含氟聚酰亚胺的设计、合成及应用性能研究进展

聚酰亚胺作为结构独特的一类功能性高分子材料,应用广泛.随着人们对材料综合性能要求的提高,含氟聚酰亚胺颇受业界关注.聚酰亚胺结构中引入氟原子既能提高材料溶解性和透光率,还能降低其吸湿率和介电常数.综述了近年来含氟聚酰亚胺在设计、合成和应用性能方面的研究进展,指出其结构设计带来的性能优势.特别是对含氟聚酰亚胺的溶解性、光学...     

含氟聚酰亚胺的研究进展

含氟聚酰亚胺是一类重要的高性能聚合物材料,因其突出的物理化学性质、光学和电学性能以及气体选择透过性等被广泛应用于电子工业、光波通讯、航空航天以及气体分离材料等领域。文章着重介绍了含氟聚酰亚胺的研究进展,同时简述含氟聚酰亚胺结构性能及应用。     

含氟聚酰亚胺的研究及其在涂料中的应用

介绍了含氟聚酰亚胺的分类和研究动向,重点介绍了含三氟甲基及六氟丙基的聚酰亚胺的特点和性能。阐述了含氟聚酰亚胺在绝缘涂料中的应用,并对含氟聚酰亚胺在光电材料、复合材料和气体分离膜等领域中的应用进行了概述。     

含氟聚酰亚胺气体分离膜研究进展

介绍了一种新型气体分离膜材料-含氟聚酰亚胺,着重介绍了含氟聚酰亚胺的物理化学性质、气体选择透过性。对其发展历史及应用作了简要概述。通过与传统聚酰亚胺膜材料进行比较,指出了该膜材料的广阔发展前景,并对其今后发展方向进行了展望。     

水溶性含氟丙烯酸酯乳液的合成研究进展

含氟丙烯酸酯类聚合物因具有突出的成膜性能及耐老化性能而成为优良的成膜材料。其中,水溶性含氟丙烯酸酯乳液的合成研究,具有广泛的单体种类,聚合方式简单多样,在涂料领域受到了广泛的应用和关注。选择合适的乳液共聚单体及聚合工艺,不仅能够根据实际需要调节含氟聚合物的分子结构,而且可以获得最佳含氟量,以满足特殊性能需要的含氟丙烯酸酯乳液。综述了水溶性含氟丙烯酸酯乳液的聚合方法、常用含氟单体和非氟单体以及改性研究进展。     

含氟丙烯酸酯类单体合成技术进展

含氟丙烯酸酯聚合物具有许多特殊优异性能,成为新型含氟材料领域研究热点。在许多要求特殊性能领域获得广泛应用,如特殊涂料、纸张和皮革涂饰剂、织物整理剂等。阐述了含氟丙烯酸酯类单体合成技术进展,并对其研究开发提出一些建议。     

含氟材料在金属防腐和表面防护方面的应用进展

含氟材料具有独特的物理化学性能,如耐热性、拒水疏油性和耐腐蚀性,目前已大量应用到电子信息、化工及各类工程建筑等领域。本文简要介绍了含氟聚合物和含氟表面活性剂在金属防腐和表面防护方面的应用,并对比了几种材料在该应用领域的优缺点,提出了一些改进方法和措施,对提高含氟材料在金属表面防腐与防护性能有重要意义。     

含氟光固化单体的研究进展

紫外光固化技术在光固化涂料、粘合剂、和油墨印刷等领域应用广泛。含氟聚合物表面能低,疏水疏油,具有优良的耐候性,耐化学品性和抗污染性,这些优异性能吸引人们研究其在光固化领域的应用。本文综述了含氟光固化单体的种类,具体包括丙烯酸酯类、环氧类、聚氨酯类、全氟乙烯基醚类、超支链低聚物和混合光固化体系类。并对其合成方法和优缺点进行了分析讨论。     

一类高透明含氟共聚型聚酰亚胺的合成与表征

以2,2′-双(三氟甲基)-4,4′-二氨基联苯(TFMB)、4,4-二氨基二苯醚(ODA)和3, 3′,4,4′-二苯醚四甲酸二酐(ODPA)为原料,间甲酚为溶剂,按不同的配比,采用一步法制备了一系列低成本含氟共聚型聚酰亚胺CPI-1～CPI-4,进一步制备成膜。通过红外光谱仪、核磁共振波谱仪对该系列含氟聚酰亚胺的结构进行了表征确认。采用UV光度计、TGA、DSC、拉伸性能试验机对其溶解性能、光学性能、热性能、机械性能进行了测试。结果表明,该系列含氟聚酰亚胺室温下能溶于二甲基亚砜(DMSO)、N,N-二甲基乙酰胺(DMAc)、三氯甲烷(CHCl_3)等有机溶剂,具有较好的溶解性和成膜性。所制薄膜具有优良的光学透明性,在紫外光波长400nm时的透光率均在70%以上。CPI-1～CPI-4的起始分解温度均大于500℃,N_2氛围下800℃的质量残留百分数均在52%以上,玻璃化转变温度在166～170℃。此外,CPI-1～CPI-4薄膜的拉伸强度在89.8～105.3MPa,弹性模量在1.3～1.7 GPa,断裂伸长率在9.7%～18.4%,表现出较好的机械性能。     

含氟丙烯酸酯单体及其聚合物在涂料中的应用

主要叙述了含氟聚合物的发展历程和含氟丙烯酸酯单体及其聚合物的制备、性能特点以及在涂料中的应用。     

Organosoluble and light-colored fluorinated semialicyclic polyimide derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride

In this study, the alicyclic dianhydrides 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) was polymerized with seven kinds of fluorinated aromatic diamines, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (1), 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (2), 1,4-bis(4-amino-2-trifluoromethylphenoxy)diphenyl (3), 1,4-bis(4-amino-2-trifluoromethylphenoxy) diphenyl ether (4), 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane (5), 4,4′-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone (6), and 2,7-bis(4-amino-2-trifluoromethylphenoxy)naphthalene (7), via a two-step polycondensation procedure to prepare seven kinds of fluorinated semialicyclic polyimides (PI) PI-1 ∼ PI-7. The structures of these polyimides were confirmed by infrared spectroscopy (IR). Solubility of the polyimides was tested in various organic solvents and their thermal properties were investigated by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). Ultraviolet-visible spectra (UV-vis) and near infrared absorption spectra (NIR) were obtained to evaluate the optical properties of these polyimides. The obtained polyimides PI-1 ∼ PI-7 displayed excellent solubility in a variety of organic solvents; they were readily soluble in amide-type polar solvent. These polyimide films exhibited good optical transparency in the visible light region (400–700 nm) with the transmittance higher than 80% at 450 nm, and these polyimide films showed little absorption at the optocommunication wavelengths of 1.30 and 1.55 μm. These polyimides showed good thermal stability with the 10% thermal decomposing temperatures higher than 443°C in nitrogen and the glass transition temperatures higher than 265°C. In addition, the effect of the structure of fluorinated diamines on the properties of polyimide films was also compared. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

含氟聚吡啶酰亚胺的合成及性能研究

以4-(4-三氟甲基苯基)-2,6-双[3-(4-胺基苯氧基)苯基]吡啶(m,p-3FPAPP)作为二胺单体,3,3’,4,4’-二苯醚四甲酸二酐(ODPA)和2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA)作为二酐单体,通过两步法成功的制备了3种含氟聚吡啶酰亚胺。利用FTIR、XRD、TGA、DSC、UV-vis以及溶解性测试对其结构和性能进行了表征。结果表明,所得聚合物都具有优异的溶解性能,玻璃化转变温度为234～259.3℃,5%失重温度为526.5～558.2℃,800℃下质量保持率为63.6%～64.7%,且聚酰亚胺膜在400～800 nm的可见光区间有很好的透过性能。     

Light‐colored fluorinated polyimides based on 2,5‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl and various aromatic dianhydrides

A novel trifluoromethyl‐containing aromatic diamine monomer, 2,5‐bis (4‐amino‐2‐trifluoromethylphenoxy)biphenyl (2), was prepared through the nucleophilic substitution reaction of 2‐chloro‐5‐nitrobenzotrifluoride and phenylhydroquinone in the presence of potassium carbonate to yield the intermediate dinitro compound (1), followed by catalytic reduction with hydrazine and Pd/C. A series of fluorinated polyimides (code 5a–f) were synthesized from diamine (2) with six commercially available aromatic dianhydrides using a standard two‐stage process with thermal or chemical imidization of poly(amic acid). Most of fluorinated polyimides showed good solubility at a concentration of 5–10 wt % and even in pyridine and dioxane. For improving solubility of 5c, copolyimides (5c/a–f) were also prepared from 2 and a pair of dianhydrides (3c/a–f), which were mixed in the molar ratio 1:1. All the polyimide films had a tensile strength in the range from 73 to 112 MPa, an elongation at break within a range of 9–23%, and an initial modulus in the range of 1.6–2.2 GPa. These polyimides exhibited glass transition temperatures of 220–267°C and showed no significant decomposition below 500°C under either nitrogen or air atmosphere. In comparison with the analogous nonfluorinated polyimides based on 2,5‐bis (4‐aminophenoxy) biphenyl (2′), the fluorinated polyimides showed better solubility as well as reduced color intensity, lower dielectric constant, and moisture absorption. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4101–4110, 2006     

Colloidal and polymer properties difference of fluorinated acrylate latex prepared with different fluorinated monomers

Fluorinated acrylate latex was prepared by copolymerizing fluorinated monomer, butyl acrylate, and methyl methacrylate, which was initiated by potassium persulfate in the water. The resultant fluorinated latex and its film were characterized with contact angle determinator, dynamic light scattering detector, and differential scanning calorimetry, respectively. Influence of type of fluorinated monomers on colloidal and polymer properties of fluorinated acrylate latex was studied. Results show that the coagulation rate, particle size, contact angle, glass transition temperature, and chemical resistance are increased with the increase of the number of fluorine atom in the fluorinated monomer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

氟表面活性剂的工业应用

介绍了氟表面活性剂的分类、结构及性质;主要综述了由于氟表面活性剂具有"三高"、"两憎"的独特性能,广泛应用于消防、皮革、石油、造纸、纺织印染及金属材料加工等工业领域,起到普通碳氢表面活性剂所不能的作用;指出了根据应用领域的不同,应从分子结构设计入手,有针对性地、有目的地研发氟表面活性剂新品种新工艺,拓展应用领域,注重氟表面活性剂与普通表面活性剂的复配研究。     

Incorporation effects of fluorinated side groups into polyimide membranes on their physical and gas permeation properties

The effects of incorporation of fluorinated alkyl side groups into polyimide membranes were investigated in terms of their physical and gas permeation properties. Four polyimides with fluorinated side groups and four polyimides without the side groups were prepared by polycondensation of 2‐(perfluorohexyl)ethyl‐3, 5‐diamino benzoate (PFDAB) and m‐PDA with four aromatic dianhydrides (6FDA, ODPA, BTDA, and PMDA), respectively. It was found that the incorporation of fluorinated side groups into the polyimide membranes decreased their surface free energies (T_gs), solubility parameters, and fractional free volume (FFV)s and therefore, enhanced the permeabilities for CO₂, O₂, N₂, and CH₄ gases but reduced the selectivities for CO₂/ CH₄, O₂ /N₂, CO₂/N₂ gas pairs depending upon the structure of dianhydride monomers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2756–2767, 2000     

Synthesis and properties of fluorinated polyimides and fluorinated poly(imide amide)s containing pendent cyano groups

A series of fluorinated polyimides and fluorinated poly(imide amide)s containing pendent cyano groups were prepared and investigated to determine their dielectric constants as a function of relative humidity and thermal characteristics. The fluorinated polymides and fluorinated poly(imide amide)s containing pendent cyano groups were prepared by reaction of bis(4-aminophenoxy) benzonitriles with a fluorinated dianhydride and with a fluorinated di(acid chloride) containing preformed imide rings. The properties of the fluorinated polyimides and fluorinated poly(imide amide)s containing pendent cyano groups were compared with those of fluorinated polyimides and fluorinated poly(imide amide)s prepared from 1,3-bis(4-aminophenoxy)benzene. The introduction of the pendent cyano groups caused an increase in the dielectric constant and an increase in the glass transition temperature of the polymers compared with the polymers prepared without pendent cyano groups.     

含氟嵌段聚酰亚胺共聚物的制备及其介电常数计算

通过顺序加料法制备了一系列不同氟含量聚酰亚胺,FT-IR、1H-NMR及GPC测试结果表明,所制备的聚合物为嵌段共聚物.Lorenz和Vogel介电常数计算公式主要用于均聚物介电常数的计算,通过对上述两计算公式进行相应变形处理,使之适用于计算嵌段共聚物的理论介电常数,并将其运用到所合成的嵌段型含氟聚酰亚胺模板聚合物的介电常数计算中,计算结果显示,Lorenz和Vogel介电常数变形公式计算所得的模板聚合物的介电常数与聚合物介电常数实测值具有较好的吻合性,能够有效指导低介电常数嵌段聚酰亚胺的设计与合成.     

含氟高分子表面活性剂的合成及其乳化性能的研究

以甲基丙烯酸十二氟庚酯(RfAA)、甲基丙烯酸(MAA)或2-丙烯酰胺-2-甲基丙磺酸(AMPS)、甲基丙烯酸聚乙二醇酯(PEGMA)为共聚单体,以亲氟-亲水-空间位阻的方式,合成了两种含氟高分子表面活性剂P(RfAA-PEGMA-MAA)和P(RfAA-PEGMA-AMPS)。考察了它们对RfAA的乳化性能,探讨了单体种类、单体含量、引发剂用量以及链转移剂用量对单体转化率和聚合物乳化性能的影响。结果表明,n(RfAA)∶n(MAA或AMPS)∶n(PEGMA)=5∶3∶2,引发剂用量为单体总质量的4%,链转移剂用量分别为单体总质量的3%、2%时,所合成的两种含氟高分子表面活性剂对RfAA均表现出了良好的乳化性能,它们的最低表面张力分别为56.3、49.1 mN/m,CMC均约为0.002 g/mL。