国内外含氟聚合物的应用及市场现状

介绍国内外含氟聚合物的应用及市场现状。2004年,全球含氟聚合物的产能约为20.3万t/a,产能利用率为65%;全球含氟聚合物的消费量累计达到13.27万t,消费额超过25亿美元。2004年,我国的含氟聚合物消费量为1.3万t,年均增长率为8%。预计,2009年我国含氟聚合物的消费量将达到1.5万～1.6万t。     

含氟聚合物及其涂料

斥油性和持久性好的斥油涂料组合物;旋转机器中运动叶片用无机物填充的氟聚物涂料;核壳型含氟丙烯酸醢共聚乳液;聚偏氟乙烯，聚丙烯酸酯复合乳液的合成与性能;全氟丙烯酸醢的特点及其水基聚合物的制法;一罐装氟树脂涂料及防污染方法;用于无机基材的涂料组合物。     

含氟树脂涂料的研究进展

概述了氟树脂的发展历程及其应用研究进展;总结了不同氟树脂的结构性能特征;归纳了PFEVE和PVDF两类典型氟树脂的基本物理性能和研究开发现状;简述了水分散氟树脂体系的制备方法。     

含氟聚合物合成

1绪言1992年3月高分子学会举办了以“含氟高分子化合物的新进展”为主题的小型研讨会,广泛地介绍了从单体合成、聚合反应到工业技术的进展。同时,作为1992年在布拉格召开的34届国际理论与应用化学联合会有关大分子国际讨论会（34thIUPACIntemationalSymposiumonMacromolecules）的后续会议,于1993年7月进行了有关含氟单体和聚合物的小型研讨会。作者在会议的邀请讲演中予以集中归纳。其后有关含氟单体的聚合研究有了稳步发展。但是乙烯聚合中三氟乙烯基（CF_2＝CF－）化合物、α－三氟甲基乙烯基化合物（CH_2＝C（CF_3）－）的聚…     

含氟聚合物及其涂料

201309003太阳能组件背板涂装用耐候性优异的核壳型氟聚物涂料的制备：W02012-124926[国际专利申请,韩]/韩国：Korea Research Institute of Chemical Technology（HaJongWook等）．-2012．09．20．-13页．-21756（2011．03．11）：IPCC08F14/18题述氟聚物以（A）氟聚物为核和（B）氟乙烯醚（CFz：CFOCF：CF。R,）为壳,其中Rf表示C1～3全氟烷基或全氟烷氧基。例如,在6．3mL浓度为20％的水性全氟辛酸铵以及溶于620mL水中的1．OmL氯仿存在下,于80℃下加热偏氟乙烯（蒸汽压为300psi）,然后以0．6mL/min的速度将1OmL浓度为2g/L的过硫酸铵加入反应釜中,同时保持偏氟乙烯蒸汽压为300psi：以0．15mL/min的速度将全氟乙烯基丙醚加入该反应釜中的同时添加180g偏氟乙烯,制得一种共聚物。将该共聚物涂覆于基材上,干煤固化,制得耐候性和防潮性优异的试样。     

含氟硅烷及其聚合物的合成与应用

着重介绍了含氟硅烷(尤其是含氟单体)及其聚合物的特性、合成方法以及应用展望。     

含氟聚合物及其涂料

200606008 延长了涂料活化期的耐沾污氟聚合物；200606009 防污处理剂用氟有机化合物；200606010 金属或玻璃底材用PTFE/非氟化聚合物混合物底漆；200606011 氟树脂乳液砂壁状涂料的研制；200606012 环境友好含氟乳液功能型氟树脂涂料的研究及应用。     

聚偏氟乙烯应用及合成技术进展

叙述了聚偏氟乙烯(PVDF)在涂料、注塑、水处理、锂电池及光伏等领域的应用,介绍了偏氟乙烯单体的合成方法、PVDF的聚合工艺,汇总了国内企业产能情况,并展望了国内PVDF产业发展趋势。     

偏氟乙烯单体的制备

综述了偏氟乙烯单体的各种工业化制备工艺路线、并对其工艺特点进行了评述。     

Bis(perfluoro-2-n-propoxyethyl)diacyl peroxide initiated homopolymerization of vinylidene fluoride (VDF) and copolymerization with perfluoro-n-propylvinylether (PPVE)

Vinylidenefluoride (VDF) has been homopolymerized and copolymerized with perfluoro-n-propylvinylether (PPVE) using bis(perfluoro-2-n-propoxyethyl)diacyl peroxide (BPPP) as the initiator in CF₂ClCFCl₂. The polymers obtained were characterized with ¹⁹F NMR and ¹H NMR spectroscopy, DSC and TGA. The ¹⁹F NMR spectra were used to determine the polymer microstructures and end groups. Both PVDF and poly(VDF–PPVE) were terminated on both chain ends by CF₃CF₂CF₂OCF(CF₃)∼ arising from the decomposition of the initiator. The concentration of end groups was used to assess the molecular weight of the polymers. Using the Fine–Ross method, the reactivity ratios of both monomers were determined (r_VDF ∼ 1.06, r_PPVE ∼ 0). The T_g of poly(PPVE) (−10.3 °C) was determined using the T_gs of VDF/PPVE copolymers with different compositions and the Flory–Fox equation. A new method to produce a modified PVDF or VDF copolymer for powder coatings with higher thermal stability was also developed.     

新型耐高温杂环聚醚砜酮酮材料的研究

合成一种新型热塑性耐高温杂环聚醚砜酮酮材料（ＰＰＥＳＫＫ）,研究了材料的热性能、力学性能、电性能、溶解性能、摩擦性能及膜性能。结果表明,ＰＰＥＳＫＫ为一类具有较高耐热性、综合性能优良、成本低的机械工程塑料。     

含氟聚合物系列产品的性能及应用

概述了四氟乙烯/六氟丙烯共聚物及其化学改性系列产品、聚四氟乙烯化学改性系列产品、偏氟乙烯/六氟丙烯共聚物及其化学改性系列产品、偏氟乙烯/六氟丙烯/四氟乙烯三元共聚物、含氟涂料用树脂等含氟聚合物系列产品的性能及应用。     

Precipitation polymerisation of vinylidene fluoride in supercritical CO2 and real-time calorimetric monitoring

Vinylidene fluoride was polymerised in supercritical carbon dioxide. Power compensation calorimetry was used to monitor the polymerisation process on-line. The polymer product was found to have a low apparent-density, leading to an observed high solid content in the autoclave at low yields. In situ calorimetry showed a sharp transition of the heat transfer in the reactor, leading to a useful parameter for monitoring the polymerisation process. The stirring rate was found to have no effect on the molecular weight, but did modify the calorimetric traces and the morphology of the polymer. The polymerisation at a lower pressure resulted in a lower molecular weight product and a lower polymerisation rate.     

偏二氯乙烯-丙烯酸酯共聚乳液的制备与性能研究

采用软单体丙烯酸异辛酯对聚偏二氯乙烯乳液进行增韧改性,得到了韧性、附着力、耐中性盐雾等综合性能优良的偏二氯乙烯-丙烯酸酯共聚乳液。研究了偏二氯乙烯、丙烯酸异辛酯、功能单体丙烯酸、引发剂的用量以及乳化剂用量与配比等因素对乳液性能的影响。结果表明:偏二氯乙烯用量为单体总量80%,丙烯酸异辛酯和丙烯酸用量分别为单体总量12%和3%,引发剂用量为单体总量0.5%,乳化剂十二烷基硫酸钠与KL-100用量为单体总量1.2%且质量比为1∶5时得到的共聚乳液具有优良的综合性能。     

Structure and dynamics of a vinylidene fluoride oligomer and its cyclodextrin inclusion compounds as studied by solid-state F MAS and H → F CP/MAS NMR spectroscopy

The molecular structure and dynamics of a vinylidene fluoride oligomer telomerized by carbon tetrachloride (Cl-OVDF) and its inclusion compound (IC) with β-cyclodextrin (β-CD) have been investigated using solid-state ¹⁹F magic angle spinning (MAS) and ¹H → ¹⁹F cross-polarization (CP)/MAS NMR spectroscopy. The preferential IC formation of the lower-molecular-weight components with β-CD was used to refine as-received Cl-OVDF. The refined Cl-OVDF with larger molecular weight readily takes γ-form (tttg⁺tttg⁻) conformation, and it also forms ICs with β-CD (Cl-OVDF/β-CD IC) under a certain condition. ¹⁹F MAS NMR indicates that Cl-OVDF chains virtually isolated in the β-CD cavities take no specific conformations even at −40 °C. The temperature dependence of the magnetic relaxation times (T₁^F, T_1ρ^F) indicates that the Cl-OVDF chains in ICs undergo molecular motions similar to the amorphous phase in the bulk, although the intramolecular spin diffusion among ¹⁹F nuclei is more significant in the former because of the one-dimensional confinement.     

Electrical and Optical Properties of Vinylidene Fluoride—Trifluoro Ethylene Copolymers Prepared by Solution Cast

Abstract

The dielectric and non-linear optical properties of a 60/40 copolymer of vinylidene fluoride with trifluoro ethylene prepared as thin films by a solution cast procedure are described. The relation of these properties with the microstructure of the system as derived by wide and small angle X-ray scattering experiments is also discussed. Some implications regarding to the use of these copolymers in electrooptics are pointed out.     

复合成盐剂对聚醚醚酮合成与性能的影响

采用4,4′-二氟二苯甲酮、对苯二酚为原料,以不同比例的碳酸钾和碳酸钠为复合成盐剂,二甲苯为脱水剂,二苯砜为溶剂成功制备了一系列聚醚醚酮(PEEK)树脂。通过傅里叶红外光谱和X射线衍射对PEEK树脂结构进行了表征,证明合成的样品是对苯二酚型PEEK树脂。其次,对所制样品分别进行力学性能、特性黏度、热性能测试,详细地探讨不同钾/钠比例的复合成盐剂对PEEK性能的影响。结果表明,所有样品均展示了优异的力学性能和热性能,其熔点和初始分解温度分别大于330℃和520℃,拉伸强度介于77~101 MPa。此外,当碳酸钾和碳酸钠的物质的量比为7∶3时,PEEK树脂的综合性能达到最优。     

氧化锆滑板制备工艺对其性能和显微结构的影响

分别以电熔CaO稳定ZrO2(CZ,粒度分为5级,最大为1 mm,最小为5μm),电熔CaO、Y2O3复合稳定ZrO2(YCZ,其d50<5μm)和两种电熔MgO、Y2O3复合稳定ZrO2(MZY1和MZY2,粒度均为d50<5μm)为主要原料,分别采用传统颗粒级配和微粉造粒料两种工艺制备了氧化锆滑板试样,研究了原料种类、原料粒度、烧成温度对氧化锆滑板力学性能和显微结构的影响。结果表明:采用微粉造粒料制备的试样比采用传统颗粒级配方式制备的具有更高的强度和体积密度,以及更低的显气孔率;采用微粉造粒料制备的试样的抗热震性与烧成温度、稳定剂的种类和含量、氧化锆原料中SiO2和A l2O3杂质的含量等有关;采用传统颗粒级配制成的氧化锆试样难以烧结致密,颗粒与基质结合稍差,存在粗大气孔;而以造粒料制成的试样烧结致密,并有相当数量的微气孔和微裂纹。