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Study on pyrolysis behavior and reaction mechanism estimation of fireproof sealant with TG/FTIR analysis 利用 TG/FTIR 分析法研究防火密封胶的热解行为和反应机理估算
IF 3.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-07-30 DOI: 10.1007/s00289-024-05440-5
Xin Liu, Jiaqing Zhang, Fengju Shang, Lingxin He, Wei Liu, Rui Liu, Yi Guo, Yanming Ding

Fireproof sealant is a common sealing material and has a wide range of applications, which has the dual performance of sealing and fireproof. To figure out its thermal degradation behavior, the thermogravimetric experiments combined with Fourier transform infrared technology were conducted at multiple heating rates. The results showed that the pyrolysis process could be separated into three stages and the explicit reaction equations were revealed corresponding to each stage: First, ammonium polyphosphate decomposed to produce a large amount of inorganic acid, along with a small amount of ammonia and water. Then, a large amount of ammonia gas was produced from melamine decomposition, and the substrate including acrylic resin began to react. Furthermore, the remaining base materials and intermediate carbonized materials continued to be decomposed to produce large amounts of carbon dioxide, water and residue. The experimental results indicated that the various components of fireproof sealant could cooperate closely and played a synergistic role in flame retardant, which could be an important reference value for guiding the improvement of fire sealing materials.

防火密封胶是一种常见的密封材料,具有密封和防火双重性能,应用广泛。为了弄清它的热降解行为,研究人员结合傅立叶变换红外技术,在多种加热速率下进行了热重实验。结果表明,热解过程可分为三个阶段,并揭示了每个阶段对应的显式反应方程:首先,聚磷酸铵分解产生大量无机酸以及少量氨和水。然后,三聚氰胺分解产生大量氨气,包括丙烯酸树脂在内的基材开始反应。此外,剩余的基底材料和中间碳化材料继续分解,产生大量二氧化碳、水和残渣。实验结果表明,防火密封胶的各种成分能够密切配合,在阻燃方面发挥协同作用,这对指导防火密封材料的改进具有重要的参考价值。
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引用次数: 0
Physicochemical properties of biocomposites prepared by thermoset resin in situ polymerization 热固性树脂原位聚合制备的生物复合材料的物理化学特性
IF 3.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-07-29 DOI: 10.1007/s00289-024-05434-3
Moise Manga, Elhadji Babacar Ly, Mamadou Lo, Ramzi Khiari, Abdou Karim Diallo, Mohamed Naceur Belgacem

The development of composite materials with fewer interface problems always helps to obtaining good properties. Two types of insulating biopolymers (7% w/w) were incorporated into a conductive matrix (polyaniline) during polymerization. The synthesis method, inspired by the synthesis of polyaniline and the coating of chitosan for the development of flexible electrodes, produces thermosets that are more thermally stable than the matrix until 350 °C. While one (gum) reduces the electrical conductivity, the other (lignin) increases the basic value of the raw material (~ 0.72 S Cm–1) by a factor of 10. The physicochemical and morphological analyses show the formation of the polymer on the surface of the biopolymer with the appearance of new chemical bonds by interactions between hydroxyls of the biopolymer and the nitrogen of amine function from the polyaniline.

开发界面问题较少的复合材料总是有助于获得良好的性能。在聚合过程中将两种绝缘生物聚合物(7% w/w)加入到导电基质(聚苯胺)中。这种合成方法受到聚苯胺合成和壳聚糖涂层的启发,用于开发柔性电极,生产出的热固性材料在 350 °C 之前的热稳定性高于基体。其中一种(树胶)降低了导电性,而另一种(木质素)则将原材料的基本值(~ 0.72 S Cm-1)提高了 10 倍。物理化学和形态分析表明,生物聚合物表面形成了聚合物,生物聚合物的羟基与聚苯胺的胺功能氮相互作用,形成了新的化学键。
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引用次数: 0
Grafting of polyester fabrics with methacrylic acid 用甲基丙烯酸接枝聚酯织物
IF 3.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-07-29 DOI: 10.1007/s00289-024-05391-x
Boonsri Kusuktham, Krisda Suchiva, Somchai Udon

Modification of polyester (poly(ethylene terephthalate)) fabric by grafting with poly(methacrylic acid) was studied. The objective was to improve the hydrophilicity of polyester and, hence, its water uptake. The modified polyester fabrics were characterized by gravimetric method, Fourier transform infrared, dynamic mechanical analysis, and scanning electron microscopy. It was found that grafting of methacrylic acid onto polyester fabrics could be effected by radical reaction using benzoyl peroxide as radical initiator. Swelling of polyester fabric with benzyl alcohol was also found to be necessary for grafting to occur. The parameters which affected the modification reaction were initiator concentration, monomer to fabric ratio, reaction temperature, and reaction time. In addition, it was shown that the percentage uptake of moisture of the modified fabric (1–4.6%) increased with increase in the extent of grafting (5–32%). The modified fabric tended to be stiffer than the unmodified fabric, but they could be softened by controlled treatment with aqueous solution of sodium hydroxide. The stability of the modified polyester fabric, however, was found to decrease with increase in the extent of modification (high monomer to fabric ratio) and increasing concentration of sodium hydroxide solution. Thus, careful control of sodium hydroxide treatment process was necessary to prevent deterioration of the modified polyester fabric.

通过接枝聚甲基丙烯酸对聚酯(聚对苯二甲酸乙二酯)织物进行改性的研究。目的是改善聚酯的亲水性,从而提高其吸水性。通过重量法、傅立叶变换红外线、动态机械分析和扫描电子显微镜对改性聚酯织物进行了表征。研究发现,使用过氧化苯甲酰作为自由基引发剂,可通过自由基反应将甲基丙烯酸接枝到聚酯织物上。研究还发现,用苯甲醇使聚酯织物膨胀是发生接枝的必要条件。影响改性反应的参数包括引发剂浓度、单体与织物的比例、反应温度和反应时间。此外,研究还表明,改性织物的吸湿率(1-4.6%)随着接枝程度(5-32%)的增加而增加。改性织物比未改性织物更硬,但可通过控制氢氧化钠水溶液的处理使其软化。不过,改性聚酯织物的稳定性会随着改性程度(高单体与织物比率)的增加和氢氧化钠溶液浓度的增加而降低。因此,必须仔细控制氢氧化钠处理过程,以防止改性聚酯织物变质。
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引用次数: 0
One-pot synthesis of copolymers through the application of the thermally reversible furan/maleimide Diels–Alder reaction. 2. preparation of polyester–polyurethane copolymers 通过应用热可逆呋喃/马来酰亚胺 Diels-Alder 反应一步合成共聚物。2. 制备聚酯-聚氨酯共聚物
IF 3.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-07-29 DOI: 10.1007/s00289-024-05441-4
Eliane Trovatti, Antonio Gilberto Ferreira, Antonio José Felix Carvalho, Alessandro Gandini

The furan/maleimide Diels–Alder (DA) reaction has been exploited to construct thermally reversible macromolecular structures, such as linear or cross-linked polycondensates, or to cross-link linear polymers, using the free end-type or pending furan and maleimide moieties as the diene and dienophile reagents. Here we report a different approach for the synthesis of homopolymers based on a diol, in which the DA adduct formed by the furan and the maleimide sits within the diol monomer structure. The OH end groups of the diol were used for the synthesis of a polyester and a polyurethane using conventional polycondensation methods and to study their retro DA (rDA) depolymerization through the thermal decomposition of their inner DA adducts. The relevant contribution of this study was however the possibility of synthesizing a copolymer by heating these two polymers together to induce their rDA deconstruction and then lowering the temperature in order to allow the ensuing fragments to recombine statistically by successive DA couplings, thus building the corresponding ester-urethane copolymer. 1H NMR spectroscopy and DSC analysis were employed to confirm the success of this promising approach.

呋喃/马来酰亚胺 Diels-Alder(DA)反应已被用于构建热可逆的大分子结构,如线性或交联的缩聚物,或利用游离端型或待定的呋喃和马来酰亚胺分子作为二烯和亲二烯试剂交联线性聚合物。在这里,我们报告了一种基于二元醇合成均聚物的不同方法,其中呋喃和马来酰亚胺形成的 DA 加合物位于二元醇单体结构中。利用二元醇的羟基端基,采用传统缩聚方法合成了一种聚酯和一种聚氨酯,并通过内部 DA 加合物的热分解研究了它们的逆 DA(rDA)解聚。不过,本研究的相关贡献在于通过加热这两种聚合物来诱导它们的 rDA 解构,然后降低温度,使随后产生的碎片通过连续的 DA 偶联进行统计重组,从而构建相应的酯-聚氨酯共聚物,从而合成共聚物。1H NMR 光谱法和 DSC 分析法证实了这一可行方法的成功。
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引用次数: 0
Shape memory polymers as new advanced loss circulation materials for drilling applications 形状记忆聚合物--钻井应用中的新型先进循环损耗材料
IF 3.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-07-29 DOI: 10.1007/s00289-024-05342-6
Kajal Yadav, Anju Singhwane, Medha Milli, Nikhil Gorhe, A. K. Srivastava, Sarika Verma

This review’s main focus is highlighting and recognizing the significant scientific advances of smart expandable lost circulation material, i.e., shape memory polymers (SMPs) composites as loss circulation material (LCM) for drilling applications as innovative and futuristic materials. This review highlights and explains ways of producing new smart materials for LCM, which can be programmed by its SMP cycle. It briefly describes loss circulation further on loss circulation material and its classification. Only very few SMPs used as LCM, like shape memory polyurethane, thermoset shape memory polymer, shape memory epoxy, etc., either used as Grout, mixed with xanthan gum, or medium-size particles combined with base fluid, while the next section focuses on shape memory polymer as loss circulation material with the shape memory effect and programming over treating wide fractures. The last section consists of conclusion, prospects, and recommendations.

Graphical abstract

本综述的主要重点是强调和认识智能可膨胀失重循环材料(即形状记忆聚合物(SMPs)复合材料)作为创新和未来材料在钻井应用中作为失重循环材料(LCM)所取得的重大科学进步。本综述重点介绍并解释了生产新型智能 LCM 材料的方法,这种材料可通过 SMP 循环进行编程。它简要介绍了损耗循环材料及其分类。只有极少数 SMP 用作 LCM,如形状记忆聚氨酯、热固性形状记忆聚合物、形状记忆环氧树脂等,或用作灌浆材料,或与黄原胶混合,或与基液结合的中等尺寸颗粒。最后一部分是结论、展望和建议。
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引用次数: 0
Development of biocomposites using cardanol oil bio-toughener, palm kernel fiber and chitosan derived from discarded biomass wastes: a characterization study with aging conditions 利用从废弃生物质废料中提取的万丹醇油生物增韧剂、棕榈仁纤维和壳聚糖开发生物复合材料:老化条件下的表征研究
IF 3.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-07-29 DOI: 10.1007/s00289-024-05418-3
J. Thamilarasan, R. Ganesamoorthy

This study focuses on the creation of high degree biocomposite with the utilization of renewable resources, including cardanol oil, palm kernel fiber and chitosan biopolymer. The principal aim of this research was to achieve high degree ratio of biocomposite for safe and eco-friendly application. The chitosan biopolymer was extracted from marine waste sea urchin spikes via deproteination. The biocomposites were prepared via hand layup technique following testing via ASTM standards. According to results, among the composites fabricated, PC5 exhibits exceptional mechanical strength with tensile strength of 88.2 MPa, flexural strength of 133.35 MPa and impact energy of 3.92 J. Therefore, PC6 composite performs better wear resistance with reduced coefficient of friction of 0.399 and Sp. wear rate of 0.01 mm3/Nm, respectively. And also, PC6 provides good thermal resistance with initial decomposition temperature of 345 °C. Similar to mechanical properties, in fatigue behavior also PC5 exhibits high fatigue life cycle counts with 19,647 for 25% UTS, 18,799 for 50% UTS and 17,571 for 75% UTS. The obtained results show that the inclusion of palm kernel fiber and chitosan significantly enhances the mechanical properties, wear and thermal resistance of the composites, while the cardinal oil binder ensures proper adhesion. However, thermal aging conditions were implemented to assess the material’s ability to withstand harsh environmental factors. Notably, among the composite materials tested, the designations with chitin (such as PC4, PC5, and PC6) exhibited lesser susceptibility to the effects of thermal aging. This resilience is attributed to the presence of NH2 functional groups within chitin, which play a role in reducing the impact of thermal aging. These discoveries highlight the promising qualities of the developed polyester biocomposites, suggesting their suitability for a wide array of industrial applications requiring materials capable of enduring high-temperature environments such as automotive door panels, structural, space, defense and sports applications.

本研究的重点是利用可再生资源(包括硬脂醇油、棕榈仁纤维和壳聚糖生物聚合物)制造高比例生物复合材料。这项研究的主要目的是实现高比例生物复合材料的安全和环保应用。壳聚糖生物聚合物是从海洋废弃物海胆钉中通过脱蛋白提取的。根据 ASTM 标准进行测试后,通过手糊技术制备了生物复合材料。因此,PC6 复合材料具有更好的耐磨性,摩擦系数降低至 0.399,磨损率降低至 0.01 mm3/Nm。此外,PC6 还具有良好的耐热性,其初始分解温度为 345 ℃。与机械性能类似,在疲劳行为方面,PC5 也表现出较高的疲劳寿命循环次数,25% UTS 为 19,647 次,50% UTS 为 18,799 次,75% UTS 为 17,571 次。结果表明,加入棕榈仁纤维和壳聚糖可显著提高复合材料的机械性能、耐磨性和耐热性,而红心油粘合剂可确保适当的粘合性。不过,为了评估材料抵御恶劣环境因素的能力,还采用了热老化条件。值得注意的是,在测试的复合材料中,含有甲壳素的材料(如 PC4、PC5 和 PC6)对热老化影响的敏感性较低。这种韧性归因于甲壳素中 NH2 官能团的存在,而 NH2 官能团在降低热老化影响方面发挥了作用。这些发现凸显了所开发的聚酯生物复合材料的良好品质,表明它们适用于要求材料能够承受高温环境的各种工业应用,如汽车门板、结构、太空、国防和体育应用。
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引用次数: 0
A novel amine- functionalized apple peel biocarbon and beta vulgaris cellulosic fiber-based rigid vinyl-based microwave shielding composite 一种新型胺功能化苹果皮生物碳和β-粗纤维素纤维基硬质乙烯基微波屏蔽复合材料
IF 3.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-07-28 DOI: 10.1007/s00289-024-05443-2
S. Somasundaram, S. Muthukumar, A. Sahaya Anselin Nisha, G. Arul Jothi

This present study investigates an eco-friendly electromagnetic interference (EMI) shielding material developed using cellulosic fiber and apple peel extracted biocarbon for safe electronic applications. The primary aim is to study how the biomass derived biocarbon influences in the wave shielding phenomenon. The fiber and filler both used from waste biomass which promotes circular economy and amine functionalization on both fiber and filler brings the novelty to this research. Further, the prepared composite under hand layup process is further assessed as per ASTM standards. Results revealed that due to the addition of surface modified cellulosic fiber and even dispersion of biochar particle into composite enhance mechanical, dielectric, EMI shielding effectiveness of the composite material. Thus, when compared to the plain vinyl ester resin (V), the amine functionalized cellulosic fiber reinforced composite material (V0) shows improved tensile, flexural and impact strength of 125 MPa, 151 MPa, and 4.1 J respectively. Further, the addition of biochar particle of 3 vol.% into the composite (V2) shows improved hydrophobicity behavior of 107° contact angle and the composite V2 further enhanced the tensile, flexural, impact strength of the composite of 145 MPa, 189 MPa, 5.1 J respectively. Moreover, the increase in biochar of 5 vol.% in to the composite (V3) shows effective dielectric loss of 0.28 in E band and 0.45 in J band. Furthermore, the composite under (V2) of 40 vol.% fiber, and 3 vol.% biochar shows maximum EMI shielding effectiveness of 8 dB in E band and 40 dB in J band, when compared to the 40 vol.% of fiber reinforced composite (V0) of EMI shielding effectiveness 9 dB in E band and 55 dB in J band respectively. Thus, this effective EMI shielding effectiveness, dielectric strength and load carrying capacity, impact strength and cost effective, light weight nature makes the composite material to be utilized in high signal protection applications, sensor, navigational devices, and various electric and electronic gadgets, etc.

本研究调查了利用纤维素纤维和苹果皮提取的生物碳为安全电子应用开发的环保型电磁干扰(EMI)屏蔽材料。主要目的是研究从生物质中提取的生物碳如何影响波屏蔽现象。纤维和填料均来自促进循环经济的废弃生物质,纤维和填料上的胺官能化为这项研究带来了新意。此外,还根据 ASTM 标准对手糊工艺制备的复合材料进行了进一步评估。结果表明,由于在复合材料中添加了表面改性的纤维素纤维和均匀分散的生物炭颗粒,复合材料的机械性能、介电性能和电磁干扰屏蔽性能都得到了提高。因此,与普通乙烯基酯树脂(V)相比,胺功能化纤维素纤维增强复合材料(V0)的拉伸强度、弯曲强度和冲击强度分别提高了 125 兆帕、151 兆帕和 4.1 焦耳。此外,在复合材料(V2)中添加 3 Vol.% 的生物炭颗粒可改善疏水性能,使接触角达到 107°,复合材料 V2 进一步提高了复合材料的拉伸强度、弯曲强度和冲击强度,分别达到 145 兆帕、189 兆帕、5.1 焦耳。此外,在复合材料(V3)中增加 5 Vol.% 的生物炭后,E 波段和 J 波段的有效介电损耗分别为 0.28 和 0.45。此外,与 EMI 屏蔽效果分别为 E 波段 9 分贝和 J 波段 55 分贝的 40 Vol.% 纤维增强复合材料(V0)相比,由 40 Vol.% 纤维和 3 Vol.% 生物炭组成的复合材料(V2)在 E 波段和 J 波段的最大 EMI 屏蔽效果分别为 8 分贝和 40 分贝。因此,这种有效的 EMI 屏蔽效果、介电强度和承载能力、抗冲击强度以及低成本、重量轻的特性,使得这种复合材料可用于高信号保护应用、传感器、导航设备以及各种电子电气设备等。
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引用次数: 0
Polymer nanocomposites of ultra-high molecular weight polyethylene 超高分子量聚乙烯聚合物纳米复合材料
IF 3.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-07-27 DOI: 10.1007/s00289-024-05439-y
Vaibhav Padhy, Balasubramanian Kandasubramanian

The growing demand for high-performance, light materials in several tertiary industries is a leading factor propelling the current polymer market. The international UHMWPE market was estimated at USD 1.87 billion in 2023 and is projected to increase by 11.3% CAGR (Compound Annual Growth Rate) from 2024 to 2030 (Ultra-high Molecular Weight Polyethylene Market Report, 2030). The aerospace, defence, and medical sectors have been this market’s primary drivers. Ultra-high molecular weight polyethylene is an excellent polymer popularly used for its enhanced strength, exceptional wear resistance, and ability to support life processes without causing undesirable reactions. Nevertheless, conventional surface modification techniques mainly focus on improving specific properties for established applications. In this article, we have explored how UHMWPE nanocomposites loaded with different nanomaterials like carbon nanotubes, graphene oxides, hydroxyapatite, and metal alloys could be used to make high-performance products. This review advances the frontiers of knowledge by concentrating explicitly on three key application areas: defence, biomedical, and electromechanical. In the defence realm, these advancements could revolutionise ballistic protection equipment, paving the way for next-generation gear with superior capabilities. Within the biomedical sector, UHMWPE nanocomposites hold great promise for creating exceptional joint replacements that possess enhanced wear resistance and biocompatibility. Lastly, in the electromechanical domain, these composites offer the possibility of developing lightweight and high-performance tribological components, thereby driving advancements in diverse mechanical systems.

Graphical abstract

一些第三产业对高性能轻质材料的需求不断增长,这是推动当前聚合物市场发展的主要因素。据估计,2023 年国际超高分子量聚乙烯市场规模为 18.7 亿美元,预计 2024 年至 2030 年的复合年增长率(CAGR)将达到 11.3%(《2030 年超高分子量聚乙烯市场报告》)。航空航天、国防和医疗行业是该市场的主要驱动力。超高分子量聚乙烯是一种优良的聚合物,因其强度高、耐磨性好、能够支持生命过程而不会引起不良反应而广受欢迎。然而,传统的表面改性技术主要侧重于改善既定应用的特定性能。在本文中,我们探讨了如何用不同的纳米材料(如碳纳米管、石墨烯氧化物、羟基磷灰石和金属合金)负载超高分子量聚乙烯纳米复合材料来制造高性能产品。本综述明确集中于三个关键应用领域:国防、生物医学和机电,从而推动了知识前沿的发展。在国防领域,这些进步可能会彻底改变防弹设备,为具有卓越性能的下一代装备铺平道路。在生物医学领域,超高分子量聚乙烯纳米复合材料有望制造出具有更强耐磨性和生物相容性的特殊关节替代物。最后,在机电领域,这些复合材料为开发轻质、高性能的摩擦学部件提供了可能,从而推动了各种机械系统的进步。
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引用次数: 0
Mechanistic interactions in polystyrene-block-poly(N-hydroxyethylacrylamide) diblock copolymer-based nano-corona toward elucidation of solvation responses 聚苯乙烯-嵌段-聚(N-羟乙基丙烯酰胺)二嵌段共聚物纳米电晕中的机理相互作用,旨在阐明溶解反应
IF 3.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-07-26 DOI: 10.1007/s00289-024-05424-5
Md. Ashaduzzaman, Shaikat Chandra Dey, Md. Kaium Hossain, Ashutosh Tiwari

Diblock copolymers consisting of higher hydrophobic styrene and hydrophilic N-hydroxyethylacrylamide (HEAAm) segments were successfully synthesized via direct two-step atom transfer radical polymerization. Polystyrene (PS) homopolymers were synthesized using methyl 4-(bromo-methyl) benzoate initiator in N,N′- dimethylformamide (DMF) in the presence of Cu(I)Br/pentamethyldiethylene tetramine (PMDETA) catalyst system at 90 and 110 °C in nitrogen atmosphere. PS was used as macro-initiator for the synthesis of PS-b-PHEAAm polymer. Block copolymerizations were carried out in pure DMF in the presence of the same catalyst system at 110 °C while argon was used for deoxygenation and inert environment. Block copolymer was purified through dialysis into deionized water using a dialysis tubing (MWCO 3500, cellulose membrane). The number average molecular weight of PS polymers (Mn = 2240, 3250 and 10,800 Da) was determined by size exclusion chromatography using tetrahydrofuran (THF) as eluent. The chemical structures, functional groups and actual compositions of copolymer were determined using instrumental data, c.f. elemental analysis, attenuated total reflectance infra-red and proton—nuclear magnetic resonance (1H-NMR) spectroscopy analysis. Thermo-gravimetric analysis confirms that diblock copolymer has higher thermal stability than PS homopolymer. Co-solvent effect on particle formation was investigated by regulating dielectric constant. It is revealed that THF/DMF (9:1) provides susceptible environment for the formation of smallest size (13 ± 4 nm) particle. This synthetic route would establish a direct synthesis of diblock copolymer with antagonistic segments for advanced technological applications.

通过直接两步原子转移自由基聚合,成功合成了由高疏水苯乙烯和亲水 N-羟乙基丙烯酰胺(HEAAm)段组成的二嵌段共聚物。聚苯乙烯(PS)均聚物是在 N,N′-二甲基甲酰胺(DMF)中使用 4-(溴甲基)苯甲酸甲酯引发剂,在 Cu(I)Br/pentamethyldiethylene tetramine (PMDETA) 催化剂体系存在下,于 90 和 110 °C 氮气环境中合成的。PS 用作合成 PS-b-PHEAAm 聚合物的大引发剂。嵌段共聚在纯 DMF 中进行,催化剂体系相同,温度为 110 °C,氩气用于脱氧和惰性环境。使用透析管(截留分子量 3500,纤维素膜)将嵌段共聚物透析到去离子水中进行纯化。以四氢呋喃(THF)为洗脱剂,通过尺寸排阻色谱法测定了 PS 聚合物的平均分子量(Mn = 2240、3250 和 10,800 Da)。共聚物的化学结构、官能团和实际成分是通过仪器数据、元素分析、衰减全反射红外光谱和质子-核磁共振(1H-NMR)光谱分析确定的。热重分析证实,二嵌段共聚物比 PS 均聚物具有更高的热稳定性。通过调节介电常数研究了共溶剂对颗粒形成的影响。结果表明,THF/DMF(9:1)为形成最小尺寸(13 ± 4 nm)的粒子提供了有利的环境。该合成路线可直接合成具有拮抗段的二嵌段共聚物,用于先进的技术应用。
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引用次数: 0
The π–π stacking effect of metallocene catalyst in olefin polymerization 茂金属催化剂在烯烃聚合中的π-π堆积效应
IF 3.2 3区 化学 Q2 POLYMER SCIENCE Pub Date : 2024-07-26 DOI: 10.1007/s00289-024-05432-5
Xin Yan, Jianming Yang, Hexin Zhang, Keun-Byoung Yoon, Min Chen

The single-sited metallocene catalyst has attracted significant attention due to its high activity and application in olefin polymerization industry. In this work, we introduced a strategy of in situ modification of metallocene catalyst with pyrene through π–π stacking to study the effect in olefin polymerization. After activated by MMAO, the pyrene-modified metallocene catalyst exhibited high activities (up to 1333 kg mol−1 h−1) in ethylene polymerization, which was 1.9 times higher than that of the pyrene free catalyst system. This could be because the electron-donating ability of cyclopentene to the transition metal was enhanced through π–π interaction of pyrene with cyclopentene. The copolymerization of ethylene and 1-hexene was also studied. The pyrene-modified metallocene catalyst system performs with higher activity in the copolymerization with a lower monomer incorporation ratio. Density functional theory (DFT) calculations indicated the formation of π–π interaction between the Zr center with pyrene molecule leading to the increase in steric hindrance and electron density.

Graphical abstract

单位茂金属催化剂因其高活性和在烯烃聚合工业中的应用而备受关注。在这项工作中,我们引入了一种通过π-π堆积对茂金属催化剂进行芘原位改性的策略,以研究其在烯烃聚合中的效果。经 MMAO 活化后,芘改性茂金属催化剂在乙烯聚合中表现出较高的活性(高达 1333 kg mol-1 h-1),是无芘催化剂体系的 1.9 倍。这可能是因为芘与环戊烯的π-π相互作用增强了环戊烯对过渡金属的电子供能能力。此外,还研究了乙烯和 1-己烯的共聚。芘改性茂金属催化剂体系在单体掺入率较低的共聚过程中表现出更高的活性。密度泛函理论(DFT)计算表明,Zr 中心与芘分子之间形成了 π-π 相互作用,从而增加了立体阻碍和电子密度。
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Polymer Bulletin
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