聚（丙烯酸丁酯／丙烯酸）的合成及其作为高分子乳化剂的应用

合成了丙烯酸丁酯和丙烯酸的共聚物P(BA/AA),并对其进行了表征,讨论了pH值、BA/AA的比例和引发剂用量对其性能的影响.将P(BA/AA)共聚物作为高分子乳化剂,进行了丙烯酸丁酯和甲基丙烯酸甲酯的乳液共聚合P(BA/MMA),并与分别使用SLS/Tx-10和P(BA/AA)Tx-10作为乳化剂合成的P(BA/MMA)共聚物乳液的涂膜吸水率进行了比较.实验结果表明P(BA/MMA)水溶液的临界胶束浓度(CMC)为(2.8～3.0)×10-2g/mL,最低表面张力可达38～40mN/m,P(BA/MMA)乳液稳定性高,其乳液涂膜吸水率由使用普通乳化剂(SLS/Tx-10)的25%降至12%～18%.     

一种梳状表面活性剂的合成及应用

以β-蒎烯/马来酸酐共聚物为主链,接枝聚乙二醇单甲醚,合成一种梳状高分子表面活性剂,并对产物进行了表征。讨论了反应物相对分子质量、反应物配比及反应时间对表面张力的影响,采用相反转乳化技术将其应用于松香酯乳液。结果表明,产物具有良好的表面活性,采用相对分子质量为6 300的β-蒎烯/马来酸酐共聚物为主链,接枝聚乙二醇单甲醚-500,2种反应物按照酸酐与羟基的摩尔比为1∶1进行反应,反应时间为12~16 h时,反应产物降低水溶液表面张力的效果最好,产物制备松香酯乳液效果良好。     

一种新型两亲性聚合物的合成研究

合成了一种新型的两亲性共聚物(丙烯酰胺/醋酸乙烯酯/丙烯酸丁酯,AM/VAc/BA),探讨了在该共聚物合成过程中AM用量和VAc与BA的配比对其表面张力、离心稳定性、乳化性及发泡力的影响,并对该三元共聚物P(AM/VAc/BA)的结构进行表征。结果表明,傅立叶红外光谱(FT-IR)分析在1 680 cm-1~1 620 cm-1处无C=C伸缩振动吸收峰出现,说明体系反应较彻底;差示扫描量热(DSC)分析得共聚物的玻璃化转变温度为37.6℃。     

气溶胶固定剂PAM-b-PVTES的合成及表征

以S,S-二苄基三硫代碳酸酯(DBTTC)为链转移剂，丙烯酰胺(AM)为第一单体，乙烯基三乙氧基硅烷(VTES)为第二单体，通过RAFT聚合制备了两亲嵌段共聚物，其水溶液可作为一种气溶胶固定剂用于涉核环境下放射性气溶胶的去除。通过FTIR、1H NMR、DSC、GPC对聚合物分子结构与性能进行了表征。通过黏度表征结果表明：随着链转剂用量的减少，黏度增加。表面张力和接触角测试结果表明：随着VTES的引入，表面张力降低到40.44 mN/m；接触角降低到11.9°；通过气溶胶沉降固定实验表明：对PTI-A2粉尘的沉降固定效率为91.04%。预期在涉核环境下作为放射性气溶胶沉降固定剂可得到应用。     

甲基丙烯酸-丙烯酰胺亲水共聚物的性能研究

采用水溶液自由基聚合法制备了甲基丙烯酸-丙烯酰胺亲水共聚物,初步研究了甲基丙烯酸的反应动力学,研究了共聚物组成、pH、基材处理等对共聚物亲水性质的影响,并用红外光谱(FTIR)对其进行了结构表征。结果表明该亲水共聚物具有优秀的亲水性能,能满足空调铝箔热翅片等应用要求。     

油酸酰胺基二苯醚双磺酸钠的合成及表面活性测定

以对硝基二苯醚、油酸酰氯、氯磺酸为主要原料,通过硝基还原反应、胺基酰化反应、磺化反应,合成了双子表面活性剂油酸酰胺基二苯醚双磺酸钠;并用IR,1HNMR,MS对产品及中间体结构进行了表征。测定了其水溶液表面活性和临界胶束浓度(CMC),结果表明,其CMC(2 14mmol/L)低于传统的单疏水基单亲水基型表面活性剂十二烷基苯磺酸钠(SDBS),并具有较高的活性,其水溶液表面张力可降至34 0mN/m。     

羟乙基纤维素接枝共聚物对头发的调理性能研究

以羟乙基纤维素(HEC)、丙烯酰胺(AM)和二甲基二烯丙基氯化铵(DMDAAC)为原料,以过硫酸铵(APS)为引发剂,通过水溶液自由基聚合,合成了HEC-AM-DMDAAC三元共聚物,并用红外光谱对其结构进行了表征。实验表明,最佳反应条件为:反应温度为70℃,引发剂用量为12 mmol/L,HEC与AM质量比为1∶1,AM与DM-DAAC质量比为1∶3,反应时间为4 h。聚合物对头发的调理性能:对湿梳理提高了17%,对干梳理提高了23.6%。     

支链型醚类全氟表面活性剂的合成与表面活性

以聚乙二醇和全氟壬烯为原料制备了全氟壬烯基聚乙二醇单醚和双醚,并以红外光谱进行表征.结果表明:全氟壬烯基聚乙二醇单醚和双醚都能使水的表面张力明显降低;C9F17O(CH2CH2O)18H和C9F17O(CH2CH2O)22H的质量浓度为1.0 g/L时,其水溶液表面张力分别为24.1和26.4 mN/m;随着聚乙二醇聚合度的增加,其水溶液的表面张力变大;C9F17O(CH2CH2O)18H水溶液的临界胶束浓度为1.32 g/L.     

二元丙烯酸共聚物的水溶性规律及其性能研究

考察了二元丙烯酸共聚物的水溶性规律、发现其与小分子有机脂肪酸及其盐的水溶规律相似。共聚物可分为不水溶、水溶和临界水溶３类。共聚物水溶怀不同，其溶液的粘度、透光度、表面张力也不同。水溶性丙烯酸共聚物具有表面活性。临界水溶性丙烯酸共聚物的临界胶束浓度（ＣＭＣ）值为０．２％。     

磺酸聚醚表面活性剂的合成与表征

以不同比例的3-氯-2-羟基丙磺酸钠(NaCHPS)和1-氯-3-丁氧基-2-丙醇(CBP)为原料采用溶液共缩聚法,合成了新型磺酸聚醚表面活性剂———环氧丙磺酸缩水甘油丁基醚共聚物,用红外、核磁对其结构进行了表征,初步考察了聚合物的溶解性,发现磺酸聚醚能溶于大多数极性和非极性溶剂。用表面张力法测定了4种不同组成磺酸聚醚水溶液的临界胶束浓度(cmc)为450 mg/L~510 mg/L,最低表面张力γmin为31.2 mN/m~37.0 mN/m,且cmc和γmin均随分子中CBP含量的增加而减小。     

Contrasts in the surface activity of polyoxypropylene and polyoxybutylene-based block copolymer surfactants

Previous studies have shown that polyoxybutylene surfactant hydrophobes are less polar than polyoxypropylene hydrophobes. Polyoxyalkylene hydrophobes can be modified by ethoxylation to give terminal polyoxyethylene block hydrophilic groups. Polyoxybutylene/polyoxyethylene copolymer surfactants exhibit differentiated interfacial tensions, and wetting and foaming properties when compared to structurally equivalent polyoxypropylene/polyoxyethylene copolymers. There have been no reported comparisons, however, of polyoxybutylene/polyoxyethylene copolymers and polyoxypropylene/polyoxyethylene analogues in terms of fundamental parameters, such as critical micelle concentration, area per molecule at the interface, efficiency, and effectiveness. In one phase of this work, four polyoxybutylene/polyoxyethylene block copolymer surfactants were compared to structurally analogous polyoxypropylene/polyoxyethylene materials. Findings showed that polyoxybutylene/polyoxyethylene copolymers exhibited enhanced cotton wetting and lower surface and interfacial tensions compared to polyoxypropylene/polyoxyethylene analogues. Polyoxybutylene-based surfactants were typically one order of magnitude better in their ability to reduce surface tension at interface saturation. Polyoxybutylene/polyoxyethylene copolymers pack more efficiently at the interface, as evidenced by a smaller area per molecule at the interface. Critical micelle concentration values were also lower for polyoxybutylene/polyoxyethylene copolymers. A second phase of experiments focused on the surface activity of polyoxypropylene/polyoxyethylene triblock copolymers with higher molecular weight hydrophobes. Enhanced surface activity was found when compared to lower-molecular weight polyoxypropylene/polyoxyethylene copolymers.     

Solution and interfacial behavior of hydrophobically modified water-soluble block copolymers of acrylamide and N-phenethylacrylamide

Hydrophobically modified water-soluble block copolymers were prepared by aqueous micellar copolymerization of acrylamide and small amounts (2 and 3 mol %) of a hydrophobe (N-phenethylacrylamide) that is characterized by a long spacer that places the aromatic ring far away from the backbone, with the objective of investigating the copolymers' rheological behavior and surface and interfacial activities under various conditions such as polymer concentration, shear rate, temperature, and salinity. As expected, the block copolymers exhibit improved thickening properties attributed to intermolecular hydrophobic associations as the solution viscosity of the copolymers increases sharply with increasing polymer concentration. Additional evidence for intermolecular association is provided by the effect of NaCl, the presence of which substantially enhances the viscosity. An almost shear rate–independent viscosity (Newtonian plateau) is also exhibited at high shear rate and a typical non-Newtonian shear thinning behavior appears at low shear rates and high temperatures. Furthermore, the block copolymers exhibit high air–liquid surface and liquid–liquid interfacial activities as the surface and interfacial tensions decrease with increasing polymer concentration, indicating strong adsorption of the copolymer at the interface. The surface and interfacial tensions exhibited by the copolymers were found to be relatively insensitive to the concentration of salt (NaCl). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 467–476, 2001     

New fluorinated polysiloxanes containing an ester function in the spacer—II. Surface tension studies

The surface tensions of fluorinated polysiloxanes prepared by hydrosilylation of unsaturated perfluoroalkyl esters derived from undecylenic acid [CH₂?CH? (CH₂)₈? COO? CH₂? CH₂? R_F, with R_F = C₆F₁₃, C₈F₁₇, and C₈F₁₇? (CH₂)₁₀COO? CH₂? CH₂? CH?CH₂] by methylhydrodimethylsiloxane copolymers of various Si? H contents have been measured. The critical surface tensions, γ_c, and the solid surface tensions, γ^D_s, were deduced from n-alkane and water contact angle data. They decrease as the perfluoroalkyl graft content of the copolymers increases. Some of them, which are in the range of the lowest surface tension fluoro polymers known, are observed when the fluorinated segments are self-organized at the interface, i.e. when the polymers are mesomorphous or crystalline at room temperature.     

Oberflächenspannung von Poly(n-butylmethacrylat)-und Poly(n-butyl-ran-methylmethacrylat)-Schmelzen

Surface tensions and temperature coefficients of the surface tension for poly(n-butyl methacrylate) and two different poly(n-butyl-ran-methyl methacrylates) between 180° and 230°C were investigated. The presence of n-butyl methacrylate in the copolymer reduces the surface tension. The consequences of such behaviour for the use of methacrylic copolymers as processing agents are discussed.     

Solution behavior of two novel anionic polyacrylamide copolymers hydrophobically modified with n‐benzyl‐n‐octylacrylamide

Two novel hydrophobically modified anionic polyacrylamides (HM‐PAMs), p(AM/NaA/NaAMC₁₂S/BOAM) and p(AM/NaA/OP‐10‐AC/BOAM) have been prepared by an aqueous micellar copolymerization technique from acrylamide, sodium acrylate (NaA), sodium 2‐(acrylamido)dodecane‐1‐sulfonate (NaAMC₁₂S), octylphenol polyoxyethylene acrylate (OP‐10‐AC), and small amounts of N‐benzyl‐N‐octylacrylamide, respectively, with the objective of investigating the copolymers' rheological behaviors and surface activities under various conditions such as polymer concentration, shear rate, temperature, and salinity. As expected, the copolymers exhibit improved thickening properties due to intermolecular hydrophobic associations as the solution viscosity of the copolymers increases sharply with increasing polymer concentration. A decrease in viscosity is observed with increasing temperature, and the solution viscosity of the copolymers decreases with increasing NaCl concentration. Furthermore, the block copolymers exhibit high air–liquid surface activities as the surface tensions (STs) decrease with increasing polymer concentration. This behavior is yet another evidence of polymolecular micelles formation of the copolymers in aqueous solution, and thus the high tendency to adsorb at an interface. The ST exhibited by the copolymers was found to be relatively insensitive to the concentration of salt (NaCl). Scanning electron micrographs showed large aggregates in solutions, which is formed by the association from the hydrophobic groups of the polymers. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Morphology and properties of crystalline polyester-siloxane block copolymers

A new series of crystalline (AB)_n type multiblock copolymers based on crystalline poly(hexamethylene sebacate) (HMS) and amorphous poly(dimethylsiloxane) (DMS) has been prepared, and their solid state properties have been examined. The copolymers range from 0-69 wt percent DMS, and they crystallize in spherulitic textures when cast in films from solution or the melt. As the DMS concentration in the copolymers increases, the spherulite sizes decrease, but only a very small melting point depression is observed. Available evidence suggests extensive microphase separation in the bulk of the solid state. Surface characterization of the copolymers indicates that phase separation is also prevalent at the polymer-air interface. The block copolymers and polyblends have critical surface tensions of wetting very similar to DMS homopolymer.     

Siloxane modification of polyamides

Polyamide–polydimethylsiloxane block copolymers were made by the BuLi or LiOSi(CH₃)₂OSi(CH₃)₂OLi catalysed polymerisation of hexamethylcyclotrisiloxane terminated by and using this substituted siloxane to initiate the polymerisation of lauryllactam or caprolactam in toluene solvent in the presence of lithium aluminium hydride as the catalyst. One or 2% of the polycaprolactam-polydimethylsiloxane block copolymers were mixed with nylon 6 and discs moulded. The presence of silicone in the surface was demonstrated by determining the critical surface tensions of wetting using ethanol–water mixtures as the contact-angle test liquids. A polylauryllactam–polydimethylsiloxane block copolymer compatible with polyethylene was similarly studied. An important application for such composites is to provide a dry lubricated surface, therefore the kinetic coefficients of friction of steel against these copolymer-treated nylon 6 samples were determined demonstrating at best a reduction to one third that of the untreated control.     

Mathematical Relations Correlating the Washing Abilities of Pluronics with Some of their Physico-Chemical Properties

Based on data in the literature, the washing abilities of block copolymers of ethylene and propylene oxides were correlated with some of their physico-chemical properties. Quantitative relations correlating washing abilities against clay or coal dirts with surface and interfacial tensions, the cloud point and the melting temperature were obtained. These results show that good washing properties in the considered system were obtained from block copolymers with the following characteristics: surface tension for c = 0.1% below 40 dyne . cm¹; cloud point near 100°C; and melting point below 30°C. The paper shows the possibilities of using modern statistical methods to obtain the optimal solutions to different technical problems.     

Application of Macromonomers for Pressure Sensitive Adhesives I. Adhesive and Surface Properties

Adhesive and surface-chemical properties of poly(styrene macromer-butyl acrylate) copolymers, poly (styrene-butyl acrylate macromer) copolymers and poly (styrene-butyl acrylate) random copolymers were investigated. The results were as follows:

(1) The adhesive properties of the copolymers which were prepared by the macromer-technique were different from the random copolymers.

(2) It was found that there were differences in the surface and molecular structure between the copotymers which were prepared by the macromer technique and the random copolymers. These differences were evident from the results of measurements of the surface free energy of the copolymers and of the interfacial tension of water/toluene in the presence of the copolymers.

(3) The reason why there were differences in the surface and molecular structure seemed to be that the copolymers which were prepared by the macromer technique had graft chains and a different inner-structure from the random copolymers. Therefore, it was suggested that the graft copolymers which were prepared by the macromer technique had a phase-separated structure.     

Synthesis and solution properties of poly(acrylamide-styrene) block copolymers with high hydrophobic content

Hydrophobically associating block copolymers of polyacrylamide/styrene with a high hydrophobe content were synthesized using micellar copolymerization under various conditions of surfactant and initiator concentrations with the objective of determining the conditions that produce optimum solution properties for enhanced oil recovery. Solubilities, aqueous solution viscosities and interfacial properties with air and oil of the copolymers were investigated. The influence of salt on the solution properties was also studied. Nature of hydrophobic sites and onset of hydrophobic association were studied by measuring the fluorescence of pyrene in polymer solutions. Optimum solution properties were obtained for copolymers synthesized under conditions of high surfactant and initiator concentrations. The copolymers displayed substantial thickening properties at low concentrations with enhanced thickening in the presence of salt. The interfacial tensions of the aqueous solutions with n-decane and air were also reduced. Interfacial properties were slightly sensitive to salt concentration. The copolymer solutions showed shear and temperature thinning behaviors typical of polymer solutions.