一种高感度深紫外正性化学增幅型抗蚀剂的制备

聚对羟基苯乙烯和环己基乙烯基醚反应得到缩醛保护的聚合物.该聚合物易溶于常见的有机溶剂,具有较好的热稳定性,在248 nm处透明性良好.该聚合物可与聚对羟基苯乙烯-甲基丙烯酸金刚烷基酯及二砜光产酸剂等组成一种三组分正性化学增幅型深紫外光致抗蚀剂,初步研究了该抗蚀剂的感光成像性能.采用KrF激光（248 nm）曝光,在较低的后烘温度下,显影得到分辨率为180 nm的线条图形.显影后的留膜率在99%以上.在光致抗蚀剂体系中引入对羟基苯乙烯-金刚烷基甲基丙烯酸酯共聚物,可提高光刻胶材料的玻璃化转变温度,有利于其实际应用.     

聚对羟基苯乙烯单体的中间体——对特丁氧酰氧基苯乙烯合成方法的改进

通过改进反应溶剂,用Wittig反应合成了对特丁氧酰氧基苯乙烯,以中性Al2O3为固定相,正己烷为流动相,采用普通液相色谱分离提纯了混合产物,改进简化了分离方法。结果表明,所得目标产物对特丁氧酰氧基苯乙烯纯度达99%以上,产率为60%~70%,中间产物对特丁氧酰氧基苯甲醛可以定量合成,反应的副产物主要是三苯基氧化膦。对目标产物、中间产物和一些反应副产物进行了红外和核磁共振分析。     

5-丁氧基亚甲基-2-降冰片烯的合成及其加成聚合反应

采用降冰片烯-5-甲醇和溴丁烷在氢化钠作用下合成了5-丁氧基亚甲基-2-降冰片烯,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系使之聚合。 考察了聚合时间对其均聚合的影响以及5-丁氧基亚甲基-2-降冰片烯和降冰片烯不同摩尔投料比对其共聚行为的影响。 采用1H NMR、FTIR和TGA测试技术对所得的聚合物进行了结构表征和性能测试。 结果表明,双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3催化体系对5-丁氧基亚甲基-2-降冰片烯均聚和共聚具有较高的催化活性。 得到的均聚物和共聚物为加成型聚合物,料液中5-丁氧基亚甲基-2-降冰片烯的摩尔分数为10%~90%时,其在共聚物中的插入率为22.1%~76.9%,所得聚合物具有较好的热稳定性（Td＞360 ℃）,在THF和CHCl3等许多普通溶剂中有很好的溶解性能。     

对特丁氧酰氧基苯乙烯的制备新方法

对特丁氧酰氧基苯乙烯;α-溴代反应;β-消除反应     

顺-5-降冰片烷-外-2,3-二甲酰亚胺的合成

以顺-5-降冰片烯-外-2,3-二甲酸酐（2）为原料,氨气为氨源,经氨化反应制得顺-5-降冰片烯-外-2,3-二甲酰亚胺（3）; 3经钯炭催化氢化合成了盐酸鲁拉西酮关键中间体顺-5-降冰片烷-外-2,3-二甲酰亚胺（1）,其结构经¹ H NMR和MS（ESI）确证。研究了2与氨气的投料比[r=n（2）/n（氨气）]、反应时间、析晶时间对3外观和收率的影响,以及氢化反应温度和反应时间对1外观和收率的影响。结果表明：合成3的最佳反应条件为：r=1.0/2.5,反应时间25~30 h,析晶时间6~8 h, 3收率93.2%。合成1的最佳反应条件为：氢化反应温度20~30 ℃,反应时间6~10 h, 1收率98.2%。 1的中试极限条件为：于40~50 ℃浓缩6 h,湿品于45~55 ℃干燥8 h,总收率91.5%。     

8-苯胺-1-萘磺酸钛配合物的合成及催化乙烯与降冰片烯共聚合反应

合成了新型催化剂8-苯胺-1-萘磺酸钛配合物, 并应用于乙烯与降冰片烯的共聚合反应中. 分别考察了助催化剂种类[甲基铝氧烷(MAO)和三乙基铝(TEA)]、 降冰片烯浓度、 Al/Ti摩尔比、 聚合温度和聚合压力对催化活性与共聚性能的影响. 通过核磁共振、示差扫描量热和凝胶渗透色谱等对所制备的共聚物进行了表征. 结果表明, 在相同条件下, 以MAO为助催化剂时, 共聚催化活性更高, 催化剂为单活性中心, 可得到分子量分布较窄(PDI≈3)的共聚产物, 其共聚反应机理为加成聚合. 另外, 随着降冰片烯浓度的升高, 共聚物中降冰片烯单元的摩尔比呈线性上升趋势, 所得共聚物的熔点随之降低.     

高分子富氧膜研究 Ⅱ.二甲基硅氧烷齐聚物与对羟基苯乙烯齐聚物交联共聚物的合成与表征

研究了α,ω-双二甲胺基聚二甲基硅氧烷与对羧基苯乙烯齐聚物(pHS)之间的溶液共缩聚反应,制得了高分子量的有机硅交联聚物。用多种方法测定了交联共聚物的结构和性能,发现它存在微观相分离结构,在一定的有机硅含量范围内均为低晶物,共聚物大分子链上尚保留可供进一步化学修饰的官能团,且具有优异的成膜工艺性,较好的氧氮气体选择透过性。     

刺激响应性共聚物修饰金纳米棒的制备及其抗肿瘤性能

以1-叔丁氧基羰基-2-丙烯酰肼(Boc-AH)、N-(3,4-二羟基苯乙基)丙烯酰胺(DA)和聚乙二醇甲醚丙烯酸酯(mPEGA)为单体,利用可逆加成-断裂链转移聚合法制备了嵌段共聚物聚丙烯酰肼-聚N-(3,4-二羟基苯乙基)丙烯酰胺-聚单甲氧基聚乙二醇丙烯酸酯(PAH-b-PAD-b-PmPEGA,缩写为HDP),该...     

苯乙烯在烷基功能化硅单晶表面的原位活性自由基聚合反应

介绍了一种在单晶硅表面制备聚苯乙烯刷子的新方法, 此方法分3步进行: (ⅰ) 将3-甲基丙烯酰氧基丙基三甲氧基硅烷接枝到单晶硅表面, (ⅱ) 以偶氮二异丁腈(AIBN)为催化剂, 将2,2,6,6-四甲基哌啶-N-氧基-1-羟基(HTEMPO·)引入3-甲基丙烯酰氧基丙基三甲氧基硅烷的末端, (ⅲ) 在HTEMPO·存在下, 苯乙烯进行活性自由基聚合反应. 可控活性自由基聚合反应可以精确控制分子量及其分布. 光电子能谱(XPS)的测试结果表明, 带有引发剂的烷氧基链已接枝到单晶硅表面. XPS和橢偏仪的测试结果表明, 聚苯乙烯以化学键的方式被锚接到了单晶硅上. 接枝聚合物层的厚度可由反应时间来精确控制. 用此方法可以在基体表面合成无规共聚物或嵌段共聚物.     

(S)-4-羟基吡咯烷-2-酮的简便合成

(S)-3-羟基-γ-丁内酯开环制得手性3,4-二羟基丁酸甲酯(2);对2的伯羟基进行对甲苯磺酰化、仲羟基进行苄基保护得4-对甲苯磺酰氧基-3-苄氧基丁酸甲酯(5);5在氨甲醇作用下合环、脱苄基保护合成了(S)-4-羟基吡咯烷-2-酮,总收率26%,其结构经1HNMR和HR-MS确认,比旋光值与文献值相符。     

248 nm深紫外光刻胶用成膜树脂的研究进展

综述了用于248 nm化学增幅型深紫外光刻胶的不同种类和结构的成膜树脂,以及所使用单体的研发进展,包括聚甲基丙烯酸甲酯及其衍生物、聚对羟基苯乙烯及其衍生物、N取代的马来酰亚胺衍生物,以及其他聚合物等,对不同结构成膜树脂的曝光条件、对光刻胶性能的影响进行了介绍。     

Synthesis of core/shell structure of glycidyl–functionalized poly(methyl methacrylate) latex nanoparticles via differential microemulsion polymerization

The differential microemulsion polymerization technique was used to synthesize the nanoparticles of glycidyl-functionalized poly(methyl methacrylate) or PMMA via a two-step process, by which the amount of sodium dodecyl sulfate (SDS) surfactant required was 1/217 of the monomer amount by weight and the surfactant/water ratio could be as low as 1/600. These surfactant levels are extremely low in comparison with those used in a conventional microemulsion polymerization system. The glycidyl-functionalized PMMA nanoparticles are composed of nanosized cores of high molecular weight PMMA and nano-thin shells of the random copolymer poly[(methyl methacrylate)-ran-(glycidyl methacrylate)]. The particle sizes were about 50 nm. The ratios of the glycidyl methacrylate in the glycidyl-functionalized PMMA were achieved at about 5–26 wt.%, depending on the reaction conditions. The molecular weight of glycidyl-functionalized PMMA was in the range of about 1 × 10⁶ to 3 × 10⁶ g mol⁻¹. The solid content of glycidyl-functionalized PMMA increased when the amount of added glycidyl methacrylate was increased. The glycidyl-functionalized polymer on the surface of nano-seed PMMA nanoparticles was a random copolymer which was confirmed by ¹H-NMR spectroscopy. The amounts of functionalization were investigated by the titration of the glycidyl functional group. The structure of the glycidyl-functionalized PMMA nanoparticles was investigated by means of TEM. The glycidyl-functionalized PMMA has two regions of T_g which are at around 90 °C and 125 °C, respectively, of which the first one was attributed to the poly[(methyl methacrylate)-ran-(glycidyl methacrylate)] and the second one was due to the PMMA. A core/shell structure of the glycidyl-functionalized PMMA latex nanoparticles was observed.     

Studies of some new bioactive acrylic esters

Four typical bioactive esters of acrylic monomers, N-p-acryloxybenzoyloxysuccinimides, 3-ac-ryloxy-4-oxo-3,4-dihydro-1,2,3-benzotriazines, N-acryloxy-5-norbornene-2,3-dicarboximides, and I-p-acryloxybenzoyloxybenzotriazoles, were Synthesized and polymerized as reactive polymers. Twelve new monomers were prepared by coupling acrylic acid, methacrylic acid, p-acryloxybenzoic acid, or p-methacryloxybenzoic acid with four N-hydroxy compounds such as N-hydroxysuccinimide (HOSu), 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine (HOObt), N-hydroxy-5-norbornene-2,3-dicarboximide (HONB), and I -hydroxybenzotriazole (HOBT) in the presence of dicyclohexylcarbodimide. All monomers polymerized readily in solution with azobisisobutyronitrile (AIBN) as free radical initiator. The resulting reactive polymers with reactive ? OSu, ? OObt, ? ONB, or ? OBT group on the side chain are equally reactive toward n-butylamine at room temperature in the formation of corresponding polyacrylamides. Reactive polymers were used to immobilizetrypsin. It has been found that poly(N-p-methacryloxybenzoyloxy-5-norbornene-2,3-dicarboximide)-trypsin matrix had high activity around three times that of the poly(N-methacryloxy-5-norbornene-dicarboximide)-trypsin matrix. It is proposed that this activity may be due to the presence of a long spacer arm with a hydrophobic and rigid benzene ring between the ligand and matrix. The reactive poly(N-p-methacryloxybenzoyloxysuccinimide-p-methacryloxybenzoic acid) copolymer was used to immobilize the serum protein. This immobilized protein was a hopeful bioactive solid immunoadsorbent.     

Synthesis and characterization of random copolymers of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate and 2,3-dihydroxypropyl methacrylate

Poly[(2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate)] [poly(solketal methacrylate) (PSMA)] was synthesized by free radical polymerization. By partial hydrolysis of the acetal group, random copolymers of SMA with 2,3-dihydroxypropyl methacrylate (DHPMA) were synthesized whereas complete cleavage lead to poly(2,3-dihydroxypropyl methacrylate) (PDHPMA). The copolymer composition was determined by ¹H NMR spectroscopy. FTIR spectroscopy indicates the synthesis of random copolymers with different degrees of hydrogen bonding as measured by a shift of the OH vibration bands. The glass transition temperature of the random copolymers increases linearly with increasing DHPMA content, resulting in a positive deviation from the Fox equation. The thermal degradation of both homopolymers and their random copolymers has been studied. Finally, the solution behaviour of the copolymers and PDHPMA in water studied by dynamic light scattering showed a strong tendency of the polymer chains to form clusters in the size range of 15-62 nm. The size and the kind of associating interactions within the clusters strongly depend on the copolymer composition.     

Photo- and radiation-induced degradation of poly(styrene-co-methyl methacrylate)

The photo- and radiation-induced degradation of poly(styrene-co-methyl methacrylate) (poly(St-co-MMA)) has been investigated by both electron spin resonance (ESR) and viscosity measurements. On ultraviolet irradiation of poly(St-co-MMA) film at 30°C in vacuum, the scission type radical from poly(methyl methacrylate) is produced in the initial stages of the photo-irradiation. The polystyryl radical from polystyrene gradually increases with irradiation time. The resulting ESR spectrum is composed of those of both radicals. The ratio of the radicals produced in poly(St-co-MMA) by photo-irradiation was estimated by comparison with simulated ESR spectra. The viscosity average molecular weight, $\text{Mv}$ of photo-irradiated poly(St-co-MMA) decreases at short irradiation times and gradually increases at longer irradiation times. This phenomenon reflects the fact that the photo-degradation of the copolymer begins from the MMA component in poly(St-co-MMA). The γ-ray-induced degradation of poly(St-co-MMA) has also been examined by the same methods as those used in the photo-degradation and confirms that the degradation begins from the MMA component in the copolymer. The protective effect of polystyrene was also found for the radiation-induced degradation of the polymethyl methacrylate units in poly(St-co-MMA).     

Synthesis of poly(2‐hydroxyethyl methacrylate) in protic media through atom transfer radical polymerization using activators generated by electron transfer

Atom transfer radical polymerization (ATRP) using activators generated by electron transfer (AGET) was investigated for the controlled polymerization of 2‐hydroxyethyl methacrylate (HEMA) in a protic solvent, a 3/2 (v/v) mixture of methyl ethyl ketone and methanol. The AGET process enabled ATRP to be started with an air‐stable Cu(II) complex that was reduced in situ by tin(II) 2‐ethylhexanoate. The reaction temperature, Cu catalysts with different ligands, and variation of the initial concentration ratio of HEMA to the initiator were examined for the synthesis of well‐controlled poly(2‐hydroxyethyl methacrylate) and a poly(methyl methacrylate)‐b‐poly(2‐hydroxyethyl methacrylate) block copolymer. The level of control in AGET ATRP was similar to that in normal ATRP in protic solvents, and this resulted in a linear increase in the molecular weight with the conversion and a narrow molecular weight distribution (weight‐average molecular weight/number‐average molecular weight < 1.3). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3787–3796, 2006     

Well‐defined glycopolymer amphiphiles for liquid and supercritical carbon dioxide applications

Well‐defined D ‐glucose‐containing glycopolymers, poly(3‐O‐methacryloyl‐1,2 : 5,6‐di‐O‐isopropylidene‐D ‐glucofuranose) (PMAIpGlc), and diblock copolymers of PMAIpGlc with poly(1,1‐dihydroperfluorooctyl methacrylate) (PFOMA) were synthesized by living anionic polymerization in THF at ?78 °C with 1,1‐diphenylhexyllithium in the presence of lithium chloride. The resulting polymers were found to possess predictable molecular weights and very narrow molecular weight distributions (MWD, M_w/M_n ≤ 1.16). Removal of the acetal protective groups from the protected glycopolymer block copolymer was carried out using 90% trifluoroacetic acid at room temperature, yielding a hydrophilic block copolymer with pendant glucose moieties. Both protected (lipophilic/CO₂‐philic) and deprotected (hydrophilic/CO₂‐philic) fluorocopolymers were proved to be CO₂ amphiphiles. Their solubility in CO₂ was heavily influenced by the amphiphilic structure, such as the copolymer compositions and the polarities of sugar block. Light‐scattering studies showed that, after removal of the protective groups, the deprotected block copolymer formed aggregate structures in liquid CO₂ with an average micellar size of 27 nm. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3841–3849, 2001     

Grafting acrylic polymers from flat nickel and copper surfaces by surface-initiated atom transfer radical polymerization

Acrylic polymers, including poly(methyl methacrylate), poly(2,2,2-trifluoroethyl methacrylate), poly( N,N'-dimethyaminoethyl methacrylate), and poly(2-hydroxyethyl methacrylate) were grafted from flat nickel and copper surfaces through surface-initiated atom transfer radical polymerization (ATRP). For the nickel system, there was a linear relationship between polymer layer thickness and monomer conversion or molecular weight of "free" polymers. The thickness of the polymer brush films was greater than 80 nm after 6 h of reaction time. The grafting density was estimated to be 0.40 chains/nm2. The "living" chain ends of grafted polymers were still active and initiated the growth of a second block of polymer. Block copolymer brushes with different block sequences were successfully prepared. The experimental surface chemical compositions as measured by X-ray photoelectron spectroscopy agreed very well with their theoretical values. Water contact angle measurements further confirmed the successful grafting of polymers from nickel and copper surfaces. The surface morphologies of all samples were studied by atomic force microscopy. This study provided a novel approach to prepare stable functional polymer coatings on reactive metal surfaces.     

Synthesis and characterization of green to orange electroluminescent copolymers derived from fluorene and 2,3-dimethylnaphthalopyrazine

Series of high molecular weight, readily soluble copolymers were synthesized by Suzuki palladium catalyzed coupling reaction from 9,9-dioctylfluorene and 2,3-dimethylnaphthopyrazine. The absorption, electrochemical and photoluminescence properties of the copolymers were studied. The external electrolu-minescence efficiencies in the devices of configuration indium-tin oxide/polyethylenedioxythiophene-polystyrene sulfonic acid/poly(fluorene-naphthopyrazine)/barium/aluminium varied with the copolymers composition, and the electroluminescence emission peaks of the copolymers were red-shifted from 530 nm to 584 nm as 2,3-dimethylnaphthopyrazine mole contents increasing from 0.5% to 30%. The best device performance was observed for devices fabricated with the copolymer of 2,3-dimethylnathphpyrazine 5% mole contents, showed maximum external quantum efficiency of 1.38% and electroluminescence peaks at around 537 nm.