Influence ofβ-nucleating Compound Agents on the Mechanical Properties and Crystallization Behavior of Polypropylene Random Copolymer

A novel polypropylene random(PPR)composite materials with optimized properties was developed by addingβ-nucleating compound agents(rare earth complex WBG-2 and aryl amide derivative TMB-5)and ternary compound modifier(TPE/WBG-2/CaCO_(3)).The effects of differentβ-nucleating agents and ternary compound modifier on the mechanical properties and crystallization behavior of PPR were analyzed.The results show that,compared with pure PPR materials,both WBG-2 and TMB-5 could significantly improve the impact strength of PPR.The crystallization temperature of PPR increased with the addition ofβ-nucleating agent.The modified PPR prepared with ternary compound modifier showed the most excellent comprehensive properties.

Rapid synthesis of biodegradable poly(epsilon-caprolactone-co-p-dioxanone) random copolymers under microwave irradiation

Biodegradable poly(epsilon-caprolactone-co-p-dioxanone)(PCDO) random copolymers have been synthesized by ring-opening polymerization of epsilon-caprolactone(CL) and p-dioxanone(PDO) under microwave irradiation.The effects of irradiation time and different CL/PDO molar feed ratios on the microwave-assisted ring-opening polymerization(MROP) of PCDO have been discussed.The resultant products were characterized by ~1H NMR,GPC and DSC.It was found that the polymerization was completed within 20 min at 140℃.In th...

Engineering Antibacterial Activities and Biocompatibility of Hyperbranched Lysine-based Random Copolymers

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.

Micelle-crosslinked hydrogels with stretchable,self-healing,and selectively adhesive properties:Random copolymers work as dynamic yet self-sorting domains

The design of crosslinking domains is a vital factor to create functional hydrogels with controlled physical,mechanical,and adhesive properties.This paper demonstrates versatile synthetic systems of micelle-crosslinked hydrogels with highly stretchable,self-healing,and selectively adhesive properties.For this,methacrylate-bearing random copolymer micelles are designed as physical and covalent crosslink domains via the self-assembly of amphiphilic random copolymers carrying hydrophilic poly(ethylene glycol)(PEG),hydrophobic butyl or dodecyl groups,and methacrylate-terminal PEG in water.The size,aggregation number,and pendant methacrylate number of the micelles are controlled by the composition and degree of polymerization.Hydrogels are efficiently obtained from the free radical polymerization of hydrophilic monomers such as PEG acrylate and acrylamide in the presence of the micelle crosslinkers in water.Owing to the dynamic yet selective chain exchange properties of the micelle domains,the hydrogels are highly stretchable up to over 1000%and show self-healing and selectively adhesive properties.The self-healing of hydrogels is promoted upon heating due to the fast chain exchange of the micelle domains,whereas hydrogels consisting of micelles with different alkyl groups are never adhesive because of their self-sorting properties.

Effect of Long Chain Branching on the Rheological Behavior,Crystallization and Mechanical Properties of Polypropylene Random Copolymer

Long chain branched polypropylene random copolymers （LCB-PPRs） were prepared via reactive extrusion with the addition of dicumyl peroxide （DCP） and various amounts of 1,6-hexanediol diacrylate （HDDA） into PPR. Fourier transform infrared spectrometer （FTIR） was applied to confirm the existence of branching and（ investigate the grafting degree for the modified PPRs. Melt flow index （MFI） and oscillatory shear rheological properties including complex viscosity, storage modulus, loss tangent and the Cole-Cole plots were studied to differentiate the LCB-PPRs from linear PPR. Differential scanning calorimetry （DSC） and polarized light microscopy （PLM） were used to study the melting and crystallization behavior and the spherulite morphology, respectively. Qualitative and quantitative analyses of rheological curves demonstrated the existence of LCB. The effect of the LCB on crystalline morphology, crystallization behavior and molecular mobility, and, thereby, the mechanical properties were studied and analyzed. Due to the entanglements between molecular chains and the nucleating effect of LCB, LCB-PPRs showed higher crystallization temperature and crystallinity, higher crystallization rate, more uniformly dispersed and much smaller crystallite compared with virgin PPR, thus giving rise to significantly improve impact strength. Moreover, the LCB-PPRs exhibited the improved yield strength. The mobility of the molecular chain segments, as demonstrated by dynamic mechanical analysis （DMA）, was improved for the modified PPRs, which also contributed to the improvement of their mechanical properties.

COMBINED EFFECT OF MODIFIED ZEOLITE 13X AND β-NUCLEATING AGENT ON IMPROVING β-CRYSTAL CONTENT AND TOUGHENING POLYPROPYLENE RANDOM COPOLYMER

Although addition of β-nucleating agent directly into homo-polypropylene （PPH） is a useful method to improve ,β-crystal content and toughen PPH, polypropylene random copolymer （PPR） makes this method powerless due to its random structure and low crystallinity. In this study, the β-nucleated PPR with high β-crystal content was prepared by a novel high effective β-nucleating system which consists of β-nucleation agent （TMB-5） and modified zeolite 13X （M13X）. It was found that M13X and TMB-5 had a synergistic influence on improving β-crystal content and toughening PPR. The content of β-crystal in PPR/M13X/TMB-5 was significantly larger than the sum of that in PPR/M13X and PPR/TMB-5. Besides, fracture behavior, phase morphology and relaxation of matrix chain segments were also investigated. The results showed that M13X and TMB-5 improved the mobility of amorphous chain segments at low temperature and contributed to much energy dissipation. This work provides a powerful method to modify PPR.

Copolymerization of PO/CO_(2)and Lactide by a Dinuclear Salen-Cr(Ⅲ)Complex:Gradient and Random Copolymers with Modificable Microstructure

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.

Enhanced Ultraviolet Resistance of Polypropylene Random Copolymer Filled by ZnO-supported Mesoporous Zeolite

To enhance the ultraviolet resistance of ZnO based polymer materials, ZnO-supported mesoporous zeolite（M-ZnO） was prepared and characterized by atomic absorption spectroscopy and scanning electron microscopy. The ultraviolet resistance, crystallization behavior and melting characteristics of ZnO and M-ZnO filled PPR composites were compared by FTIR spectra and differential scanning calorimetry. The ultraviolet resistance of M-ZnO filled PPR composites is higher than that of ZnO filled PPR composites, indicating higher ultraviolet resistance of M-ZnO than that of ZnO. The crystallization temperatures of mesoporous zeolite filled PPR were higher than those of M-ZnO and decreased with increasing UV-irradiation time. But the crystallization temperatures of M-ZnO filled PPR composites were not influenced by UV-irradiation time. The ZnO supported on the surface of zeolite is effective in enhancing the ultraviolet resistance of ZnO based polymer materials.

Organostibine mediated controlled/living random copolymerization of styrene and methyl methacrylate

The first example of organostibine mediated controlled/living random copolymerization of styrene(St) and methyl methacrylate(MMA) was achieved by heating a solution of St/MMA/organostibine mediator at 100 °C or St/MMA/organostibine mediator/AIBN with various monomer feed ratios at 60 °C.The addition of AIBN significantly decreased the reaction temperature and enhanced the rate of copolymerization.The structure of poly(St-co-MMA) was verified by 1H NMR.The reactivity ratios at 60 °C were determined by the extended Kelen-Tüds method to be YSt = 0.40 and YMMA = 0.44.The ln([M]0/[M]) increased linearly with increasing reaction time.The number-average molecular weights of poly(St-co-MMA) increased linearly with conversion.Poly(St-co-MMA) with expected number-average molecular weight and low polydispersity index was formed.The living characteristic was further confirmed by chain-extension of poly(St-co-MMA) to form poly(St-co-MMA)-b-PMMA.

Enhanced Mechanics in Injection Molded Isotactic Polypropylene/Polypropylene Random Copolymer Blends via Introducing Network-like Crystal Structure

The crystallization behavior, rheological behavior, mechanical properties and microstructures of injection molded isotactic polypropylene （iPP）, polypropylene random copolymer （co-PP） and iPP/co-PP blends were investigated. Differential scanning calorimetry （DSC） and dynamic rheological analysis illustrated that iPP and co-PP were compatible in the blends and co-PP uniformly dispersed in the/PP phase. Polarizing optical microscope （POM） was adopted to observe the crystal size and morphology evolution. The results of mechanical properties and scanning electron microscopy （SEM） indicated that the crystal size of iPP in iPP/co-PP blends （10 wt% co-PP ＋ 90 wt% iPP and 30 wt% co-PP ＋ 70 wt% iPP） radically decreased after the incorporation of co-PP. During crystallization, the molecular chain segments of co-PP could penetrate iPP spherulites and form a network-like crystalline structure. The network-like crystal structure could effectively transmit stress and consume more energy to overcome intermolecular forces to resist stretching. In this way, the strength would improve to a certain degree. The impact fracture mechanism of iPP/co-PP blends is quasi ductile fracture by multiple crazes. Our work discovered that the blends containing 10 wt% and 30 wt% ofco-PP exhibited prominent toughness and reinforcement.

Random Copolymers Based on Thieno[3,4-c]pyrrole-4,6-dione and Isoindigo Building Blocks for Polymer Solar Cells

Three random conjugated polymers,RP-TiI,RP-2TiI and RP-TVTiI based on both thieno[3,4-c]pyrrole-4,6-dione and isoindigo units have been synthesized by Stille cross-coupling reaction.The optical and electrochemical properties of new polymers have been investigated.The resulted polymers showed broad absorption spectra and appropriate energy levels for polymer solar cell applications.The bulk heterojunction devices based on the blend of the polymer RP-TiI and PC_(61)BM showed a power conversion efficiency of 1.75%.

TIME AND POLING HISTORY DEPENDENT ENERGY STORAGE AND DISCHARGE BEHAVIORS IN POLY(VINYLIDENE FLUORIDE-CO-HEXAFLUOROPROPYLENE) RANDOM COPOLYMERS

We studied cycle time （0.01-10 s with triangular input waves） and poling history （continuous versus fresh poling） dependent electric energy storage and discharge behaviors in poly（vinylidene fluoride-co-hexafluoropropylene） [P（VDF- HFP）] films using the electric displacement -- the electric field （D-E） hysteresis loop measurements. Since the permanent dipoles in PVDF are orientational in nature, it is generally considered that both charging and discharging processes should be time and poling history dependent. Intriguingly, our experimental results showed that the charging process depended heavily on the cycle time and the prior poling history, and thus the D-E hysteresis loops had different shapes accordingly. However, the discharged energy density did not change no matter how the D-E loop shape varied due to different measurements. This experimental result could be explained in terms of reversible and irreversible polarizations. The reversible polarization could be charged and discharged fairly quickly （〈 5 ms for each process）, while the irreversible polarization depended heavily on the poling time and the prior poling history. This study suggests that it is only meaningful to compare the discharged energy density for PVDF and its copolymer films when different cycle times and poling histories are used.

无规共聚透明聚丙烯的研发

研究了不同成核剂种类和用量对无规共聚聚丙烯(PP)RP210M透明性的影响。通过优化复合助剂配方,成功工业化生产了无规共聚透明PP产品(PP-E800),综合性能好于对标产品。

三元无规策略在高性能非富勒烯有机太阳能电池活性层的应用

近年来,由于窄带隙小分子受体的快速发展以及高性能聚合物给体不断出现,非富勒烯有机太阳能电池(NF-OSCs)取得了突破性进展,其能量转换效率(PCE)已接近20%。然而,随着D-A交替共聚聚合物材料设计逐渐饱和,迫切需要开发更高效的共轭聚合物材料。而利用无规共聚策略制备的D-A型无规共聚物具有能级易调节、有宽且强的吸收以及较高的吸光系数等优势,因此备受关注。本文首先讨论了无规D-A共聚策略在调控聚合物性质和器件性能方面的优势。其次,分别从无规聚合物给体材料和受体材料两方面综述了无规共聚策略在活性层材料的应用研究。最后,对于三元无规聚合物在有机太阳能电池中的进一步发展进行了总结与展望。

无规共聚聚丙烯研究进展

综述了用于生产无规共聚聚丙烯的Ziegler-Natta催化剂和茂金属催化剂的性能及由两种催化剂制备的无规共聚聚丙烯的特点,并总结了近年来关于乙烯-丙烯无规共聚物、丙烯-1-丁烯无规共聚物和其他几种典型的无规共聚聚丙烯产品的聚合机理、聚合工艺及共聚物物理性能的研究进展。

丁烯基弹性体的制备与性能

采用自制的负载钛系催化剂催化丁烯-1与己烯-1进行本体聚合制备了丁烯基弹性体,开展了聚合工艺优化研究,通过核磁共振波谱和差示扫描量热表征了共聚物的结构,考察了共聚物的物理机械性能。结果表明,最佳聚合工艺条件:n(单体)/n(催化剂)为20000~25000,n(三乙基铝)/n(负载钛系催化剂)为250~300,聚合温度为45℃,聚合时间为4 h,氢气压力为0.10~0.15 MPa;共聚物含有丁烯-1与己烯-1的无规共聚结构且无固定熔点;随着共聚单体己烯-1用量的增加,共聚物的拉伸强度和弹性模量均减小,当加入己烯-1质量分数为20%时,共聚物的断裂标称应变达到534%。

Synthesis and Characterization of Poly(L-lactide-co-ε-caprolactone) Copolymers

A series of random and block poly（ L-lactide-co-e-caprolactone ） （ PCLA ） copolymers whh different composition are prepared using stannous octaoate as catalyst.The effects of the amount of initiator on the intrinsic viscosity have been investigated. The structure of the PCLA copolymers is characterized by means of nuclear magnetic resonance（ NMR ）, Fourier transform infrared spectrum （ FTIR ）, differential scanning calorimetry （ DSC ） and X- ray diffraction （ XRD ） methods. It is shown that the synthesis condition and the composition of copolymers obrious influence on the structure of PCLA copolymers. Hydrolytic degradation of the copolymers in a PBS solution of pH 7.4 at 37.0℃ shows that the copolymers of different composhions degrade at different rates.

无规共聚型聚小分子受体聚合物的发展和应用

有机太阳能电池(OSCs)对实现低碳经济的发展具有重要意义。因其具有质轻、制备柔性、便携式设备等独特优势,具有巨大的商业开发价值。全聚合物太阳能电池(All-PSCs)凭借良好的光热稳定性及机械性能,被认为更有潜力应用于未来的柔性、可穿戴设备中。然而,目前的能量转换效率(PCE)相比基于小分子受体材料的光伏器件还相对较低,其中一个最重要的原因是缺乏高效的聚合物受体。本文首先将对发展节点以及目前应用高效率All-PSCs中的受体聚合物的研究进展进行简要介绍,随后将重点对其中通过无规共聚策略合成的聚小分子受体聚合物的优势与发展进行综述并对未来聚小分子受体聚合物的发展进行展望。

Sequence design in terpolymerization ofε-caprolactone,CO_(2) and cyclohexane oxide:Random ester-carbonate distributions lead to large-span tunability

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.

无规抗冲共聚聚丙烯的非等温结晶动力学

在Spheripol工艺中试装置上制备了丙丁无规抗冲共聚聚丙烯(记作PP-1)和乙丙丁无规抗冲共聚聚丙烯(记作PP-2),对两种聚丙烯的非等温结晶行为进行了研究,针对无规抗冲共聚聚丙烯实际生产过程中的结晶特点,分别结合Caze法和Mo法提出的理论对非等温结晶动力学Ozawa模型进行了修正。结果表明:采用修正过的两种方法更加符合无规抗冲共聚聚丙烯实际生产过程中的非等温结晶行为。采用Caze法修正Ozawa模型后求出的PP-1和PP-2的Avrami指数分别为2.44,2.37,说明乙烯单体的引入并不会使PP-1的成核机理和生长方式发生改变。采用Mo法修正Ozawa模型后求出的动力学参数F(T)在同一相对结晶度下PP-1小于PP-2,表明在同一时间内PP-2要达到某一结晶度所需冷却速率更大;采用Kissinger法计算的PP-1和PP-2的结晶活化能分别为11.12,14.14 kJ/mol,进一步证实了上述结果。