锆螯合物交联丙烯酸酯共聚物无皂水溶胶的研究Ⅰ丙烯酸酯三元共聚物合成条件对无皂水溶胶性能的影响

三乙醇胺螯合锆烷氧化物;交联反应;锆螯合物交联丙烯酸酯共聚物无皂水溶胶的研究 Ⅱ锆螯合物与丙烯酸酯三元共聚物无皂水溶胶的交联反应     

锆螯合物交联丙烯酸酯共聚物无皂水溶胶的研究Ⅰ丙烯酸酯三元共聚物合成条件对无皂水溶胶性能的影响

三乙醇胺螯合锆烷氧化物;交联反应;锆螯合物交联丙烯酸酯共聚物无皂水溶胶的研究 Ⅱ锆螯合物与丙烯酸酯三元共聚物无皂水溶胶的交联反应     

锆螯合物交联丙烯酸酯共聚物无皂水溶胶的研究Ⅱ锆螯合物与丙烯酸酯三元共聚物无皂水溶胶的交联反应

研究了三元丙烯酸酯共聚物(MMA/BA/AA)无皂水溶胶中加入三乙醇胺锆螯合物对水溶胶及涂膜性能的影响. 在水溶胶中,螯合物增加了共聚物的亲水性,改变了水溶胶的流变性、稳定性、表面张力. 螯合物也提高了共聚物涂膜的耐水性. X光电子能谱(XPS)研究表明,在固化成膜过程中螯合物与共聚物发生交联反应,用IR、1H NMR、DSC、TGA和UV等分析方法对其交联机理作了初步探讨.     

金属离子络合交联丙烯酸酯共聚物无皂水溶胶涂料 Ⅰ.丙烯酸酯共聚物的合成和表征

金属离子络合交联丙烯酸酯共聚物无皂水溶胶涂料Ⅰ．丙烯酸酯共聚物的合成和表征杨立群谢志明李卓美＊（中山大学高分子研究所广州５１０２７５）关键词交联丙烯酸酯共聚物，无皂水溶胶，水性涂料，合成１９９７－０６－１６收稿，１９９８－０１－０８修回广州市科委科技...     

锆螯合物交联丙烯酸酯共聚物无皂水溶胶的研究Ⅱ锆螯合物与丙烯酸酯三元共聚物无皂水溶胶的交联反应

研究了三元丙炮酸酯共聚物（MMA／BA／AA）无皂水溶液中加入三乙醇胺锆螯合物对水溶胶及涂膜性能的影响，在水溶胶中，螯合物增加了共聚物的亲水性，改变了水溶胶的流变性、稳定性、表面张力、螯合物也提高了共聚物涂膜的耐水性，X光电子能谱（XPS）研究表明，在固化成膜过程中螯合物与共聚物发生交联反应，用IR、^1HNMR、DSC、TGA和UV等方法对其交联机理作了初步探讨。     

金属离子络合交联丙烯酸酯共聚物无皂水溶胶涂料 Ⅱ.Zn(NH_3)_4~(2 )交联无皂水性涂料的性能

金属离子络合交联丙烯酸酯共聚物无皂水溶胶涂料Ⅱ．Ｚｎ（ＮＨ３）２＋４交联无皂水性涂料的性能杨立群谢志明李卓美＊（中山大学高分子研究所广州５１０２７５）关键词交联丙烯酸酯共聚物，无皂水性涂料，流变性，耐热性，硬度１９９７－０６－１６收稿，１９９７－１２...     

丙烯酸酯共聚物无皂水溶胶稳定性的研究

用溶液聚合法合成了四种AA含量不同的丙烯酸酯共聚物(MMA/BA/HEMA/AA)，通过中和AA使共聚物带有—COO~-能起自乳化作用分散于水中而成为无皂水溶胶．TEM观察表明水溶胶粒子呈球状，单分散性好，粒径随AA含量增加而变小，在30～90 nm范围．用电导滴定法测定水溶胶粒子中—COOH和—COO~-的分布，表明绝大部分—COO~-处于粒子表面，并且随AA含量增加，粒子表面的—COO~-增多，Zeta电位增大，这是导致水溶胶的抗电解质稳定性(以C.C.C.值反映)和贮存稳定性(以表现粘度反映)随AA含量增加而提高的主要原因。     

两亲性RAFT试剂存在下丙烯酸六氟丁醋和苯乙烯的无皂乳液聚合

合成了具有两亲性结构的可逆加成断裂链转移(RAFT)试剂,在RAFT试剂的作用下,通过无皂乳液聚合方法合成了丙烯酸六氟丁酯与苯乙烯的共聚物.研究了RAFT试剂浓度和聚合温度对聚合动力学、聚合反应可控性及乳胶粒粒径的影响.通过红外光谱(FTIR)、核磁共振谱(1H NMR)、示差扫描量热仪(DSC)、凝胶渗透色谱仪(GPC)及表面张力仪表征了共聚物的结构、玻璃化转变温度(Tg)、分子量和分子量分布及乳胶膜表面性能.结果表明,得到的苯乙烯和丙烯酸六氟丁酯共聚物无皂乳液的乳胶粒粒径在100 nm左右且呈单分散分布.当RAFT试剂浓度高于0.016 mol/L时聚合体系有较好的可控性.共聚物乳液的乳胶膜对水和二碘甲烷的接触角都很高.     

表面活性单体NaAMC14S/丙烯酰胺共聚物的分子链微结构与疏水缔合性

在实施丙烯酰胺型阴离子表面活性单体2-丙烯酰胺基十四烷磺酸钠(NaAMC14S)与丙烯酰胺(AM)水溶液均相共聚合过程中,分别通过改变AM与NaAMC14S的投料比、改变外加电解质NaCl的加入量以及引发剂的用量,制备了分子链微结构系列变化的具有微嵌段结构的共聚物NaAMC14S/AM;采用荧光探针法与表观粘度法研究了共聚物分子链微结构与其疏水缔合性能之间关系,探索了共聚物分子链中疏水微嵌段含量、疏水微嵌段长度及共聚物分子量诸微结构因数对共聚物疏水缔合性的影响.结果表明,共聚物NaAMC14S/AM的疏水缔合性随着疏水微嵌段含量的增加而增强,随着疏水微嵌段长度的增长而增强,当疏水微嵌段含量和嵌段长度一定时,共聚物的疏水缔合性随分子量的增大而增强.     

丙烯酰胺型阴离子表面活性单体与丙烯酰胺共聚物水溶液的流变特性

以丙烯酰胺型阴离子表面活性单体2-丙烯酰胺基十四烷基磺酸钠(NaAMC14S)为共单体,与丙烯酰胺(AM)的水溶液均相共聚合,使NaAMC14S的浓度分别处于临界胶束浓度上下,分别制备了具有无规结构与微嵌段结构的两类共聚物;用红外光谱法对共聚物的结构进行了表征,使用乌氏粘度法测定了特性粘数,相对表示出了共聚物的分子量;采用荧光探针法与表观粘度法重点研究了两类共聚物的疏水缔合性与水溶液的流变特性.研究结果表明,具有微嵌段结构的共聚物具有很强的疏水缔合性,当其水溶液的浓度达0.2wt%后,表观粘度迅速提高;其水溶液的切力变稀行为具有明显的可逆性,表现出强的抗剪切性能.本研究中特别发现,具有微嵌段结构的共聚物其盐水溶液的表观粘度远高于纯水溶液的表观粘度,当共聚物浓度为0.3wt%、CaCl2浓度为2wt%时,溶液的表观粘度竟然提高了3个数量级,表现出独特的正性盐敏性(即遇盐变稠).     

Mechanical Properties of Films from Hybrid Acrylic‐Polyurethane Polymer Colloids

A variety of polyurethane based on the polyaddition of isophoronediisocyanate and polypropyleneglycol has been used to prepare acrylic‐polyurethane hybrid polymer colloids, through either mini‐emulsion polymerization of their solutions in a mixture of monomers or seeded emulsion polymerization of this mixture from seeds of modified polyurethane containing dimethylolpropionic acid neutralized with triethylamine. The mixture of monomer is composed of 30% styrene, 30% methylmethacrylate, and 40% butylacrylate. The mechanical properies of films prepared through coalescence of these latexes where studied. The effect of various parameters such as the composition and the amount of polyurethane as well as the synthesis process are discussed.     

Poly(acrylate/epoxy) hybrid adhesives for low‐surface‐energy plastic adhesion

The formulation, polymerization, and performance of a new class of low‐surface‐energy adhesives for plastics are described. The polymerization involves the simultaneous room‐temperature polymerization of polyoxirane monomers in an acrylic monomer phase. The polymerization of the acrylic phase and adhesion promotion to plastics are catalyzed after the decomplexation and oxidation of trialkylborane–amine complexes. The polymerization of the epoxy phase is catalyzed with a Lewis acid such as BF₃, ZnCl₂, or SnCl₄ complexed with ether or amine. This article explores the resulting adhesives as a function of the epoxy monomer functionality, concentration, solubility in the acrylic monomer, Lewis acid catalyst concentration, phase crosslinking, and postprocessing thermal history. The adhesive morphology exhibits a finely dispersed epoxy phase strongly interacting with the major acrylic phase resulting from a nucleation‐and‐growth phase‐separation mechanism. Excellent adhesion to plastics, including polyethylene, polypropylene, poly(tetrafluoroethylene), poly(ethylene terephthalate), and nylon, is achieved with a much higher thermal performance than that achievable with acrylic polymers alone. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 989–998, 2007     

Effectiveness of Graft Synthetic Polymers in Preventing Biodeterioration of Cellulose-Based Materials

Synthetic polymers have been occasionally applied to the consolidation and protection of paper and cellulose-based textiles especially when traditional conservation methods were not sufficient to improve the mechanical resistance of the degraded artefacts. In this paper, the potential of the innovative technique of grafting polymerisation with synthetic polymers was investigated to prevent biodeterioration. Cotton, linen and Whatman paper were consolidated by a) coating Paraloid B72®, b) coating ethyl acrylate/methyl methacrylate (EA/MMA) preformed copolymer, and c) grafting onto cellulose chains EA and MMA monomers in the ratio 75/25. All the samples were artificially biodeteriorated to obtain biodegraded model samples of both consolidated and non-consolidated substrates, according to the ASTM G21-96(2002) “Standard Practice for Determining Resistance of Synthetic Polymeric Materials to Fungi”. The consolidating effect was examined evaluating the mechanical behaviour of the grafted and coated samples, before and after the artificial biodeterioration. In addition, SEM observations were applied to monitor both the grafting level and the biodeterioration of the samples. With the grafting of acrylic monomers, the mechanical strength of cellulose-based textiles and paper was greatly improved, as well as the resistance to biological agents. Therefore, with regards to biodeterioration, the graft copolymer EA/MMA (75/25 wt) was proved to be a suitable method to help prevent possible deterioration of paper and textiles.     

聚硅氧烷-聚丙烯酸酯-聚氨酯三元复合乳液的制备与表征及其胶膜性能

用异佛尔酮二异氰酸酯与仲羟基封端的聚硅氧烷(PMTS)反应在聚硅氧烷分子链端引入异氰酸酯基团, 然后将其与聚丙二醇、二羟甲基丙酸等反应制备聚硅氧烷改性聚氨酯(PSU)预聚体, 再以甲基丙烯酸甘油酯(GM)为偶联剂在PSU链上引入双键, 最后加入丙烯酸酯单体和交联剂乳化后通过乳液聚合制备了偶联型聚硅氧烷聚丙烯酸酯改性聚氨酯(PSU-X-AC)三元复合乳液. 同样条件下不使用偶联剂制备了非偶联型三元复合乳液(PSU-AC). 无论是否使用偶联剂, 三元复合乳液的稳定性都明显优于不含PAC的PSU二元乳液. 对于三元复合乳液及其胶膜的性能表征结果显示, 与非偶联型PSU-AC三元乳液相比, 偶联型PSU-X-AC乳液的乳胶粒尺寸较小, 粒径分布更均一|偶联型三元乳液的表面张力较小|其胶膜的力学强度远优于非偶联型|除非在PMTS分子量较高的情况下, 偶联型乳胶膜中未观察到非偶联型所见的相分离, 偶联剂GM的使用对提高材料的憎水及力学性能有明显作用. PMTS分子量及其用量对乳液的乳胶粒径、表面张力和粘度影响不明显. 但对于复合胶膜的性能来说, 三元复合乳液聚合物中PMTS分子量及其用量存在上限, 分子量上限值约为2000, 其用量上限约为PSU二元聚合物的10%, 在此之下PMTS的使用可以明显提高胶膜的力学及耐水性能.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.