefore, the controlled ROMP of brush polymers was critical at the CDP limit with increased macromonomer molecular weight.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
·
2017
·Vol. 56
·期 2
·203-212
·
IF 2.952
Hai-Chao Huang,Zong-Jun Li,Bin Wang,Xiaolu Chen,Yue-Sheng Li
A series of novel aluminum complexes containing bulky aryl-β - ketiminato ligands [ArNCH C 10 H 7 C 6 H 5 O]Al(CH 3 ) 2 ( 3a , Ar = C 6 F 5 ; 3b , Ar = C 6 H 5 ; 3c , Ar = 2,6- i Pr 2 C 6 H 3 ) have been synthesized in high yields. These complexes were identified by 1 H and 13 C NMR spectroscopy, elemental analysis, and X - ray structural analysis. All the aluminum complexes could efficiently catalyze the ROP of ɛ- caprolactone ( ɛ -CL) and Lactide (LA) in a controlled manner. It was found that the steric effect of the ligand has less effect on the ROP of CL, while the polymerization rate of L -LA was suppressed significantly. More interestingly, this kind of catalysts can promote the random copolymerization of ɛ -CL and L -LA. The transesterification side reaction and the polymer composition could be adjusted by modulating the electronic and steric effects of the ligand. In paticular, compound 3c could produce quasi-random copolymers without transesterification side reactions, as indicated by both the values of the reactivity ratios of the two monomers ( r LA = 1.31; r CL = 0.99) and the similar average lengths of the caproyl and lactidyl sequences ( L CL = 2.34; L LA = 2.44). Finally, a drug-random copolymer conjugates could be easily prepared by using 3c , indicating a potential application of 3c in pharmacutical and biomedical field. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56 , 203–212
研究领域:
高分子化学
·
有机化学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2024
·
IF 4.1
Liu Xin-Yu,Zhu Liang,Jie Su-Yun,Li Bo-Geng
Due to their excellent biocompatibility and biodegradability, aliphatic polyesters are widely used in the biomedical, packaging and agricultural fields, which are usually accessed by the ring-opening polymerization (ROP) of lactones and the catalysts particularly play an important role. Herein a series of quinolinyl-urea catalysts have been synthesized via the reaction between isocyanate and aminoquinoline with an amino group at different substitution positions and characterized. In combination with 7-methyl-1, 5, 7-triazabicyclo[4,4,0]dec-5-ene (MTBD) as a cocatalyst and benzyl alcohol (BnOH) as an initiator, 1-(3,5-bis(trifluoromethyl)phenyl)-3-(quinolin-3-yl)urea ( 3-QU ) was observed to be most active for the ROP of δ -valerolactone ( δ -VL). The polymerization conditions were optimized by varying the type of organic base, catalyst concentration and reaction temperature. By changing the ratio of [M] 0 /[I], linear polyvalerolactones (PVLs) with different molecular weights and narrow molecular weight distribution were prepared. The kinetic and chain extension experiments were carried out to prove the “living”/controllable feature. And the NMR experiments were used to support the proposal of possible mechanism.
研究领域:
材料科学
·
生物医学工程
✓ 已验证
产品关联
DOI
高影响因子
Polymer Chemistry
·
2014
·Vol. 5
·期 16
·4726-4733
·
IF 5.368
Jinbao Xu,Junzhe Song,Stergios Pispas,Guangzhao Zhang
Narrowly distributed poly(ε-caprolactone) (PCL) was synthesized by the ring-opening polymerization (ROP) of ε-caprolactone (CL) using tris(pentafluorophenyl)borane (B(C6F5)3) as an acidic catalyst and benzyl alcohol (BnOH) as the initiator in bulk at 80 °C. The use of functional initiators such as 2-hydroxyethyl methacrylate (HEMA), propargyl alcohol (PGA), 6-azido-1-hexanol (AHA) and methoxy poly(ethylene glycol) (mPEG) leads to end-functionalized PCLs. 1H NMR, SEC and MALDI-TOF MS measurements clearly indicate the presence of an initiator residue at the chain end of the obtained PCL homopolymers. The study on polymerization kinetics confirms the controlled/living nature of the B(C6F5)3-catalyzed ROP of CL. Accordingly, the block copolymerization of CL with δ-valerolactone (VL) and trimethylene carbonate (TMC) successfully proceeded to give PCL-b-PVL and PCL-b-PTMC copolymers. Macrocyclic PCL was also prepared by the intramolecular click reaction of the heterotelechelic α-azido,ω-ethynyl-PCL.
研究领域:
高分子化学
·
材料科学
✓ 已验证
DOI
高影响因子
JOURNAL OF POLYMER SCIENCE
·
2020
·Vol. 58
·期 8
·1069-1078
·
IF 0
Deyong Xia,Qimin Jiang,Li Jiang,Wenyan Huang,Hongjun Yang,Xiaoqiang Xue,Bibiao Jiang
Herein, we report one-step synthesis of polymethacrylates-based macromonomers (MMs) in the presence of an organocatalyst phosphazene base ( t -BuP 4 ) and a functional initiator N -butyl-4-vinylbenzamide ( N -BVBA) containing a secondary amide and a styrenic double bond. A series of styrenic MMs with controlled molecular weight and relatively narrow polydispersity were synthesized under mild conditions. Detailed NMR analyses of the initiation process suggested that the anionic polymerization was initiated by nitrogen anion generated from abstraction of the proton from the secondary amide. NMR and MALDI-TOF MS analyses confirmed: (1) the selective polymerization of methacrylate-type double bonds, (2) controlled chain-end functionality of MMs with an unreacted styrenic double bond, as well as (3) the absence of transesterification between N -BVBA and methacrylate monomers. Furthermore, the homopolymerization and copolymerization of the MMs with comonomers were carried out for the preparation of graft copolymers. Through conventional radical polymerization, graft copolymers with different grafting densities were obtained at high MMs conversions, indicating the high reactivity of MMs. Thus, the one-step approach demonstrates a simple metal-free access to the controlled synthesis of MMs, and the prepared MMs can polymerize efficiently to convert into graft copolymers. Graphical Polymethacrylates-based macromonomer with a reactive styrenic double bond at the polymer chain-end was successfully synthesized by a one-step polymerization of methacrylates initiated by N -butyl-4-vinylbenzamide in the presence of t -BuP 4 as the organocatalyst. The macromonomers featured with controlled molecular weights and high fidelity chain-ends are highly reactive in the conventional radical polymerization to prepare graft copolymers with variable grafting densities.
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
JOURNAL OF POLYMER SCIENCE
·
2023
·Vol. 61
·期 14
·1486-1494
·
IF 3.4
Chenqi Zhao,Penghua Yan,Ruofan Liu,Wei Li,Yushun Jin,Qisong shi,Yibo Wu
The cationic polymerization of isobutene vinyl ether(IBVE) contains waters system was achieved by using triphenylmethylium tetrakis-(pentafluorophenyl)borate [Ph 3 C][B(C 6 F 5 ) 4 ], which overcame the harsh experimental requirements of traditional cationic polymerization. The influences of water content, solvent polarity, and reaction temperature on polymerization were studied. The end structure of the polymer was analyzed by 1 H-NMR. Combined with the effect of the proton trapping agent and triethylamine salt which can trap [H + ], it was found that there was a reversible equilibrium between [Ph 3 C + ] and [H + ] active species during the polymerization process. The cationic polymerizations of isobutyl vinyl ether were initiated by these two active species simultaneously. The controllable cationic polymerization of isobutyl vinyl ether was achieved by the addition of ethyl methyl carbonate and ethyl benzoate. Gaussian 09 W simulation confirms the polymerization mechanism. Graphical
研究领域:
高分子化学
·
有机化学
✓ 已验证
DOI
高影响因子
EUROPEAN POLYMER JOURNAL
·
2020
·
IF 3.862
Xiuzhe Yin,Linan Wang,Xiaomeng Zhang,Haitao Zhao,Zhe Cui,Peng Fu,Minying Liu,Xinchang Pang,Xiaoguang Qiao
Photo-induced metal free ATRP method was employed for the synthesis of star-shaped polymers. By using 21-Br-β-CD as the macroinitiator, 10-phenylphenothiazine as the photoredox catalyst, star-shaped PtBA homopolymers were synthesized. The photo-induced ATRP displayed all the characteristics of controlled/living polymerization systems and the good light control over the polymerization process. The successful chain extension with MMA demonstrated the high livingness of PtBA “arms” and good controllability of the Photo-induced metal free ATRP. Finally, the achieved PtBA-b-PMMA star-shaped copolymers were used as templates for the preparation of precisely size-tunable CdSe quantum dots after a simple hydrolyzing process.
研究领域:
高分子化学
·
纳米医学
·
药物递送
·
生物材料
·
胶体与界面科学
✓ 已验证
DOI
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
·
2013
·Vol. 51
·期 11
·2409-2415
·
IF 3.543
Jing Li,Xufeng Ni,Jun Ling,Zhiquan Shen
Polymerization of diethyl vinylphosphonate (DEVP) is achieved by using lanthanide tris(borohydride) complexes, Ln(BH 4 ) 3 (THF) 3 (Ln = Y, La, Nd, Sm, Gd, Dy, Lu) as an initiator. The characteristics and mechanism of polymerization as well as the properties of the resulting poly(diethyl vinylphophonate)s (PDEVPs) are studied. The effects of the lanthanide elements, the molar ratios of monomer to initiator ([ M ]/[ln]), reaction temperature and time on polymerization have been investigated in detail. The optimized polymerization conditions are 40 °C, 1 h in bulk with [ M ]/[ln] = 300. The kinetic study indicates that the polymerization of DEVP undergoes a controlled manner as the molecular weights (MWs) of PDEVPs increase with monomer conversion linearly maintaining moderate MW distribution (1.7–1.9). Additionally, a coordination anionic polymerization mechanism is proved by end-group analysis with ESI mass and 1 H NMR spectroscopy. The obtained PDEVPs have low glass transition temperature ( T g = −62 °C) and high thermal decomposition temperature ( T d > 300 °C) determined by differential scanning calorimetry and thermogravimetric analysis respectively. The thermosensitive behavior of PDEVP is characterized by evaluating the lower critical solution temperature of PDEVP in water by ultraviolet transmittance. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2409–2415
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
POLYMER BULLETIN
·
2025
·
IF 4
Zhao Xuan,Yang Liu,Sun Xinyu,Zhou Kun,Yuan Shuai
A novel class of 3-methylphenol alkoxy aluminum complexes was developed for the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) under mild conditions (60 °C, 30 min). Through systematic optimization of Al/CL molar ratios (5:1000 ~ 4:1000), monomer concentrations (1 mol/L), and reaction parameters, high polymer yield (99.9% ± 0.1%) was achieved, yielding polycaprolactone (PCL) with tunable molecular weights (M n up to 34 kg/mol) and narrow dispersity (PDI = 1.38). Structural characterization via 1 H NMR and FTIR confirmed successful PCL formation. GPC analysis validated controlled chain growth and uniformity (PDI < 1.5), while thermal properties were assessed via DSC and TGA, showing semicrystalline behavior and high thermal stability. Kinetic studies showed linear molecular weight progression with polymer yield, while sequential monomer feeding experiments confirmed living polymerization characteristics, with M n increasing proportionally and maintaining low PDI. Compared to conventional metal-based systems, this catalytic platform operates at lower temperatures with reduced toxicity risks, enabling energy-efficient synthesis of biodegradable polyester for biomedical and packaging applications.
研究领域:
高分子化学
·
生物材料
·
药物递送
·
组织工程
·
可降解聚合物
·
生物医学工程
✓ 已验证
产品关联
DOI
高影响因子
PETROLEUM SCIENCE AND TECHNOLOGY
·
2024
·
IF 1.3
Liqin Ding,Sifan Liu,Jie Deng,Hanbin Zhong,Shengrong Liang
Traditional free radical polymerization has poor controllability, and traditional petroleum-based lubricant additives have adverse effects on the environment. Poly (lauryl methacrylate (LMA)-soybean oil (SBO)) (P(LMA-SBO) was synthesized using Salen-Cu(II) complex as a catalyst and azodiisobutyronitrile (AIBN) as an initiator by the Schlenk techniques. The structure of P(LMA-SBO) was characterized by infrared spectroscopy (FT-IR), nuclear magnetic resonance (1H NMR), and gel permeation chromatography (GPC) followed by evaluating the solidification point depression performance by the Chinese standard method GB/T 510-2018, and the wax crystal morphology was studied by optical microscopy. The results show the catalytic activity could be 22.88 × 104 g·mol−1·h−1 and the number average molecular weight (Mn) of the copolymer is 8.71 × 104 with a low dispersity (Ɖ) of 1.37 under the optimal conditions, which indicates good controllability of the polymerization. Adding 1.0%(w) P(LMA-SBO) to the lubricating oil fraction (350–500 °C) could reduce the solidification point by 15 °C. Therefore, the Salen-Cu (II) catalyst was successfully applied to the controlled polymerization of LMA and SBO. The vegetable oil-based solidification point depressant of P(LMA-SBO) could be used as a potential alternative to replace the traditional solidification point depressant in the future.
研究领域:
材料科学
·
化学工程
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）