有机硅聚氨酯丙烯酸酯预聚物的合成

以异佛尔酮二异氰酸酯（IPDI）、烷羟基硅油（SD9134）和丙烯酸β-羟乙酯（HEA）为原料,合成了一种UV固化有机硅聚氨酯丙烯酸酯预聚物（PSUA）。探讨了原料、催化剂用量、反应温度等因素对反应的影响。确定最佳反应条件为：以烷羟基硅油SD9134和IPDI为主要原料,DBTDL为催化剂,其加入量为0．05％～0．1％,反应前3步在20～40℃下反应,第4步反应温度不超过70℃,并通过IR和GPC表征了PSUA的结构。     

光敏有机硅聚氨酯丙烯酸酯预聚体性能的研究

考查了光引发剂、活性单体对光敏有机硅聚氨酯丙烯酸酯预聚体（PSUA）胶膜的耐水性、拉伸强度、伸长率、硬度、柔韧性和热稳定性的影响。结果表明，胶膜具有优良的耐水性，吸水性低于4％。含单官能度单体的PSUA胶膜的接触角大于含多官能度单体的，含有IBOA的体系接触角达103．6°；当选择引发效率高的裂解型光引发剂，用量为0.5％～1％时，胶膜具有较高的接触角。含多官能度单体胶膜的拉伸强度高于含单官能度单体的体系，但伸长率较小。含TMPTA体系的胶膜的硬度最大，为0．575。胶膜具有较好的柔韧性和热稳定性，其柔韧性达到1mm级，在300℃时失重为4.61％。     

聚氨酯丙烯酸酯/环氧丙烯酸酯分散体系的制备

用水性聚氨酯丙烯酸酯改性环氧丙烯酸酯,制备了聚氨酯丙烯酸酯/环氧丙烯酸酯分散体系。随着分散体中聚氨酯丙烯酸酯浓度的增加,体系稳定性增加,当其浓度达到30%时,可制得稳定的分散体系。这种分散体系可作为一种紫外光固化水性涂料,其涂膜的耐磨性、柔韧性都比环氧丙烯酸酯涂膜增强,而硬度变化不大。     

Morphology and mechanical properties of urethane acrylate resin networks

A series of urethane acrylate resins (UARs) having various amounts of hard segment were synthesized from poly(oxypropylene) diols (PPOs) with different molecular weights and characterized. The relationship between the morphologies and mechanical properties of these UAR (UARX‐Y‐Z, in which X means the molecular weight of PPO, Y means the content of hard segment, and Z means the content of comonomer) networks was investigated in detail. It was found that the morphology of the UARX‐Y‐Z network was related to the contents of hard segment and the comonomer (methyl methyacrylate—MMA) as well as the molecular weight of PPOs. The UAR1000‐0‐34 network synthesized from PPO210(M_n = 1000) is a homogeneous system due to the good compatibility between the PPO210 and the MMA segment. TheUAR1000‐0‐60 network exhibits the morphology of partial microphase separation resulting from increasing the length of the MMA segment, so as to decrease the miscibility between the soft and hard segment. For the UAR1000‐30‐34 network having a higher content of the hard segment, the hard segments tend to form domains with the limited short‐range and long‐range order, leading to the formation of the microcrystallites, and therefore it shows higher tensile strength and elastic modulus. For UAR400‐0‐34 network with lower molecular weight PPO204 (M_n=400), a high glass transition temperature and some microcrystallites were observed. Such a network exhibits the best mechanical properties over all UAR networks studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1532–1537, 2000     

Synthesis and characterization of urethane/acrylate composite latex

Polyurethane dispersion and urethane/acrylate composite latex were synthesized and characterized by using a particle size analyzer, gel permeation chromatograph (GPC), Fourier transform infrared spectroscopy coupled with attenuated total reflectance (FTIR‐ATR), dynamic mechanical analysis (DMA), and instron test machine. The amount of solvent and dimethylolpropionic acid (DMPA) used during synthesis of polyurethane resin straightway affected the average particle size and stability of aqueous polyurethane dispersion. The particle size of polyurethane dispersion had nothing to do with that of composite latex. FTIR‐ATR analyses displayed both air‐facing and substrate‐facing surfaces, containing more polyurethane component than the average composition. Some crosslinking reactions occurred in preparing urethane/acrylic composite latex, as indicated by FTIR analyses and solvent extraction. DMA demonstrated three glass transitions for the film from composite latex. Instron tests exhibited better film performance properties for the composite latex than for the corresponding blend latex. A possible particle growth mechanism for preparing urethane/acrylate composite latex was proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1620–1628, 2002; DOI 10.1002/app.10526     

Synthesis of new pH-sensitive polyurethane gels using polyethylene glycol modified urethane acrylate and urethane acrylate anionomer

New type of amphiphilic pH-sensitive polyurethane networks, derived from the mixture of polyethylene glycol-modified urethane acrylates (PMUA) and urethane acrylate anionomer (UAA), were prepared and their swelling behaviors were evaluated. Three kinds of polymerization methods were employed in the synthesis of polyurethane networks. Polyurethane networks prepared by a process similar to that of soap-free emulsion polymerization (UAHG) showed the highest swelling ratio and pH-sensitivity. Additionally, four kinds of UAHG gels were prepared at different composition of UAA. As the composition ratio of UAA to PMUA increased, swelling of UAHG gels in alkali pH buffer solution and their pH-sensitivity greatly increased. Additionally, swelling of UAHG gels changed reversibly with the change of pH. Received: 18 November 1996/Revised: 10 January 1997/Accepted: 14 January 1997     

遇水膨胀聚氨酯弹性体的合成及性能

以亲水性聚醚多元醇、甲苯二异氰酸酯(TDI)、三羟甲基丙烷(TMP)、三异丙醇胺(TIPA)和3,3′-二氯-4,4′-二氨基-二苯基甲烷(MOCA)等为主要原料,采用预聚物法合成了双组分浇注型遇水膨胀聚氨酯弹性体。研究了多元醇种类及配比、扩链剂种类及配比、增塑剂、异氰酸酯含量等对遇水膨胀聚氨酯弹性体性能的影响。结果表明,采用TDI/MOCA/TMP体系制备的遇水膨胀弹性体具良好的综合性能。     

丙烯酸酯低聚物的制备及其改性PUA乳液

以丙烯酸丁酯(BA)、乙酸乙烯酯(VAc)、丙烯酸羟乙酯(HEA)、丙烯酸(AA)等为主要原料合成了丙烯酸酯低聚物,以该低聚物为改性剂,制备了丙烯酸酯改性水性聚氨酯乳液(PUA)。考察了低聚物中单体组成、引发剂种类及用量、合成PUA时低聚物加入方式对PUA性能的影响。通过傅里叶变换红外光谱、偏光显微镜照片和热重曲线研究了乳液微观结构和耐热性能,通过气相色谱测定了单体残留量。结果表明:当低聚物中单体组成为BA,VAc,HEA,AA,所用引发剂为偶氮二异丁腈(用量为单体总质量的1.17%),将低聚物与异氰酸酯基单体同时加入反应时,可得到综合性能好、单体残留量极低的水性PUA,其初黏性可达13号球,持黏性为45 min,且乳液稳定。     

聚酯丙烯酸酯预聚物的合成研究

采用分步加料法,以己二酸、1,4-丁二醇、季戊四醇、二羟甲基丙酸(DMPA)和丙烯酸为原料合成了光固化聚酯丙烯酸酯预聚体;采用FT-IR和DSC对产物进行了表征和分析;探讨了羟羧比(物质的量比,下同)、DMPA等对合成树脂附着力和粘度的影响。结果表明:羟羧比在1.2左右时树脂的附着力最好;催化剂质量分数为0.1%,阻聚剂质量分数为0.02%时,聚酯丙烯酸酯预聚体性能最佳。     

氨酯丙烯酸酯树脂与氯化聚乙烯的共混

将聚酯二元醇与二苯甲院二异氰酸酯反应[n(NCO):n(OH)=2:1] 的预聚物用甲基丙烯酸-β-羟乙酯封端，得到氨酯丙烯酸酯树脂，将其与CPE共混，并对影响氨酯丙烯酸酯/氯化聚乙烯共混硫化胶的力学性能、热老化性能以及耐油性的一些因素进行了讨论。     

Elasticity of urethane networks

Various polymer networks have been prepared based on poly(propylene oxide) which has been linked either by urethane groups or ester groups. These networks have been examined by stress-strain measurements to find the degree of deviation from ideal rubber elasticity (as specified by the statistical theory) and by neutron scattering to find the mobility of the poly(propylene oxide) chain. The stress-strain results showed the urethane-linked networks to be identical to the ester-linked networks as long as there were no short chain polyols in the formulation. Networks containing short chain polyols have a greater deviation from ideal rubber elasticity. The neutron scattering results showed the ester-linked poly(propylene oxide) to have the same mobility as an uncrosslinked poly(propylene oxide), whereas urethane-linked networks have a lower mobility, similar to an analogous urethane-linked polymer. A small effect of crosslinking was observed. The results are explained in terms of some phase separation occurring in the polyurethanes only when short chain polyols are present. In the simple urethane-linked networks the poly(propylene oxide) chain mobility is reduced by hydrogen bonding to the urethane groups, but this has no effect on the equilibrium stress-strain properties.     

Creep/recovery behavior of open-cell foams

Static measurements have been used to predict the dynamic response of ldquo;unboundedrdquo; open-cell noninked (dry) and inked foam materials. Creep, e_c(t), and recovery, e_r(t), were determined in compression from static and dynamic modes. Force measurements, f(t), and strain decay, e(t), were used to determine the change in creep, δe_c(t). The change in creep represents the plastic strain, e_p1(t=t_h), and is uniquely defined by the recovery function, e_r(t=t_h), where t_h is the hold time. Creep and recovery results of various classes of foam materials and nonfoam materials were found to fit a master curve of the form F_r(t) =exp[–k′_r(t_h)t] = [e_r(t) - e₀₀( t_h)]/[e₀ (t = 0) - e₀₀(t_h)] at a reduced time of k′_r(t_h) t [k′_r(t_h)] C₀/(t_h)^a (where Co depends on the material's “dry” or “wet” state), a is a function of the type of material, and em is the permanent set]. These empirical results are applicable to printing ink transfer and print quality. Other important factors of concern are diffusion processes within the polymer matrix and the nature of the polymer (e. g., chemical constitution, porosity, molecular weight, and solubility). © 1995 John Wiley & Sons, Inc.     

Creep,creep recovery and dynamic mechanical measurements of a poly(propylene glycol) oligomer

Measurements have been made of the viscoelastic properties of a low molecular mass poly(propylene glycol), P4000, in shear creep and creep recovery. Taken together with previous dynamic mechanical measurements in alternating shear at frequencies of 30 MHz and 454 MHz and additional dynamic measurements at 40 kHz, it is shown that the observed behaviour can be ascribed to two processes. The major contribution can be associated with the normal modes of the polymer molecule as a whole but a significant contribution is attributed to motions of smaller backbone units, akin to the behaviour of supercooled non-polymeric liquids. The latter are described by a complex compliance which must first be inverted to the modulus form before addition to the summation of Rouse modes in order to calculate the effective overall modulus. Retardation times associated with motions of the backbone units overlap the relaxation times of the higher order Rouse modes which are apparently rendered inactive, the polymer mode contribution being accounted for by either the first or, at most, the first two Rouse modes. The equilibrium compliance, J⁰_e, decreases markedly with decreasing temperature within 15K above the glass transition temperature. At higher temperatures (>T_g + 15 K) J⁰_e decreases gradually with increasing temperature in agreement with calculations based upon the combined polymer mode and backbone processes. Particular care was necessary in order to obtain thoroughly dry samples of P4000: the presence of relatively small amounts of water increased the value of J⁰_e by up to four orders of magnitude.     

Preparation and properties of urethane/acrylate composite by emulsion polymerization technique

Aqueous polyurethane–acrylic hybrid emulsions were prepared by semibatch emulsion polymerization of a mixture of acrylic monomers (styrene, butyl acrylate and acrylic acid) in the presence of polyurethane dispersion. Equivalent physical blends were prepared by mixing acrylic emulsion and polyurethane dispersion. The weight ratio between acrylic and polyurethane components was varied to obtain enhanced performance properties and microphase structure of hybrid latexes. The synthesized emulsion hybrids and physical blends were characterized by fourier transform infrared spectroscopy, thermogravimetric analysis. The experimental results indicate better acrylic–polyurethane compatibility in hybrid emulsions than in physical blends, resulting in improved chemical and mechanical properties. The blend ratio 50:50% (w/w) exhibited synergistic effects between the two polymers and revealed remarkable improvement in various coating properties over other blend ratios and the individual resin components.     

Polyurethane acrylate/epoxy–amine acrylate hybrid polymer networks

New classes of hybrid polymer networks (HPNs), having variable polyurethane acrylate (PUA) and epoxy–amine acrylate (EAA) compositions, were prepared using initially miscible systems in methyl methacrylate (MMA). The initial systems were based on PUA prepolymer and EAA monomer solutions in MMA. HPNs were a result of epoxy–amine and radical polymerization competition. Phase separation occurred during the course of HPN formation. Mechanical dynamic analysis of the prepared HPNs showed good affinity between the PUA and PMMA phases and lower affinity between the EAA and PMMA phases. Mechanical property evolution and transmission electronic microscopy showed that, for all the composition ranges used in this study (PUA/EAA/PMMA 15/45/40–45/15/40 wt %), the PUA‐rich phase was the continuous phase. EAA‐rich phases, 20–50 nm, in the PUA‐rich matrix were obtained for HPNs containing up to 30 wt % EAA. For higher EAA concentration (45 wt %), 2 μm EAA‐rich phases were obtained in the PUA‐rich matrix. A substructure was also observed in each phase. PUA/EAA copolymers were prepared and used successfully for the compatibilization of the different phases of the HPNs. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2711–2717, 2000     

聚氨酯预聚体增韧酚醛泡沫保温板的性能

研究了聚氨酯改性剂改性酚醛泡沫,测试了改性酚醛泡沫的性能,采用热重、红外光谱、扫描电子显微镜分析改性酚醛泡沫的微观结构,最终得到一种保温效果好、力学性能优异的新型酚醛泡沫。改性后酚醛泡沫具有如下特点:保温效果好,导热系数为0.030 W/(m·K);硬度大,表观密度可达40~60 kg/m3;韧性好,弯曲强度达2.1MPa,压缩强度提高16.5%,可达0.134 MPa。     

Preparation and properties of UV-curable polydimethylsiloxane urethane acrylate

A new type of a UV-curable polyurethane acrylate resin based on hydroxyterminated polydimethylsiloxane (PDMS) soft segments with molecular weight 1800 and 2,4-toluene diisocyanate (TDI)/2-hydroxyethyl methacrylate (HEMA) hard segments were synthesized. The reactivity of 2,4-TDI with the hydroxy groups of silanol and HEMA was discussed by means of IR measurements. The characteristic absorption peaks of the —NCO groups of 2,4-TDI in the para- and ortho-position should decline with increasing the reaction time. The measurements of fundamental physical properties of this type of UV-curable materials had been widely studied in addition to the effects of using various reactive diluents and some pigments. This kind of resin with good optical, electrical insulating, and adhesive properties on various matrices, could be improved in chemical properties and reduced in viscosity while promoting the coating processability by mixing with various reactive diluents. The excellent adhesive properties on glass plates can be attributed to the similar structure between the PDMS soft segments and glass which makes the application in the coating industry possible.     

UV固化低聚物及其涂料研究进展

综述了UV固化低聚物(主要是环氧丙烯酸酯和聚氨酯丙烯酸酯)的研究进展。环氧丙烯酸酯研究进展包括:降低黏度、改善柔韧性、光敏活性、耐热性、耐磨性和阻燃性能;聚氨酯丙烯酸酯的研究进展包括:紫外光固化的聚氨酯丙烯酸酯预聚物合成方法;聚氨酯丙烯酸酯/无机纳米复合材料;光固化无机/有机杂化材料;水性UV固化聚氨酯丙烯酸酯和UV固化超支化聚氨酯丙烯酸酯。较为详细地论述了氧阻聚的3种作用机理及解决方法(物理和化学2种方法),最后对光固化技术的5大发展趋势进行了展望。     

非离子型聚氨酯预聚体可聚合乳化剂的合成及性能

采用甲苯二异氰酸酯 (TDI) ,聚乙二醇 10 0 0 (PEG -10 0 0 ) ,丙烯酸为原料 ,通过分子设计合成了带有双键的非离子型可聚合乳化剂。并对其CMC值、流变行为及乳化力进行了表征。结果显示 :此乳化剂的CMC值在 6.0 %左右、浊点为 (54± 1)℃、HLB值为 16.1可以取代OP -10的乳化能力 ;该乳化剂可以与丙烯酸酯类单体进行乳液共聚 ,得到性能优异的共聚乳液     

Interfacial spectroscopic studies of UV cured urethane acrylate coatings

Interfacial structural changes of UV cured urethane acrylate coating films were investigated using ATR FTIR spectroscopy. These studies show that at the film–air (F–A) interface, when photo-initiator levels do not exceed 0.1% w/w, the band area ratio of H-bonding to non-H-bonding carbonyl stretching vibrations is proportional to UV energy density. However, when the initiator level is increased to 5% w/w, an increase of up to 200 mJ/cm² UV power is required in order to achieve a similar band ratio, and at higher photo-initiator levels, the amount of energy levels off. Analysis of the H-bonded to non-H-bonded band ratio near the film–substrate (F–S) interface shows that the band area ratio increases further away from the interface. At shallower depths, around 0.84 μm from the F–S interface, the magnitude of the H-bonding/non-H-bonding is smaller than that observed for the same penetration depths before UV exposure for lower photo-initiator concentration or lower energy UV exposure.