Pandemic-Driven Development of a Medical-Grade,Economic and Decentralized Applicable Polyolefin Filament for Additive Fused Filament Fabrication

A polyolefin with certified biocompatibility according to USP class VI was used by our group as feedstock for filament-based 3D printing to meet the highest medical standards in order to print personal protective equipment for our university hospital during the ongoing pandemic. Besides the chemical resistance and durability, as well as the ability to withstand steam sterilization, this polypropylene (PP) copolymer is characterized by its high purity, as achieved by highly efficient and selective catalytic polymerization. As the PP copolymer is suited to be printed with all common printers in fused filament fabrication (FFF), it offers an eco-friendly cost–benefit ratio, even for large-scale production. In addition, a digital workflow was established focusing on common desktop FFF printers in the medical sector. It comprises the simulation-based optimization of personalized print objects, considering the inherent material properties such as warping tendency, through to validation of the process chain by 3D scanning, sterilization, and biocompatibility analysis of the printed part. This combination of digital data processing and 3D printing with a sustainable and medically certified material showed great promise in establishing decentralized additive manufacturing in everyday hospital life to meet peaks in demand, supply bottlenecks, and enhanced personalized patient treatment.     

Supramolecular self‐assembly modification of ammonium polyphosphate and its flame retardant application in polypropylene

In order to improve its water resistance and compatibility with polymer matrix, ammonium polyphosphate (APP) is modified with melamine‐trimesic acid (MEL‐TA) aggregates by supramolecular self‐assembly technology. Chemical structure and morphology of APP@MEL‐TA are investigated by Fourier transform infrared spectroscopy and scanning electron microscopy (SEM), respectively. Intumescent flame retardant system of APP@MEL‐TA and charring‐foaming agent is introduced into polypropylene (PP) matrix. The flammability and combustion behavior of PP composites are investigated by limiting oxygen index (LOI), UL‐94 vertical burning, and cone calorimetry tests. In terms of LOI values and cone combustion results, APP@MEL‐TA performs better than pristine APP. Char residue of PP composites is investigated by SEM and Raman spectra. Flame retardant mechanisms are proposed based on thermal decomposition, combustion results, and analysis on char residue.     

Switchable Polymerization Triggered by Fast and Quantitative Insertion of Carbon Monoxide into Cobalt–Oxygen Bonds

A strategy that uses carbon monoxide (CO) as a molecular trigger to switch the polymerization mechanism of a cobalt Salen complex [salen=(R,R)‐N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine] from ring‐opening copolymerization (ROCOP) of epoxides/anhydrides to organometallic mediated controlled radical polymerization (OMRP) of acrylates is described. The key phenomenon is a rapid and quantitative insertion of CO into the Co?O bond, allowing for in situ transformation of the ROCOP active species (Salen)Co^III‐OR into the OMRP photoinitiator (Salen)Co^III‐CO₂R. The proposed mechanism, which involves CO coordination to (Salen)Co^III‐OR and subsequent intramolecular rearrangement via migratory insertion has been rationalized by DFT calculations. Regulated by both CO and visible light, on‐demand sequence control can be achieved for the one‐pot synthesis of polyester‐b‐polyacrylate diblock copolymers (?<1.15).     

基于响应面法的复合改良膨胀土无侧限抗压强度研究

为提高膨胀土的无侧限抗压强度,降低工程危害。本文在木质素改良膨胀土的研究基础上,通过单因素试验研究纤维长度、纤维掺量及木质素掺量对膨胀土抗压强度的影响规律,基于单因素试验结果,通过BBD响应面设计法进行响应面试验,建立二次回归模型,研究了双因素作用下对膨胀土无侧限抗压强度的影响。结果表明:单因素作用时,膨胀土无侧限抗压强度在各因素下均呈现先增大后减小的趋势;双因素交互作用时,木质素掺量和聚丙烯掺量二者交互作用显著性最好。由BBD响应面法得到的最优组合为:聚丙烯纤维长度为9 mm、纤维掺量为0.3%、木质素掺量为3%,该变量下平行试验组的平均抗压强度为552.48 kPa,相比于素膨胀的抗压强度提升了76.97%。可见此方案下对素膨胀的抗压强度提升效果最好。     

对乙烯基苯磺酸钠接枝聚丙烯纤维

利用超声波的分散原理,以二甲苯作为界面剂,把引发剂过氧化苯甲酰(BPO)分散到聚丙烯(PP)纤维表层里,然后在水溶液中接枝对乙烯基苯磺酸钠(VSB),得到接枝产物PP-g-VSB纤维．研究反应条件对接枝率的影响,以及接枝率对接枝纤维性能的影响,并用热重分析加以表征．结果表明,反应温度为90℃、VSB和 BPO质量分数分别为8％,4％,可得到接枝率34％、离子交换当量1．2 mmol·g-1的强酸型离子交换纤维．     

PP/HGB复合材料熔体的挤出胀大行为

应用XNR-400A型熔体流动速率仪,在190～230℃及荷载P为1．0～8．0kg的范围内,考察了中空玻璃微珠（HGB）填充聚丙烯（PP）复合材料的挤出胀大行为．结果表明,在200℃下,挤出胀大比B随着剪切应力的增加而提高,两者之间大致上呈线性函数关系;当P为3．80kg时,B随着温度的升高而下降,两者之间基本上呈线性关系．在190℃时,B随着HGB体积分数（φf）的增加而呈非线性减小;当φf为10％,P为3．80kg时,B随着HGB粒径的增加而有所提高．     

13C CP/MAS NMR studies of morphological changes in polypropylene: 2. The double melting endotherm of spunbonded fabrics

The double melting endotherm of spunbonded isotactic polypropylene (iPP) fabrics was investigated by monitoring changes in the solid-state NMR spectrum that result from thermal annealing. The DSC melting thermogram was found to change from a double to a single endotherm at anneal temperatures ≥156°C, with a concomitant increase in percent crystallinity. All of the carbon resonances in the CP/MAS NMR spectrum of the purely crystalline phase of iPP were found to be composed of multiple peaks with relative intensities that depend on anneal temperature. By monitoring the changes in the distribution of intensity among the various peaks of a given resonance, a transition temperature of 156°C was identified. Arguments are presented that this redistribution of intensity within a given carbon resonance characterizes the transformation from the α₁ to the α₂ monoclinic crystal form. The exothermicity associated with this transformation is responsible for the observation of a double melting endotherm by DSC. The splitting patterns observed in the NMR spectrum are discussed in terms of interlayer distances between layers of isochiral helices and the density of exposed methyls at the contact faces of these interlayers. © 1996 John Wiley & Sons, Inc.     

Maleic anhydride homopolymerization during melt functionalization of isotactic polypropylene

The homopolymerization of maleic anhydride was attempted at 190°C, during the melt-functionalization of polypropylene, either with or without organic peroxide using a Brabender plastograph. The free radical homopolymerization of pure maleic anhydride was also attempted either with or without organic peroxide, at 190°C, in vacuum-sealed glass vials. In all cases, free low molecular weight maleic anhydride oligomers were observed by low molecular weight size exclusion chromatography (SEC). This maleic anhydride homopolymerization tends to prove that the ceiling temperature of poly(maleic anhydride) probably lies above the previously published value of 160°C for these specific experimental conditions. © 1996 John Wiley & Sons, Inc.     

Crystallization behavior of isotactic polypropylene based nanocomposites

The effect of clay dispersion on the crystallization behavior of isotactic polypropylene (iPP)-based nanocomposites is reported. The T _m⁰ of the materials was calculated by the method proposed by Marand, the kinetics of crystallization was evaluated by the Avrami analysis and also the Hoffman-Lauritzen theory of crystallization regimes was applied. Montmorillonite was found to depress T _m⁰, to enhance the rate of crystallization and to ease the chain folding of macromolecules. These effects were magnified if clay was exfoliated, rather than intercalated.     

高密度聚乙烯/全同立构聚丙烯共混物超拉伸纤维的热行为与力学行为

用热拉法制备了高密度聚乙烯(HDPE)/全同立构聚丙烯(iPP)共混物超拉伸纤维,研究了拉伸比对其热行为及力学行为的影响,随拉伸比增加,纤维中HDPE与iPP的结晶度增大,熔融温度升高、熔程变宽;纤维中HDPE与iPP的结晶度低于其纯组分,熔融湿度与熔程基本不受组分比的影响,随拉伸比增加,纤维的模量增高,以HDPE为主的纤维的拉伸强度增大,以iPP为主的纤维拉伸强度增至一定值后,不再随拉伸比增加而增大,并有下降趋势。