纤维素在NMMO水溶液中的溶解机理研究进展

被称之为绿色纤维的Lyocell纤维,其成功开发的基础在于纤维素溶剂N-甲基吗啉-N-氧化物(NMMO)的发现。尽管在发现初期,就有人根据溶解现象和实验证实纤维素在NMMO水溶液中的溶解过程是一个大分子间氢键被破坏的物理过程,但人们对其溶解机理的认识还是经历了一个长期的过程。以往的实验方法局限于纤维素分子与溶剂分子间弱相互作用的研究,随着计算机技术的发展,分子模拟的方法填补了这一空白,使纤维素的溶解机理得到了新的认识,例如纤维素分子和NMMO分子的两亲性,以及疏水缔合相互作用。纤维素溶解机理的深入认识不仅可以促进Lyocell过程稳定性、溶剂回收效率的提升,还会为新溶剂的开发奠定理论基础。本文从NMMO的认识过程、纤维素在NMMO水溶液中溶解过程的实验发现和分子模拟计算等方面,全面总结和理解纤维素在NMMO水溶液中的溶解机理。     

超分子聚合机理

与共价键聚合物由单体(M1)通过共价键连接不同,超分子聚合物是由单体(M2)通过非共价键连接而成的长链大分子。聚合包括分子聚合和超分子聚合。超分子聚合描述M2通过非共价键自组装形成超分子聚合物的过程,涉及氢键、π-π堆砌型和立体匹配等驱动力以及分子识别、协同性等特征,与M1通过共价键形成聚合物的过程(分子聚合)不同。为了理解超分子聚合物链结构形成机理,本文分析和讨论超分子聚合的三个主要机理:(1)线性链生长;(2)螺旋链生长;(3)拓扑链生长。     

可持续高分子-纤维素新材料研究进展

21世纪"绿色"化学已成为世界各国社会经济发展中的研究与开发战略方向.纤维素是自然界中储量最丰富的天然高分子,是重要的可再生资源以及未来的主要工业原料.然而由于纤维素存在着大量的分子内以及分子间氢键,其结构致密,难以溶解或熔融进一步加工.本文简要介绍了近几年来关于直接使用物理溶剂方法(非衍生化)对纤维素材料开发利用的新进展,主要包括以下4个方面:(1)纤维素在"绿色"溶剂-碱/尿素以及离子液体体系中的溶解和再生;(2)纳米纤维素的制备以及组装;(3)木材纳米技术的开发及利用;(4)细菌纤维素基材料等,旨在推进"绿色"技术实现纤维素资源的研究开发及利用.     

无机药物:问题和解决思路

进入本世纪以来,无机药物及相关基础研究获得巨大的发展,同时也面临着巨大的困难。本文综述了两类金属药物——抗癌金属药物和抗糖尿病钒化合物的研究进展和目前存在的严重瓶颈问题,并提出未来发展应重视下列方面:(1)发现新的金属药物分子机制,在此基础上实现理性药物设计;(2)基于分子机理实现对金属药物毒性的控制;(3)理性设计和建立基于纳米、分子复合物和药物分子转运体的新的金属药物转运体系;(4)发展金属配合物的合成生物学。     

高能质子辐射作用的分子机理——DNA空间结构微观损伤的Raman光谱特征

高能质子是空间辐射的重要类型。本文用激光Raman光谱技术,研究了高能质子(27.9 MeV)对水溶液中DNA辐射作用的分子机理。通过解析其特征Raman谱线,获得DNA空间结构微观损伤的以下信息:(1)维系双螺旋结构的碱基间氢键部分断裂;(2)4种碱基均被损伤,其中腺嘌呤环的破坏最重;(3)脱氧核糖发生了明显的变化;(4)骨架磷酸离子(PO_2~-)和磷酸二酯(PO_2)的损伤严重,并出现单、双链的断裂;(5)B型构象的数量显著减少。     

β-环糊精及其衍生物对两种农药的不同光解特性

研究了β-环糊精(β-CD)及其衍生物羟丙基-β-环糊精(HPCD)对两种疏水性有机农药(甲基对硫磷和五氯酚)的增溶作用和光解影响．实验结果表明，对农药的增溶作用或光解的影响主要是由于农药与β-CD或HPCD形成包合物而引起的．β—CD能提高五氯酚的水溶性，但对甲基对硫磷的增溶作用表现为低浓度促进溶解而高浓度抑制溶解；HPCD则能显提高两种疏水性农药的水溶性．β—CD及HPCD与甲基对硫磷形成包合物，选择性定向客体分子而促进其光解；与五氯酚形成稳定的包合物，能保护客体分子而抑制其光解．HPCD对农药的增溶效果和光解的影响比β—CD更显．     

修订ISO标准方法—重量法测定硫的试验报告

对《ISO 4934-1980(E)钢和铸铁-硫含量的测定-重量法》中(1)不溶于稀硝酸的试样的溶解;(2)铬干扰的消除;(3)坩埚的恒重;(4)BaSO_4真换算成硫(S)的换算系数提出了修改意见。     

聚二苯基乙炔耐溶剂纳滤膜的制备与性能

聚二苯基乙炔(PDPA)不溶于有机溶剂,是理想的新型耐溶剂纳滤膜材料。采用溶液浇铸法制备聚[1-(4-三甲基硅基)苯基-2-苯乙炔](PTMSDPA)均质膜,经脱硅反应得到PDPA膜,研究其乙醇渗透性能和染料截留性能。结果表明,乙醇渗透通量与压力呈正相关性,传质机理可能介于孔流机理和溶解扩散机理之间的过渡区。染料的分子尺寸、电荷性质以及染料和膜之间的相互作用共同影响PDPA膜的截留性能。     

銻电极在浓的硫酸和盐酸溶液中的阳极溶解行为

1.测定锑电极在硫酸溶液(从0.64N到6.23Ⅳ)和盐酸溶液(从1.04N到4.21N)中的阳极极化曲线φ_A-logi_A。其线性部份的斜率均为23毫伏。当[2log a±(H_2SO_4)-log a_w]和log a±(HCl)每增大一单位时,在恒定的电流密度下阳极极化电位分别朝正方向移动21毫伏和朝鱼方向移动82毫伏。 2.根据上述结果曾讨论锑电极在硫酸和盐酸溶液中可能的阳极溶解机理。     

亲核性调节剂在异丁烯阳离子聚合中的作用机理

亲核性调节剂在异丁烯活性阳离子聚合中发挥着极其重要的作用 ,其作用机理主要包括 :(1)碳阳离子稳定化作用 ,即亲核性试剂或它们与Lewis酸生成的络合物与增长链的末端结合 ,来降低活性中心阳离子的“阳离子性” ,抑制副反应 ,使聚合反应呈现活性聚合特征 ;(2 )质子捕获作用 ,即亲核性试剂捕获质子 ,抑制质子的不可控引发和链转移反应 ;(3)增长链表观稳定作用 ,即亲核试剂降低了增长速率与引发速率之比 ,提高引发效率 ,降低增长速率 ,降低分子量分布 ;(4)抑制自由离子增长作用 ,即亲核试剂与质子源和Lewis酸反应 ,生成同阴离子 ,产生同离子效应 ,抑制自由离子活性中心的引发增长作用。     

The molecular mechanism of novolak-diazonaphthoquinone resists

Novolak-diazonaphthoquinone (DNQ) resists are photosensitive varnishes that are used in the fabrication of more than 80% of today's integrated circuits. They have played a crucial role in an unprecedented technical revolution, yet until quite recently nobody really knew how they work. We have been concerned with this problem for some time and we realize now that the principal functions of novolak resists, namely the inhibition by DNQ derivatives of the dissolution of novolak films, and the cessation of inhibition on exposure to radiation, are essentially physical phenomena. Dissolution inhibition is caused by an electric stress imposed on the phenol groups of the resin by the inhibitor. This effect penetrates deep into the material through the formation of hydrogen-bonded phenolic strings. Exposure relieves the stress by uncoupling the strings from the source of induction. The concept of phenolic strings is new and unusual, but it is essential for the understanding of dissolution inhibition. With it, all the many aspects of novolak resists can be interpreted in a unified manner.     

DNQ–novolac photoresists revisited: 1H and 13C NMR evidence for a novel photoreaction mechanism

Photoactive compounds, such as diazonaphthoquinone (DNQ) esters, blended with novolac resins, solvents and certain additives, serve as photoresists. These are used for printing of electronic circuits at the micron or sub‐micron level. Patterns are generated based on changes in the physical and chemical properties of the exposed and unexposed photoresist surfaces (printed circuit boards). The huge polarity change between the exposed and unexposed photoresists is exploited in the technique of microlithography. It is believed that the large polarity difference is due to acid formation in the exposed photoresist by a photochemical reaction of DNQ on exposure to light. However, it has also been suggested that in the unexposed part of a photoresist, the novolac resin undergoes an azo coupling reaction with DNQ, leading to an increase in the molecular weight of the resin, rendering it more insoluble in base. The protons in the para positions of the m‐cresol units incorporated in the novolac resin are believed to take part in this azo coupling reaction with DNQ. In this paper, we propose a novel mechanism of action of positive photoresists in the unexposed part of photoresists for dissolution inhibition using molecular modelling, ¹H NMR, ¹³C NMR and DEPT‐135 NMR spectroscopic techniques. Our results enable us to propose that the diazo group of DNQ attacks the methylene bridges rather than the aromatic moiety of the resin. This mechanism explains the pattern formation observed using even p‐cresol‐based resins, where no free para positions are present in the aromatic ring. Copyright © 2003 John Wiley & Sons, Ltd.     

Resist performances and structure of phenolic resins using multi-substituted phenols

Positive photoresist systems comprising phenolic resin and quinonediazide are studied in detail. The structure of several novolak resins, which were synthesized from multi-substituted phenols, are analyzed with ¹³C-NMR. It is proved that these phenols are useful for the structural control of novolak resins. Phenols with two methyl substituents at meta-positions especially show a remarkable structural effect to control methylene bond types of novolak resins. The alkaline dissolution rate is also investigated on novolak resins synthesized from multi-substituted phenols to understand both the dissolution inhibition effect and the dissolution promotion effect. Key-structure of novolak resins for realizing high resolution is elucidated. In addition, the molecular design concept of novolak resin is clarified from several standpoints. Unsubstituted aromatic carbon of resin, hydrophobic effect of methyl substitutent and suitable structure of low M_w parts of novolak resin are also explored. Furthermore, it is proposed that a resist using a resin, which is based on the molecular design concept, has enough potential to produce critical dimensions of 0.2 μm or less taking advantage of phase-shifting technology.     

I-Line光刻胶材料的研究进展

酚醛树脂-重氮萘醌正型光刻胶由于其优异的光刻性能,在g-line(436 nm)、i-line(365 nm)光刻中被广泛使用.g-line光刻胶胶、i-line光刻胶,两者虽然都是用线型酚醛树脂做成膜树脂,重氮萘醌型酯化物作感光剂,但当曝光波长从g-line发展到i-line时,为适应对应的曝光波长以及对高分辨率的追求,酚醛树脂及感光剂的微观结构均有变化.在i-line光刻胶中,酚醛树脂的邻-邻'相连程度高,感光剂酯化度高,重氮萘醌基团间的间距远.溶解促进剂是i-line光刻胶的一个重要组分,本文对其也进行了介绍.     

New Positive‐Type Photoresists Based on Enzymatically Synthesized Polyphenols

Summary: New positive‐type photoresist systems based on enzymatically synthesized polyphenols have been developed. The photoresist thin film consisting of the polyphenol and a diazonaphthoquinone derivative was prepared on copperfoil‐coated epoxy resins and exposed to UV light with different doses. The polyphenols from the bisphenol monomers exhibited high photosensitivity, comparable with a conventional cresol novolac. The sensitivity could be controlled by changing the structure of the polyphenols. Furthermore, the present photoresist showed excellent etching resistance.

Characteristic exposure curves of poly( 1 )/DNQ and poly( 5 )/DNQ (both 70:30 wt.‐%) with different phenylene unit contents.     

Acid generation and deprotecting reaction by diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate in a novolak positive photoresist based on chemical amplification

In a positive photoresist composed of diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate as a novel photoacid generator, bisphenol A protected with tertbutoxycarbonyl group as a dissolution inhibitor, and a novolak resist matrix, the efficiency of photo-acid generation and deprotective reaction were investigated by means of UV-visible and IR spectroscopies. The quantitative measurement of photogenerated acid by using the acid-sensitive dye exhibited 0.18 as the quantum yield of acid generation in novolak resin film. The lithographic evaluation of this system as a chemically amplified resist was studied. The catalytic chain length for the acid-catalyzed deprotection step was determined as about 100 when 10 min post-exposure bake (PEB) at 80°C was given. The sensitivity and the resolution as a positive resist are 180 mJ/cm² and higher than 1 μm, respectively under the PEB conditions mentioned above.     

Fundamental investigation on interaction between hexafluoroisopropylalcohol‐containing styrene and photochemical acid generator for rationale design of photoresist system

This article presents the effect of some ionic photochemical acid generators (PAGs) to inhibit the dissolution of hexafluoroisopropylalcohol (HFA)‐containing polystyrene to an aqueous alkaline developer, which is a highly important effect in photoresist application to enhance resolution of patterning. The dissolution inhibiting factors and mechanisms were investigated by evaluating the solubility and the ¹H‐NMR analysis of OH proton in HFA moiety. The dissolution inhibition effect was enhanced when the structures of PAGs fulfill some requirements: (a) their anions should have higher basicity and smaller van der Waals volume; (b) their cations should be stabilized by conjugation with electron‐rich aromatics. In the dissolution inhibition, the HFA moiety interacts with the anionic part of PAGs liberated from the electrostatic interaction with the counter cation. These interactions were predicted and quantified by DFT calculations using Gaussian 09, leading to the rational designs of PAGs with higher dissolution inhibiting effect in photoresist systems. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 531–538     

Vis‐sensitive photopolymer containing vinyl ether compound and pyrromethene dye

A visible light(vis)‐sensitive photoresist based on the concept of chemical amplification was developed utilizing poly(p‐hydroxystyrene) (PHS), 2,2‐bis[4‐(2‐(vinyloxy)‐ethoxy)phenyl]propane (BPA‐DEVE) as a crosslinking agent, N‐trifluoromethylsulfonyloxy‐1,8‐naphthalimide (NIT) as a photoacid generator (PAG) and pyrromethene dyes such as 1,3,5,7,9‐pentamethylbipyrromethene difluoroborate (PRH) and 2,8‐diethyl‐1,3,5,7,9‐pentamethylbipyrromethene difluoroborate (PRE) and 3,3′‐carbonylbis(7,7′‐diethylaminocoumarin) (KCD). On irradiation with an argon ion laser, the photopolymer comprising PRH and PRE exhibited a high sensitivity of 65 and 46 mJ cm^?2, respectively. It is suggested that the sensitization mechanism of the pyrromethene dye/PAG system involves singlet electron transfer. The sensitivity of the photoresist increased with the decreasing molecular weight of PHS because of the high dissolution rate. Copyright © 2002 John Wiley & Sons, Ltd.     

Neutron reflectivity characterization of the photoacid reaction-diffusion latent and developed images of molecular resists for extreme ultraviolet lithography

Lithographic feature size requirements have approached a few radius of gyration of photoresist polymers used in thin-film patterning. Furthermore, the feature dimensions are commensurate with the photoacid diffusion length that defines the underlying latent image. Smaller imaging building blocks may enable reduced feature sizes; however, resolution limits are also dependent upon the spatial extent of the photoacid-catalyzed reaction diffusion front and subsequent dissolution mechanism. The reaction-diffusion front was characterized by neutron reflectivity for ccc stereoisomer-purified, deuterium-labeled tert-butoxycarbonyloxy calix[4]resorcinarene molecular resists. The spatial extent of the reaction front exceeds the size of the molecular resist with an effective diffusion constant of (0.13 ± 0.06) nm(2)/s for reaction times longer than 60 s, with the maximum at shorter times. Comparison to a mean-field reaction-diffusion model shows that a photoacid trapping process provides bounds to the spatial and extent of reaction via a reaction-limited mechanism whereas the ratio of the reaction rate to trapping rate constants recovers the effective diffusion peak. Under the ideal step-exposure conditions, surface roughness was observed after either positive- or negative-tone development. However, negative-tone development follows a surface-restructuring mechanism rather than etch-like dissolution in positive-tone development.     

New synthetic route for photosensitive poly(benzoxazole)

A new positive working photosensitive poly(benzoxazole) (PBO) precursor based on poly(o‐hydroxyazomethine) ( 3 ) and 1‐{1,1‐bis[4‐(2‐diazo‐1‐(2H)naphthalenone‐5‐sulfonyloxy)phenyl]ethyl}‐4‐{1‐[4‐(2‐diazo‐1(2H)naphthalenone‐5‐sulfonyloxy)phenyl]methylethyl}benzene (S‐DNQ) as a photosensitive compound was developed. 3 was prepared by the condensation of 2,2‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane with isophthalaldehyde in 1‐methyl‐2‐pyrrolidinone/toluene under azeotropic conditions. The photosensitive PBO precursor containing 30 wt % S‐DNQ showed a sensitivity of 120 mJ cm^?2 and a contrast of 2.2 when it was exposed to 436‐nm light and developed with a 2.38 wt % aqueous tetramethylammonium hydroxide solution at room temperature. A fine positive image featuring 10‐μm line and space patterns was observed on the film of the photoresist exposed to 200 mJ cm^?2 ultraviolet light at 436 nm by the contact mode. The positive image was successfully converted into the PBO pattern by a thermal treatment. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3399–3405, 2002