A novel method for determination of polyester end-groups by NMR spectroscopy

An efficient, convenient and quantitative method for characterising polyester end-groups is described. We have found that trichloroacetyl isocyanate (TAI) reacts rapidly and quantitatively with both carboxyl [C(O)OH] and hydroxyl (OH) chain ends to form derivatives that can be readily determined by ¹H NMR spectroscopy. The TAI capped end-groups give rise to characteristic imidic NH resonances in a normally clear region of the ¹H NMR spectrum [δ∼10-11.5 for C(O)-O-C(O)-NH-C(O)CCl₃ from C(O)OH, δ∼8-9 for O-C(O)-NH-C(O)CCl₃ from OH]. The method has been successfully applied to quantitative determination of the end-groups of a wide variety of oligomeric polyesters. It has also been applied to higher molecular weight polyesters including commercial, bottle grade, poly(ethylene terephthalate) (PET) and PET based copolyesters (e.g. PETG).     

Synthesis and characterisation of N-toluyl methacrylatoethyl carbamates,homopolymers and copolymers with methyl methacrylate

The paper describes the synthesis of N-2/4-toluyl methacrylatoethyl carbamates using 2/4-toluyl isocyanate and 2-hydroxyethyl methacrylate. Homopolymerisation and copolymerisation of these novel monomers with methyl methacrylate was carried out using benzoyl peroxide as an initiator and tetrahydrofuran as solvent. Photopolymerisation of N-4-toluyl methacrylatoethyl carbamate could be carried out without the use of photosensitiser. Structural characterisation of copolymers was done using ¹H-NMR. Thermal stability of copolymers was evaluated in a nitrogen atmosphere by dynamic thermogravimetry.     

BPO和AIBN作引发剂对阳离子交换膜性能的影响

改进传统制备聚偏氟乙烯(PVDF)均相阳离子交换膜的方法,利用引发剂和浓硫酸磺化直接制备PVDF均相阳离子交换膜。通过溶剂蒸发法制备了含引发剂过氧化苯甲酰(BPO)和/或偶氮二异丁腈(AIBN)的PVDF阳离子交换膜,研究不同引发剂及其含量对膜结构和膜性能的影响。利用FE-SEM和FTIR分析了膜的形貌结构。结果表明:含有BPO的阳离子交换膜中PVDF与苯乙烯形成了半互穿网络结构,而含有AIBN的阳离子交换膜中苯乙烯接枝在线性PVDF链上并形成相分离结构。PVDF阳离子交换膜的结构和性能受膜制备时AIBN和BPO的添加量影响。当AIBN占PVDF5%(质量分数)、BPO占PVDF2%(质量分数)时,离子交换膜的膜电阻达最低值4.2Ω×cm~2,离子交换容量最高为1.59 meq/g;当AIBN占PVDF 3%(质量分数)、BPO占PVDF2%(质量分数)时,离子交换膜的迁移数为95.15%。最后通过循环伏安法和计时电位法进一步验证了引发剂对膜电阻和迁移数影响的实验结论。     

水性丙烯酸树脂的合成研究

以甲基丙烯酸甲酯、丙烯酸丁酯为主要单体,以过氧化苯甲酰为引发剂,通过引入亲水性基团羧基和羟基,制备了水性丙烯酸树脂。确定了最佳反应条件,讨论了水性基团的用量对树脂性能的影响,并用红外光谱(FT-IR)和差示扫描量热分析(DSC)对所合成树脂的结构进行了分析和表征。     

国内外异氰酸酯生产状况及展望

介绍近年来国内外主要异氰酸酯生产厂商生产能力的现状及发展前景，并提出了对我国异氰酸酯工业的建议。     

Environmental etch performance, and scratch and mar of automotive clearcoats

Environmental etch damage to automotive coatings, and scratch and mar of these coatings are an important element of customer satisfaction as well as a significant warranty repair consideration for automotive companies. The conditions that result in environmental etch are examined and a laboratory test proposed. Data from this test are compared to automotive hoods exposed in Florida. The performance of various crosslinking chemistries is discussed and the requirements for improved environmental etch are outlined. Scratch and mar performance of these systems is also reviewed. We have found that coatings respond to physical stress by elastic recovery, by plastic flow and by brittle fracture. Classifying types of damage in this way is important for understanding the chemistry needed for improved scratch and mar of coatings.     

封闭型异氰酸酯固化剂的制备及应用

以甲苯二异氰酸酯、三羟甲基丙烷为原料合成预聚物,分别与甲乙酮肟和多种醇醚类混合物进行封端反应,合成溶剂性和水性封闭异氰酸酯固化剂。采用红外光谱和化学滴定等方法对预聚物和固化剂进行表征和分析。合成的固化剂与树脂按比例混合,制备涂膜,并对漆膜的性能作了初步探讨。     

采用DSC和FTIR对木材和API胶粘剂间反应的研究

采用差示扫描星热法(Differential Scanning Calormelry,简称DSC)和傅立叶变换红外吸收光谱(Fourier Transform Infrared Spectroscopy,简称FTIR)对木材和水性高分子异氰酸酯胶粘剂(Aqueous Polymer Isocyanate,简称API)的胶接机理进行了研究。DSC和FTIR的试验结果均表明:API胶粘剂和木材间发生了化学反应:API胶粘剂和木材间发生的反应所需活化能远小于API胶粘剂的主剂+固化剂的活化能,亦即用API 胶粘剂胶接木材时发生的反应要比API胶粘剂本身的固化反应容易得多,同时从理论上证明使用API胶粘剂胶接木材时装配时间最长不应超过其活性期的一半时间,且装配时间越短越好;文中还研究了升温速率对API胶粘剂DSC图谱的影响。     

Effects of apitong (Dipterocarpus spp.) extractives on bond strength development and curing rate of adhesives

Emulsion polymer isocyanate ( ), polyvinyl acetate ( ) and resorcinol-formaldehyde ( ) adhesives were used to produce single lap shear specimens using resinous and non-resinous apitong (Dipterocarpus spp.) timbers. Tests showed that joints made with highly resinous apitong were about 40% weaker than similar joints made with non-resinous apitong. The resinous apitong was treated with different solvents to yield five different extractives which were characterized by infra-red analysis. Apitong extractives were then added to and adhesives and joints made with buna (Fagus crenata), a timber known to be low in extractives and easy to bond. Joints prepared using extractive-containing adhesives were generally weaker than those made with the unmodified adhesives. RF adhesives containing extractives cured more slowly than unmodified . It is thought that the acidic nature of the extractives changes the pH of the system sufficiently to affect the curing mechanism     

Studies on urethane–allophanate networks based on hydroxyl‐terminated polybutadiene: Modeling of network parameters and correlation to mechanical properties

Hydroxyl‐terminated polybutadiene (HTPB)‐based allophanate–urethane networks were prepared by reacting HTPB with di‐isocyanates, such as toluene–di‐isocyanate (TDI), isophorone–di‐isocyanate (IPDI), and 4,4′‐di(socyanatocyclohexyl)methane (H₁₂MDI) at stoichiometric ratios (r‐values) ranging from 1.0 to 1.5. The networks were characterized for mechanical and swell properties. The network parameters, such as “X,” which is the fraction of urethane groups involved in the allophanate formation, and effective chain length (L_x) were calculated from experimental crosslink density values determined from swell data, using α‐model equations developed by Marsh. Excellent linear correlations were obtained between mechanical properties and the calculated network parameters. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2986–2994, 2006