N-（p-羟基苯基）甲基丙烯酰胺的合成与表征

N-芳基取代的甲基丙烯酰胺(结构式如图1所示)是一类非常有用的共聚单体,它们可以与甲基丙烯酸酯或N-取代马来酰亚胺等单体共聚,使共聚物的一些性能,如耐热性、耐水性、透明度、硬度等都有不同程度的改进[1-4].关于N-芳基取代的甲基丙烯酰胺的制备,文献[5-8]曾有报道,通常采用甲基丙烯酰氯与芳基胺在乙醚、苯等溶剂中反应,并加入适当的缚酸剂来完成.而N-(p-羟基苯基)甲基丙烯酰胺(此处R＝OH)是N-芳基取代甲基丙烯酰胺中一种比较特殊的单体,它即含有碳碳双键,又含有酚羟基,属于双官能团物质.关于它的制备及用途,尚未见有文献报道.文献[5]曾报道说,采用对胺基苯酚与甲基丙烯酰氯反应仅能得到甲基丙烯酸(N-(p-甲基丙烯酰胺基)苯酚酯(即酰胺-酯化合物).本文合成出了这种物质,并对其进行了表征和证实;我们推测它与一些单体(如N-取代马来酰亚胺等)的共聚物可以溶于碱性水溶液,并且有好的耐热性,因此在紫外光刻胶中可能有比较大的应用潜力[9-11],有关这方面的内容我们将另文报道.     

N-(对甲苯基)马来酰亚胺的自由自聚合与光敏诱导聚合及共聚合

N-烷基与N-芳基马来酰亚胺,是属于1,2-二取代乙烯结构的单体,文献[1—3]报道这类单体能进行自由基聚合与共聚合。但对于N-(对甲苯基)马来酰亚胺(PMPMI)的自由基聚合与共聚合中,溶剂对聚合物分子量的影响尚未有详细报道。至于N-烷基与N-芳基马来酰亚胺分别和丙烯酸甲酯(MA)、甲基丙烯酸甲酯(MMA)的共聚合也有一些报道,由竞聚率的测定,计算出N-芳基马来酰亚胶的e值是2.12—2.29和1.35—1.75。表明N-芳基马来酰亚胺是一缺电子的单体,即负性单体。我们研究室曾报道N,N-二甲基-对甲苯胺(DMT)和其它芳胺能光诱导引发负性单体丙烯腈聚合。PMP-     

N-[4-(N′-取代酰胺基)苯基]马来酰亚胺的合成与表征

N-取代马来酰亚胺(RMI)是一类重要的新型树脂改性单体,由于其具有刚性五元环的结构,能显著提高聚合物的玻璃化温度和热分解温度,改善材料的工艺性和力学性能[1-9]。但文献对于在N-取代基团中引入杂环结构的单体合成报道很少。本文报道了由顺丁烯二酸酐、8-氨基喹啉、对甲苯胺为主要原料合成N-[4-(N′-8-喹林基)苯甲酰胺基]马来酰亚胺(QPM)和N-[4-(N′-4-甲基苯基)苯甲酰胺基]马来酰亚胺(TPM)的方法,并对产物进行了元素分析和1H-NMR、FT-IR表征。同时,由于8-氨基喹啉具有与8-羟基喹啉类似的结构,能表现出较好的光学性能[10,11],以N…     

己内酯与N-苯基马来酰亚胺的杂化共聚

以膦腈碱(t-BuP4)为催化剂催化了己内酯(CL)和N-苯基马来酰亚胺(NPMI)的杂化共聚反应.用核磁(1H-NMR)、红外光谱(FTIR)、凝胶渗透色谱(GPC)和热失重(TGA)对聚合物及聚合反应过程进行了表征.结果表明,t-BuP4能成功催化CL和NPMI的杂化共聚,合成具有CL和NPMI两种结构单元的共聚物.聚合反应过程中NPMI以打开双键的方式进入聚合物.聚合物中己内酯结构单元的含量随CL和NPMI单体摩尔比的增加而增加,但其含量始终小于NPMI结构单元的含量.合成共聚物的热稳定性介于己内酯和N-苯基马来酰亚胺均聚物之间.     

苯乙烯-N-苯基马来酰亚胺-马来酸酐三元共聚物的合成与性能

以过氧化对苯二甲酸二叔丁酯为引发剂, 以一次投料方式, 采用溶液聚合法合成了苯乙烯-N-苯基马来酰亚胺-马来酸酐三元共聚物. 通过控制单体配比, 实现产物中N-苯基马来酰亚胺质量分数在48%~63%之间可调. 采用FTIR, ¹H NMR, ¹³C NMR和GPC技术对三元共聚物的化学组成、链序列结构和分子量进行了测试. 利用FOX方程计算的共聚物NPMI含量与¹H NMR核磁测试结果一致. DSC和TGA测试的结果表明, 当N-苯基马来酰亚胺质量分数>48%时, 共聚物的玻璃化转变温度(T_g)从202 ℃提高到215 ℃, 5%热失重温度高于363 ℃, 所以三元聚合物是一种优异的聚合物耐热剂.     

N-[4-(N''''-取代酰胺基)苯基]马来酰亚胺的合成与表征

N-取代马来酰亚胺(RMI)是一类重要的新型树脂改性单体，由于其具有刚性五元环的结构，能显著提高聚合物的玻璃化温度和热分解温度，改善材料的工艺性和力学性能。但文献对于在N-取代基团中引入杂环结构的单体合成报道很少。本文报道了由顺丁烯二酸酐、8-氨基喹啉、对甲苯胺为主要原料合成N-[4-(N’-8-喹林基)苯甲酰胺基]马来酰亚胺(QPM)和N-[4-(N’-4-甲基苯基)苯甲酰胺基]马来酰亚胺(TPM)的方法，     

高玻璃化温度化学增幅光致抗蚀剂的制备

本文合成了一种具有高玻璃化温度的苯乙烯和N-(4-羟基苯基)马来酰亚胺的共聚体,并将其应用于紫外负性水型化学增幅抗蚀剂中,并初步确定了该光致抗蚀剂的光刻工艺操作条件,得到了分辨率为1.39µm的光刻图形。     

一种新型紫外正型光刻胶成膜树脂的制备及光刻性能研究

本文合成了N-(p-羧基苯基)甲基丙烯酰胺单体,并将其与N-苯基马来酰亚胺共聚得到共聚物聚N-(p-羧基苯基)甲基丙烯酰胺共N-苯基马来酰亚胺(poly(NCMA-co-NPMI)).将此共聚物作为成膜树脂,与感光剂、溶剂等复配得到一种新型耐高温紫外正型光刻胶.本文探讨了该光刻胶的最佳配方组成和最佳光刻工艺.最佳配方组成为:15%—20%成膜树脂,4.5%—6%感光剂和70%—80%溶剂;最佳光刻工艺为:匀胶30 s(4000 rpm),前烘4 min(90℃),感度为30—35mJ/cm²,在0.2%TMAH溶液显影10 s和后烘2 min(90℃).     

N-(4-羟基苯基)马来酰亚胺的合成及其光谱分析

利用对氨基酚和马来酸酐反应制取N-(4-羟基苯基)马来酰亚胺(HPM),并采用红外光谱及核磁光谱对其结构进行了表征.研究了HPM在甲醇、四氢呋喃及二氯甲烷3种溶剂中的紫外光谱.结果发现,在这3种溶剂中,HPM在210～250 nm范围内的吸收峰对溶剂极性及溶液浓度敏感;而275 nm左右的吸收峰在各种极性不同溶剂中位置...     

6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪及其共聚物的合成

以6-甲基-3-羟乙基-3,4-2H-1,3-苯并噁嗪(MB-OH)和甲基丙烯酰氯为原料, 通过酯化反应合成了6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪(MBEM). 采用自由基溶液聚合法, 以偶氮二异丁腈(AIBN)为引发剂, 以甲苯为溶剂, 以MBEM与N-苯基马来酰亚胺(NPMI)为单体, 合成了6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪-co-N-苯基马来酰亚胺共聚物[P(MBEM-co-NPMI)]. 分别对MB-OH, MBEM, P(MBEM-co-NPMI)进行加热固化, 得到相应的交联聚合物PMB-OH, PMBEM和P[P(MBEM-co-NPMI)]. 对其结构、分子量和热性能进行了表征. 结果表明, PMB-OH, PMBEM, P[P(MBEM-co-NPMI)]的最大损耗因子tanδ_max对应的玻璃化转变温度(T_g)分别为92, 129和181℃, 最大损耗模量G"_max对应的T_g分别为56, 91和156℃. 在N₂气氛围下, PMB-OH, PMBEM, P[P(MBEM-co-NPMI)]失重5%的温度分别为257, 244和260℃; 失重10%的温度分别为280, 266和284℃; 800℃的残炭率分别为23.2%, 17.8%和14.0%. 表明P[P(MBEM-co-NPMI)]具有优异的耐热性能.     

STUDY ON THE SYNTHESIS AND PROPERTIES OF POLY(ESTER-IMIDEETHER)MULTIBLOCK COPOLYMERS

A new class of poly(ester-imide-ether) multiblock copolymers was synthesized by transes-terification and meltcopolymerization of dimethyl terephthalate (DMT) and N-(4-carbomethoxyphenyl)-4-(carbomethoxy)-phthalimide withethylene glycol (EG) and polytetramethylene glycol (PTMG). The structure of the above copolymers was characterized by~1H-NMR and IR spectroscopy. Some properties of the coplymers were also examined. It was found that their mechanicalproperties and heat stability, compared with poly(ether-ester) copolymers, were obviously improved.     

Thermal stability and degradation of poly(N-(4-chlorophenyl) acrylamide) homopolymer and copolymer of N-(4-chlorophenyl) acrylamide with methyl methacrylate

Different concentrations of copolymer of (N-(4-chlorophenyl) acrylamide) (CA) with methyl methacrylate (MMA) were prepared and the reactivity ratio values of copolymerization were calculated using ¹H NMR technique. Thermal analysis of the copolymers showed that the thermal stability is intermediate between poly(N-(4-chlorophenyl) acrylamide) (PCA) and poly(methyl methacrylate) (PMMA) homopolymers. Thermal degradation products of the PCA were identified by GC–MS techniques. It seems that the mechanism of degradation of PCA homopolymer is characterized by free radical formation followed by recombination along the backbone chain. The activation energies of the thermal degradation of the copolymers were calculated using Arrhenius relationship.     

N-苯基马来酰亚胺/对氯甲基苯乙烯活性可控超支化交替共聚合的研究

采用核磁共振氢谱, 研究了N-苯基马来酰亚胺(NPMI)与对氯甲基苯乙烯(PCMS)在氘代氯仿中的络合性能. 以PCMS作为引发剂单体, 通过原子转移自由基聚合(ATRP)引发NPMI-PCMS电子转移络合物(CTC)进行活性可控超支化共聚合. 考察了单体初始摩尔分数对共聚物组成和其玻璃化转变温度的影响, 用Kelen-Tudos法计算得到两种单体的竞聚率分别为 r_NPMI＝0.11和r_PCMS＝0.25. 结果表明, 当单体配比f_NPMI＝0.4～0.7时, 共聚物具有交替结构, 其耐热性随着NPMI含量的增加而提高. 此外还考察了溶剂、聚合温度等对共聚合反应动力学的影响. 并进一步用所得超支化交替共聚物作为大分子引发剂, 引发甲基丙烯酸甲酯(MMA)聚合, 制得了多臂超支化接枝共聚物 poly(NPMI-co-PCMS)/poly(MMA).     

Synthesis of molecular imprinted organic-inorganic hybrid polymer binding caffeine

Random copolymers of poly{(methacrylamide)-co-(vinyl trimethoxysilane)} and poly{(methacrylic acid)-co-(vinyl trimethoxysilane)} were synthesized via a free radical polymerization reaction. Acid catalyzed sol-gel process of tetraethylorthosilicate (TEOS) with aforementioned polymers in the presence of methyl xanthine class of alkaloid like caffeine resulted in the formation of highly transparent monoliths. Solvent extraction of the template leaves behind the recognition sites intact with high selectivity towards the print molecule. The ionic and non-specific adsorptions, which are considered to be the main disadvantages of the molecularly imprinted polymers (MIP), are prevented to a considerable extent by the end capping of surface silanol groups. The template binding efficiencies of MIP were determined by HPLC analysis.     

以苯甘氨酸基为侧链的光学活性甲基丙烯酰胺聚合物的合成及手性识别能力

合成了N-[(R)-α-叔丁氧基羰基苄基]甲基丙烯酰胺((R)-BCBMAM),通过自由基聚合法获得相应的光学活性聚合物(P(R-BCBMAM)),并以三氟乙酸为水解催化剂除去叔丁基而得到(P(R-CBMAM)).用1H-NMR,IR,CD和GPC对聚合物进行了结构表征,发现聚合溶剂和聚合物分子量对所得聚合物P(R-BCBMAM)的光学活性没有明显影响,P(R-BCBMAM)水解后光学活性有较大的改变.与单体相比,聚合物的比旋光度有较大的区别,且在对应于其侧基的紫外吸收处呈现明显不同于单体的Cotton效应,说明聚合物的主链可能形成了一定的二级结构.以P(R-BCBMAM)和P(R-CBMAM)制备的2种涂敷型高效液相色谱用手性固定相,对部分对映体具有一定的手性拆分能力.利用1H-NMR技术研究了上述2种聚合物与1,1'-联-2-萘酚(BINOL)的相互作用,它们对BINOL都具有良好的手性识别能力.     

Amphiphilic copolymers with poly(meth)acrylic acid chains “grafted from” caprolactone 2‐(methacryloyloxy)ethyl ester‐based backbone

Well‐defined amphiphilic graft copolymers containing hydrophilic poly((meth)acrylic acid) (PMAA) or poly(acrylic acid) (PAA) side chains with gradient and statistical distributions were synthesized. For this purpose, the hydroxy‐functionalized copolymers with various gradient degrees, in which 2‐(6‐hydroxyhexanoyloxy)ethyl (meth)acrylate units (caprolactone 2‐[methacryloyloxy]ethyl ester, CLMA) formed strong gradient with tert‐butyl acrylate (tBA), slight gradient copolymers with tert‐butyl (meth)acrylate (tBMA), and statistical copolymers with methyl (meth)acrylate (MMA) were modified to bromoester multifunctional macroinitiators, P(tBMA‐grad‐BrCLMA), P(BrCLMA‐grad‐tBA), and P(BrCLMA‐co‐MMA). In the next step, they were applied in controlled radical polymerization of tBMA and tBA yielding graft copolymers with various lengths of side chains as well as graft densities. Further, the tert‐butyl groups in copolymers were successfully removed via acidolysis in the presence of trifluoracetic acid, which caused transformation of the hydrophobic graft copolymers into amphiphilic ones with ability of self‐assembly for the future biomedical applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Photoacid generating polymers based on sulfonyloxymaleimides and application as single-component resists

Three sulfonyloxymaleimides (RsOMI), N-(tosyloxy)maleimide (TsOMI), N-(methane-sulfonyloxy)maleimide (MsOMI), and N-(trifluoromethanesulfonyloxy)maleimide (TfOMI), have been synthesized and used to make novel photoacid generating polymers. The sulfonyloxymaleimides easily copolymerized with styrene derivatives to give high molecular weight polymers having an alternating structure of both monomer units. Terpolymers based on RsOMI and p-(tert-butyloxycarbonyloxy)styrene (t-BOCSt) were prepared for enhancing resist properties such as adhesion to substrates, solubility in aqueous alkaline solutions, or transparency in the deep-UV region. The RsOMI copolymers were found to produce corresponding sulfonic acids (RsOH), TsOH, MsOH, and TfOH, by deep-UV irradiation in the film state. Thus, the polymers having both the RsOMI and t-BOCSt units show the capability of a single-component, chemically amplified resist system in the deep-UV region without addition of any photoacid generator. Positive- and negative-tone images were obtained by exposure of the polymer films to deep-UV and post-exposure bake followed by development with organic solvents or aqueous alkaline solutions. © 1996 John Wiley & Sons, Inc.     

N-异丙基丙烯酰胺类共聚物温敏性研究

制备了N-异丙基丙烯酰胺(NIPAAm)与N,N-二甲基丙烯酰胺(DMAAm)和/或甲基丙烯酸羟乙酯(HEMA)的二元及三元共聚物,研究了组成和链转移剂用量对共聚物温敏性的影响,并在上述三元共聚物上接枝聚己内酯(PCL)得到温敏性两亲聚合物.结果表明,随着DMAAm增加、HEMA减少或共聚物分子量降低,共聚物的最低临界溶解温度升高,且PCL链段的接枝度和长度对聚合物的温敏性影响明显.