六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合体系的研究

六甲氧基甲基三聚氰胺 (HMMM) 多元醇 丙烯酸酯 酸催化剂混杂聚合体系在高温下同时进行缩聚和自由基聚合并表现出协同效应 .体系中的活泼亚甲基在HMMM的催化下被空气氧化成过氧化氢物 ;过氧化氢物在酸催化下分解成自由基进而引发自由基聚合反应 .研究结果表明 ,体系中存在固化加速的协同效应 ;同时体系中还存在热互补效应 ,丙烯酸酯的自由基聚合反应放出的热可以传递给缩聚反应 ,满足缩聚反应吸热的要求 .混杂聚合得到的高分子合金膜具有优良的机械性能和耐溶剂性能 ,这是由于在混杂聚合过程中形成了互穿聚合物网络 (IPN)结构 .使用潜酸催化剂作为酸的来源 ,可以提高体系的储存稳定性 ;交联 引发剂的使用可以拓宽它的使用范围 ;对超枝化聚合物在混杂体系中的应用也进行了初步研究     

六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合中酸的双重作用

六甲氧基甲基三聚氰胺 (HMMM) 多元醇 丙烯酸酯混合体系在较高温度下可同时进行缩聚和自由基聚合并表现出加速固化、热互补、原位形成高分子合金等协同效应 .通过凝胶化时间和聚合反应速度的研究 ,发现酸既是HMMM 多元醇缩聚反应的催化剂 ,也是促进过氧化氢物分解产生自由基引发丙烯酸酯自由基聚合的催化剂 .研究还发现 ,以潜酸催化剂作为酸的来源可以使体系达到室温稳定 ,高温快速固化的目的     

Distribution of melamine in polyester–melamine surface coatings cured under nonisothermal conditions

The influence of experimental cure parameters on the diffusion of reactive species in polyester–melamine thermoset coatings during curing has been investigated with X‐ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared. The diffusion of melamine plays a vital role in the curing process and, therefore, in the ultimate properties of coatings. At a low (<20%) hexamethoxymethylmelamine (HMMM) crosslinker concentration, the matrix composition is uniform, but at high HMMM concentrations, excess HMMM rapidly segregates to the air–coating interface. The rate of migration is governed by the difference in the surface free energies of polyester and HMMM and the concentration gradient of HMMM between the bulk and the surface. An increased rate of energy absorption also increases the rate of migration of HMMM to the surface. A physical model has been proposed to explain this surface segregation phenomenon in terms of cocondensation and self‐condensation reactions. It suggests that an appropriate amount of melamine can be segregated on the surface and allowed to self‐condense to form a desired thickness of a melamine topcoat through the control of the binder composition and cure conditions. This technique can be implemented to apply a melamine topcoat during cure. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 83–91, 2004     

Hydrolysis and polycondensation of acid-catalyzed Phenyltriethoxysilane (PhTES)

The effects of acid catalyst, water content and reaction temperature on the hydrolysis and polycondensation of phenyltriethoxysilane (PhTES) were studied using ²⁹Si NMR spectroscopy. The sol catalyzed by hydrochloric acid showed the simultaneous progress of hydrolysis and polycondensation. In addition, the reaction rate was almost independent of reaction temperature. On the other hand, the polycondensation in the PhTES-derived sol mixed with an excess amount of water and acetic acid as a catalyst proceeded after completion of the hydrolysis. In the acetic acid-catalyzed system, the degree of the hydrolysis and polycondensation largely depends on the reaction temperature.     

六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合过程热互补效应的研究

六甲氧基甲基三聚氰胺（HMMM）－多元醇－丙烯酸酯－酸催化剂的混合体系在较高温度下同时进行缩聚和自由基聚合并表现出协同效应，DSC研究结果表明，丙烯酸酯在HMMM和酸的催化作用下可在较低温度下发生自由基聚合反应，并把反应释放出来的大量的热量有效地传递给缩聚发反应，满足缩聚反应吸热的要求，从而节省固化所需要的能量，为了提高储存稳定性。本文以潜酸催化剂作为酸的来源，对该混杂聚合体系进行了研究，仍有明显的热互补效应。     

六(甲氧基甲基)三聚氰胺/多元醇/二甲基丙烯酸酯的混合体系的聚合

六(甲氧基甲基)三聚氰胺(HMMM)-二缩三乙二醇(T_3EG)和二缩三乙二醇二甲基丙烯酸酯(T_3EGMA)的混合体系加入潜酸催化剂后,在较高温度下可同时进行缩聚和自由基聚合并表现出协同效应.在这一混合聚合体系中HM-MM不仅是交联剂,而且是体系中活泼亚甲基氧化为过氧化氢物的催化剂,由潜酸催化剂分解出的酸是缩聚的催化剂,也是过氧化氢物分解为自由基的催化剂,生成的自由基可引发T_3EGMA聚合.有关凝胶时间实验,吸氧实验和活性氧测定的结果支持上述论断.     

Acid-Base and Catalytic Properties of Metal Compounds in the Preparation of Polyethylene Terephthalate)

Catalytic activity of a metal complex for both the transesterification of DMT (dimethyl terephthalate) and the polycondensation of BHET (bis(2-hy-droxyethyl terephthalate)) is described in terms of an acidity function formulated from the physical properties of the metal ion. Catalytic activity for both reactions is governed by the acidity of the metal ion, not by the type of anionic ligand. Maximum catalytic activity is observed with optimum bond strength between the metal ion and the double-bonded oxygen in the ester carbonyl group of DMT or BHET. Thus, a basic (less acidic) metal ion exhibits high catalytic activity for a more basic oxygen in the ester carbonyl of DMT, while a more acidic metal ions exhibits high catalytic activity for a less basic oxygen in the ester carbonyl of BHET. in the polycondensation reaction, a semiconductor metal ion shows higher activity than an insulator metal ion when compared at the same acidity value, but the former also catalyzes side reactions which can cause discoloration of the final polyethylene terephthalate) polymer. Discoloration is enhanced when a semiconductor metal ion has a redox couple during polycondensation.     

Mechanistic investigations of antimony‐catalyzed polycondensation in the synthesis of poly(ethylene terephthalate)

The chemical aspects of poly(ethylene terephthalate) synthesis via the antimony‐catalyzed polycondensation of hydroxy ethylene terephthalate end groups were studied to elucidate its mechanism. A polycondensation mechanism was proposed in which activation occurs by the formation of a chelate ligand on antimony composed of the hydroxyl end group and alcoholic oxygen of the ester of the same end group. The rate‐determining step of the polycondensation reaction was concluded to be the coordination of a second chain end to antimony. The low activity of antimony at a high concentration of hydroxyl end groups was proposed to result from the competition between hydroxyl end groups and the chelate structure leading to the transition state. The high selectivity of antimony is probably due to its relatively low Lewis acidity. Moreover, antimony was found to stabilize hydroxyl end groups against degradation by preventing their complexation to carbonyl functionalities. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1049‐1059, 2006     

高醚化三聚氰胺甲醛树脂交联水性聚氨酯的制备与表征

合成了高醚化三聚氰胺甲醛树脂(HMMM)交联改性含聚乙二醇单甲醚(Ymer N120)亲水基团的阴离子型水性聚氨酯。 通过全反射红外(ATR-FTIR)、差示扫描量热仪(DSC)、电子拉力机等技术手段表征了改性后的水性聚氨酯胶膜结构、热性能和力学性能。 结果表明,随着HMMM质量分数的增加,聚氨酯胶膜中氢键相互作用减弱,胶膜耐热性、耐水性、拉伸强度、粘接性均有所提高;当HMMM为8%时,聚氨酯胶膜的拉伸强度增加了125%,T-型剥离强度增加了7.4 N/cm,硬段最大热分解速率对应温度增加了38 ℃。 此外,交联水性聚氨酯胶膜的耐水性也得到了很大程度的提高。     

Kinetics of formation of polybisbenzimidazobenzophenanthroline-dione (BBB polymer)

The kinetics of the polycondensation of 3,3′-diaminobenzidine with 1,4,5,8-naphthalenetetracarboxylic acid (NTC) have been investigated. Polymerizations were carried out in solution in either polyphosphoric acid (PPA) or in PPA mixed with some sulfuric acid. The reaction is heterogeneous in PPA owing to partial solubility of NTC, whereas it is homogeneous in the mixed solvent. The rate of disappearance of NTC and of dicarboxylic endgroups on oligomers was followed as a function of time at several reaction temperatures. The results show that NTC is more reactive than oligomers, so that the principle of equal reactivity is not valid for the initial steps in the polycondensation reaction.     

The roles of hydroxyl radicals, photo-generated holes and oxygen in the photocatalytic degradation of humic acid

This article is aimed at studying on the roles of the hydroxyl radicals, photo-generated holes, and oxygen in the photocatalytic degradation of humic acid (HA) in acid and alkaline conditions. The results indicate that hydroxyl radicals?? scavenger alone can inhibit the photocatalytic degradation process completely in alkaline condition, which implies that photo-generated holes cannot directly degrade the organic matter in alkaline condition. Moreover, the reaction sites between hydroxyl radicals and HA is on the TiO₂ surface in acid condition. But in alkaline condition, hydroxyl radicals diffuse and react with HA in the solution. The generation of hydroxyl radicals almost stops and the photocatalytic degradation is inhibited seriously without oxygen, which illustrates that oxygen plays an important role in the photocatalytic degradation of HA.     

Polycondensation kinetics of orthosilicic acid in a hydrothermal solution

The polycondensation kinetics of orthosilicic acid in hydrothermal solutions was studied experimentally at different temperatures, pH, and ionic strengths. As a result of the mathematical processing of experimental data, equations approximating the time dependence of the polycondensation process and the dependence of the polycondensation rate constant on the solution ionic strength were obtained. Experimental data on the kinetics of the reverse process of dissolving colloidal silica were obtained at different temperatures and pH.     

Polyarylates. V. The influence of phase transfer agents on the interfacial polycondensation

The effect of various phase transfer agents on the interfacial polycondensation of bisphenol A with isophthaloyl chloride was investigated. It was found that the transfer rate of bisphenolate and, thus, the reaction rate of polycondensation were increased with an increasing lipophilicity of the phase transfer agent, i.e. TBAC > TEBAC > TEAC, whereas the equilibrium of bisphenolate between the organic phase and the aqueous phase was hardly affected. Moreover, experimental evidence indicated that a phase transfer agent of high lipophilicity reduced the hydrolysis of the acid chloride, an important aspect in interfacial polycondensation.     

The formation of polyethylene terephthalate in the presence of dicarboxylic acids

The process of polyethylene terephthalate (PET) formation in the presence of dicarboxylic acids has been studied. Certain amounts of terephthalic acid (TPA) have two- to threefold accelerating efficiency in the polycondensation process. To elucidate the causes of the acceleration the main reactions leading to PET formation in the presence of dicarboxylic acids have been investigated by the use of models. The evaluation of kinetic and equilibrium parameters obtained for model reactions made it possible to conclude that the influence of carboxyl-containing additives on the apparent rate of polycondensation manifests itself in accelerating direct reactions and facilitating the liberation of the eliminated by-product; that is, ethylene glycol (EG) from the polymer melt. Carboxylic acid acts as a catalyst on the ester interchange of 2-hydroxyethyl ester end groups and thus increases the rate of polymer formation in this reaction 10–40 times. The parallel interaction between the 2-hydroxyethyl ester end group and the carboxyl group of the added acid is also catalyzed by the acid and its rate constant is four times larger than that of the catalytic polycondensation of 2-hydroxyethyl ester end groups. Unlike EG, the reaction water formed in the process is more readily removed from the reaction system and thus promotes the intensification of the process. In addition, the carboxyl groups react with the eliminated EG to decrease its amount and shift the equilibrium toward polymer formation. The investigation of the consequent parallel reactions on models made it possible to draw a conclusion about the higher reactivity of 2-hydroxyethyl esters in the esterification processes. This fact has been explained by strengthening the nucleophilicity of the oxygen atom in the hydroxyl of a 2-hydroxyethyl ester group compared with that of EG; for example, by the formation of an intramolecular cycle involving a hydrogen bond. Simultaneously, it has been found that in the system simulating PET polycondensation in the presence of dicarboxylic acids the reaction mechanism involves the catalysis by a proton formed during the carboxyl group dissociation and accepted by the 2-hydroxyethyl ester group.     

甲酚醛树脂—HMMM负性水型化学增幅抗蚀剂的研究

本文利用二苯碘 盐为光敏产酸物,吩噻嗪为敏化剂,配制了一种甲酚醛树脂——六甲氧基甲基三聚氰胺(HMMM)负性水型紫外化学增抗蚀剂,并研究了光敏产酸物和增感剂对体系光敏性的影响及体系中存在的拉平效应,通过优化后的光刻工艺条件得到了分辨率为1.24μm的光刻图形。     

Poly(2,5-benzoxazole)/carbon nanotube composites via in situ polymerization of 3-amino-4-hydroxybenzoic acid hydrochloride in a mild poly(phosphoric acid)

Poly(2,5-benzoxzole) (ABPBO)/carbon nanotube (CNT) composites were prepared via in situ polycondensation of “protonated” AB monomer, 3-amino-4-hydroxybenzoic acid hydrochloride, in a mildly acidic poly(phosphoric acid) medium. In situ generated hydrochloric acid during the dehydrochlorination process provided additional acidity to the reaction medium. The enhanced acidity was advantageous for both the purification and dispersion of CNTs. Specifically, it was evident for the purification of as-received single-walled carbon nanotube (SWCNT), which was contained a large portion of impurity (60-70 wt%). On the basis of the data obtained from elemental analysis (EA), thermogravimetric analysis (TGA), infrared spectroscopy (FT-IR), and X-ray diffraction (XRD) as well as scanning electron microscopy (SEM) and transmission electron microscopy (TEM), the resultant composites implicated that individual tube of multi-walled carbon nanotube (MWCNT) and bundles of SWCNT were homogeneously dispersed into the ABPBO matrix. After in situ polymerization in harsh temperature at 175 °C and subsequent work-up processes, CNTs were remained structurally intact in a mild reaction medium. Thus, the PPA medium is indeed viable for the preparation of composite.     

Synthesis of oligoesters and polyesters from oxalic acid and ethylene glycol

High molecular weight poly(ethylene oxalate) with fiber-forming properties was obtained from oxalic acid and ethylene glycol. The process was carried out on two stages in the melt. A new method was used for aliphatic oligoester synthesis in the melt, because the decomposition of oxalic acid takes place in the presence of glycol. The process was carried out at low temperatures with azeotropic water removal. Investigations of the polycondensation of oxalic acid and ethylene glycol with a compound forming a heteroazeotrope with water showed that the process is subject to the general laws of the polycondensation in melt: it depends on the ratio of initial components, presence of accelerating compounds, etc. However, the reaction time of polycondensation was dependent on the stirring intensity. High molecular weight poly(ethylene oxalate) was obtained by oligomer polycondensation in the melt. Thorium carbonate and tin dichloride were used as catalysts.     

Poisoning Effect of Acid Soluble Oil on Triflic Acid-Catalyzed Isobutane Alkylation

The rate of the isobutane alkylation reaction with secondary butenes catalyzed by trifluoromethanesulfonic acid at –20°C is experimentally found to depend on the concentration of acid soluble oil (ASO), which poisons TfOH. With an increase in the ASO molar fraction from 0.13 to 0.16, the reaction rate decreases by a factor of ten. The Hammett acidity function was determined for TfOH solutions at 25°C in the concentration range from 0 to 0.2 ASO molar fractions. The results obtained suggest that the alkylation reaction rate is proportional to the proton activity in the acid phase determined by the Hammett acidity function.     

米氏酮和二苯基碘盐光产酸体系及其在印刷版材中的应用研究

在高压汞灯的照射下 ,4,4’ 二 (N ,N’ 二甲基 氨基 )苯甲酮 (米氏酮 )与六氟磷酸二苯基碘盐可以有效地发生电子转移反应 ,产生的强酸能够有效地催化六甲氧基次甲基三聚氰胺 (HMMM )与间甲酚树脂之间的交联反应 .这个体系在作为印刷版材研究中获得了很好的结果 .版材的分辨率可达到 7μm ,网点的再现性为 2 % .同时研究了对版材性能产生影响的其它一些因素 .     

Effect of chelation on the polycondensation of monomers having an active ester group

Various amino acid esters and dicarboxylic acid esters having a β-thioether group have been synthesized and their polycondensation with diamine was found to occur at room temperature to form polyamide thioether. The effect of solvents or chelating agents on their polycondensation reaction was investigated. Metal acetylacetonates or inorganic salts had a great influence on the rate of the polycondensation reaction, and the catalytic activity of metal acetylacetonates M(AcAc)_n or inorganic salts decreased in the following order: Mg(AcAc)₂?Th(AcAc)₄>Cu(AcAc)₂>Li(AcAc)>None>Zr(AcAc)₄, MgCl₂·6H₂O>CuCl₂·.2H₂O>ZnCl₂>MgCl₂>None. It was also found that the amount of polyamide thioether was dependent on solvents or the presence of chelating agents because the polycondensation rate and the apparent equilibrium between ring and chain structures were both greatly influenced by solvents or chelating agents. These effects of solvents or chelating agent on the polycondensation may be attributable to formation of a complex with the thioether group which enhances the reactivity of ester.