互穿网络聚合物的某些进展

综述近年来热塑性互穿网络聚合物及以蓖麻油为原料合成的互穿网络聚合物的进展。     

互穿网络聚合物某些进展

综述近年来热塑性穿网络聚合物及以蓖麻油为原料合成的互穿网络聚合物的进展。     

紫外光同步固化合成互穿聚合物网络研究

A new series of Interpenetrating polymer networks (IPN) was prepared by using both free radical and cationic photoinitiators simultaneously under ultraviolet radiation. The systems studied were castor oil based ure'thane acrylates (Network I) and epoxy resin (Network II) (UV-IPN). In order to compare the effect of different crosslinking operations, urethane-acrylate/ amine cured epoxy resin (AC-IPN) and urethane-acrylate/epoxy-acrylate conetwork (EA-CPN) systems were also synthesized and their dynamic mechanical and stress-strain properties were examined. The results show that UV-IPN exhibits only one Tan δ peak,while two Tan δ peaks can be seen in AC-IPN systems. This suggests that the former is much more compatible than the later.The stress at break was found to increase as epoxy resincomponent increased in both UV-IPN and AC-IPN,while appeared to decrease in EA-CPN as epoxy-acrylate increased.     

紫外光同步固化合成互穿聚合物网络研究

互穿聚合物网络是研制高阻尼材料的理想结构,但从目前国内外文献报道的同步法互穿网络体系来看,由于在制备中采用了两种不同的聚合方法,实际上在形成网络结构的过程中都不是十分理想的同步反应,其反应速度均存在着一定程度的差别。     

含偶氮苯并噻唑发色团的二阶非线性光学互穿网络聚合物

合成了含偶氮苯并噻吩（ＢＴ）发色团的聚氨酯／环氧树脂互穿网络聚合物（ＩＰＮ）,其中聚氨酯网络由（丙烯酸β羟丙酯 ＢＴ ２甲基丙烯酸酯）共聚物与苯酚封闭的双端异氰酸酯的ＢＴ １反应形成,而环氧树脂网络由含环氧基的ＢＴ与含ＢＴ的苯二胺反应形成．同时实施这二种反应即形成ＩＰＮ．ＩＰＮ经红外光谱、凝胶含量测定及ＤＳＣ等表征．其薄膜经１６０℃、８５ｋＶ电晕极化,由可见光谱测量及一维刚性取向气体模型计算得到宏观二阶非线性光学极化系数χ（２）为２１８×１０－７ｅ．ｓ．ｕ．,在１２０℃经２４０ｈ序参数几乎不变．     

丁腈羟聚氨酯/聚环氧树脂互穿网络高聚物的研究

本文用同步法合成了丁腈羟聚氨酯/聚环氧树脂(PU/PE)体系的互穿网络高聚物(IPN),研究了各种因素对其形态和玻璃化转变行为的影响,并用扭辫及扭摆(TPA)在-100℃-+150℃温度区间内,测试全部试样的动态力学谱。结果表明,PU/PE是不相容体系,在电镜片上呈现细胞状结构(400-800Å)。由于两组份网络互穿,发生“强迫互容”,使T_g内移,通过调整组份比和加不同扩链剂等能提高阻尼值,加宽T_g转变区。     

POLYIMIDE/INORGANIC INTERPENETRATING POLYMER NETWORKS FOR STABLE SECOND-ORDER NONLINEAR OPTICS

Thermally stable NLO interpenetrating polymer networks (IPNs) based on an organosoluble polyimides functionalized with methacryloyl groups (PIB), and an alkoxysilane dye (ASD) have been developed. IPNs were formed through the free radical polymerization of methacryloyl group containing PIB, and sol-gel process of ASD. Optically clear samples exhibit large second-order optical nonlinearity (d₃₃ = 6.9-39.6 pm/V at 1064 nm) after poling and curing at 180°C for 2 hours. The temporal stability of the PIB/ASD IPN samples was much better than the inter-chain crosslinking polyimide/inorganic samples. The high rigidity of the polymer backbone and the interpenetrating structure of the polymer networks prevent the randomization of the aligned NLO chromophores     

PMPS/PMAc相容性与同步互贯聚合物网络的阻尼性能研究

互贯聚合物网络是一种聚合物合金 ,其组分的热力学性质决定组分间的相容性和微相结构 ,从而影响材料的阻尼性能 .采用同步互贯聚合物网络 (SIN)技术制备了一种新型的聚苯基硅氧烷 (PMPS) 聚甲基丙烯酸酯 (PMAc)阻尼材料 ,用DMA和AFM等表征研究了其玻璃化温度转变行为与微观相态结构 .结果表明 ,由相容性好的组分制备的SIN材料阻尼值最高 ,tanδmax 可达 1 4,只有一个玻璃化温度转变峰 ,其微相结构为双相连续 ;组分介于相容与不相容之间时 ,所构成的SIN样品的tanδ≥ 0 3的温度区间最宽 ,可达 170℃ ,微相结构为单相连续 ;由相容性差的组分制得的SIN阻尼材料的内耗峰裂分为两个区间 .PMPS PMAcSIN材料的阻尼性能可以通过调节组分的相容性进行控制 .     

SYNTHESIS AND PROPERTIES OF POLYURETHANE ACRYLATE/EPOXY RESIN INTERPENETRATING POLYMER NETWORKS

In this paper, a series of interpenetrating polymer networks (IPNs) based on polyurethane acrylate and epoxy resin was prepared by simultaneous photoinitiating by both free-radical and cationic polymerization. The effects of the polyurethane acrylate prepolymer's molecular weight, various components ratio and polymerization methods on IPN's dynamic mechanical and mechanical properties were investigated.     

环氧树脂/氨酯丙烯酸酯树脂互穿聚合物网络生成动力学研究

用ＦＴＩＲ跟踪研究了由不同分子量聚氧化丙烯（ＰＰＯ）合成的氨酯丙烯酸酯树脂（ＵＡＲ）／环氧树脂（ｅｐｏｘｙ）同步互穿网络（ＳＩＮ）的生成动力学．结果表明,在聚合反应初期（转化率＜０４）环氧基和不饱和双键的转化率均和反应时间呈近似线性关系,聚合反应主要由单体的扩散控制;由不同分子量ＵＡＲ合成的ｅｐｏｘｙ／ＵＡＲＳＩＮ的生成动力学有较大差异,与ＳＩＮ形成过程中的形态发展有关．通过不同用量的ＡＩＢＮ,可以调节ＵＡＲ网络的形成速度,导致ＳＩＮ中两个网络的生成顺序发生改变．     

聚苯乙烯/聚丙烯酸丁酯乳胶互穿聚合物网络的动态力学性能研究

<正> 互穿聚合物网络(IPN)是一种新型聚合物共混物.自Sperling在1969年合成聚丙烯酸乙酯/聚苯乙烯异步IPN(Sequential IPN)后,该领域进展很快.乳胶IPN(latex IPN)是用改进的乳液聚合法合成的一种微观互穿IPN.在前文中,我们报道了聚苯乙烯/聚丙烯酸丁酯(PS/PBA)乳胶IPN的合成,本文研究一些因素对PS/PBA乳胶IPN动态力学性能的影响.     

液体氯丁二烯-甲基丙烯酸羟乙酯共聚物基聚氨酯-聚苯乙烯互穿网络聚合物

合成了一系列液体氯丁二烯-甲基丙烯酸羟乙酯共聚物(CP-HEMA)聚氨酯-聚苯乙烯互穿网络聚合物(PU-ST-IPN)。表征了物理性能和密度行为。密度效应在体系中较为明显,其增值为0.030g/cm³,同时其抗张强度的提高也是显著的。通过60%PU透射电镜照片,观察了微相分离形态结构。分散于PU相中的ST微区尺寸大约为500-4000Å。与PU-MMA-IPN体系比较,该体系相界分明,相分离程度大。直到60%PU,没有相转变发生,ST相是分散相,PU相是连续相。形成PU相的相对反应速率比苯乙烯的聚合速度快是造成上述现象的主要原因。微区尺寸分布和密度效应证明,此IPN体系在分散相的界面上两个网络是互穿缠结的。     

INTERPENETRATING POLYMER NETWORKS BASED ON OIL MODIFIED CASTOR OIL URETHANE AND POLY(METHYL METHACRYLATE)

Castor oil was initially subjected to an interesterification reaction with linseed and tung oils and the resulting intermediate was used for the preparation of polyurethanes and their IPNs with poly(methyl methacrylate). They were characterized for their physico-mechanical, swelling, and thermal properties. The morphologies of IPNs were studied with the aid of scanning electron microscopy and differential scanning calorimetry. On comparing the mechanical properties of castor oil polyurethane (CU) and their IPNs (C-IPNs) with those of the castor oil modified with linseed and tung oil (L-IPN and T-IPN, respectively) it was found that L-IPNs showed higher tensile strength, hardness, and better compatibility than C-IPNs. All IPNs showed synergistic effect in elongation and exhibited similar thermal behavior with no significant change with respect to their composition. However, the castor oil polyurethane and their IPNs showed relatively higher elongation and better resistance to solvents.     

甲苯二异氰酸酯形成的聚氨酯脲与接枝乙烯基酯树脂互穿网络研究

本文首先通过分子设计技术合成了一系列侧链长度可以控制的接枝乙烯基酯树脂 (接枝VER :BO g VER ,2 0 0 g VER ,390 g VER) ,并用它们与甲苯二异氰酸酯合成的聚氨酯脲 (PUU)形成同步互穿网络(SIN) .通过DSC、SEM等考察了接枝VER的结构对PUU/接枝VERSIN的形态与力学性能的影响 .在PUU/BO g VERSIN中 ,BO g VER网络主要与PUU网络中的硬段相容和互穿 ;对于PUU/ 2 0 0 g VERSIN而言 ,2 0 0 g VER网络与PUU网络中的软段和硬段均有一定的相容性 .由于这两种SIN中两个网络间均有一定的相容性和互穿 ,故这类接枝网络能显著地增强PUU网络 ,使材料的力学性能有较大幅度的提高 .390 g VER网络本身存在的微相分离结构 ,使PUU/ 390 g VERSIN两个网络也存在显著的相分离形态 ,导致390 g VER网络对PUU网络的增强效果并不明显 .     

预聚法丁腈羟聚氨酯/聚丙烯酸甲酯互穿网络聚合物的研究

采用同步法合成了预聚法丁腈羟聚氨酯/聚丙烯酸甲酯类互穿网络聚合物,研究了不同NCO基含量,不同组份比对聚合物抗张强度、剪切强度的影响,还以热失重方法对该体系的耐热性作了探讨。结果指出,聚合物的机械性能和耐热性皆比单一组成聚合物高,而且在组份比(PU/PMA)=8/2时机械性能有最大值,其协同效应显著。     

SPECTRAL CHARACTERISTICS OF FREE AND LINKED PYRENE-TYPE CHROMOPHORES IN SOLUTION,POLYMER MATRICES,AND INTERPENETRATING NETWORKS

Monomers, 1-pyrenylmethyl methacrylate (PyMMA), 1-pyrenylbutyl methacrylate (PyBMA), 4-(1-pyrenyl)methoxymethyl styrene (PyMMS) and allyl-(1-pyrenylmehtyl) ether (PyMAE), with pyrene as chromophore, were prepared. Their spectral properties (absorption, emission and emission decay) in solution, and doped or bonded in polymer matrices and complex polymer systems as interpenetrating polymer networks (IPN), were investigated. Spectral properties of pyrene-containing monomers doped in polystyrene (PS), polymethylmethacrylate (PMMA), polyvinylchloride (PVC), polyethylene (PE) and grafted on PE as well as copolymerized in buthylmethacrylate-co-styrene copolymer (BMA-co-S) have been compared. Absorption and emission spectra of pyrene type probes in solution and in IPN matrices exhibit typical absorption of the pyrene moiety. For IPN with grafted probes on PE, the absorption is slightly shifted to red wavelength. For monomers, PyMMA, PyBMA and PyMAE grafted to PE, the shape of the emission spectrum depends on the wavelength of excitation. The ratio of intensity of the vibrational band, I₁/I₃, (I₁ peak at 377 nm and I₃ peak at 388 nm) has been a quite useful indicator of polarity of IPN. The relative quantum yields of fluorescence in IPN matrices are lower in comparison to polymer matrices of PE, PS, PMMA for all probes under study. The fluorescence life-times for bound and free probes have been in the range 100–200 ns, which is substiantialy shorter than for the parent pyrene chromophore under the same or similar condition. Grafted probes on PE alone, or as a part of IPN, exhibit substantially shorter life-time around 10 ns and decay is rather complex.