聚甲醛耐老化性能及其改进研究

以研制耐候性聚甲醛为目标，将自制高分子改性剂、其它改性剂与聚甲醛共混(POM)以提高POM的耐老化性。通过拉伸强度、断裂伸长率、冲击强度和色差的测定，比较了未改性聚甲醛和改性聚甲醛的耐紫外光老化、热氧老化和热水老化性能，结果表明：自制改性剂与其它改性剂共混用于聚甲醛，能显著改善聚甲醛的稳定性及耐老化性。     

耐候聚甲醛的制备及其性能研究

通过紫外光老化箱对聚甲醛进行了长期老化实验研究,以万能材料试验机、冲击试验机、热重分析仪、色差仪等仪器对长期老化后的聚甲醛的力学性能、热稳定性、色差等进行分析。结果表明,不同自由基捕获剂复配能达到良好的协同抗光老化效果,可明显改善聚甲醛材料的力学性能保持率、热稳定性及色差变化。     

聚甲醛的耐沸水稳定化研究

讨论了聚甲醛的沸水老化机理、沸水老化行为及改善聚甲醛耐沸水性的方法。     

聚甲醛在沸水中的老化行为

本文考察了聚甲醛在沸水中的老化行为。结果表明，在沸水处理过程中，因沸水所引起的聚甲醛化学性质的变化较小。其老化现象主要表现为，试样表现的龟裂，添加剂的析出，变色以及拉伸断裂伸长率的下降等力学性能方面的变化。     

光屏蔽剂对聚甲醛耐老化性能的影响

采用炭黑和纳米级氧化锌两种光屏蔽剂对共聚甲醛进行耐老化改性,对比了改性前后聚甲醛耐紫外光、耐热氧及耐热水老化性能的变化。结果表明,紫外光老化对聚甲醛性能影响最显著,两种光屏蔽剂均能减缓聚甲醛的光降解过程。炭黑的光屏蔽效果优于氧化锌,但会加速聚甲醛热氧降解。聚甲醛试样表面层相对分子质量的变化规律基本上与试样断裂伸长率、冲击强度以及色差变化规律保持一致。     

改性聚甲醛的摩擦性能

为进一步提高聚甲醛的摩擦性能,加入超高分子量聚乙烯等材料进行改性,摩擦系数由纯聚甲醛的0.26降为0.20,磨耗由3.5mg降为1.0mg。同时,在不同负荷及转速下对含有不同固体润滑剂(如聚四氟乙烯、石墨等)的改性聚甲醛的摩擦性能进行了测试。     

聚甲醛加速老化试验研究

对聚甲醛（POM）进行了光加速老化试验和湿热老化试验研究。利用电子显微镜，差示扫描量热仪和X光电子能谱对材料在老化过程中的物理和化学性能进行了分析。结果表明，POM在老化过程中物理力学性能下降的主要原因是表面无定形区域的光氧化。     

聚甲醛热降解性能研究

通过测定聚甲醛的熔融指数、拉伸强度及断裂伸长率,分析、比较其热老化的速度;同时应用扫描电镜、X-射线光电子能谱观察和分析了聚甲醛（POM）的表面形貌、表面官能团的类型。试验结果表明：120％热老化试验条件下,随着老化时间的延长,熔融指数逐渐增大,说明发生了缓慢的热氧化降解过程;20天短期热老化对聚甲醛拉伸强度及断裂伸长率影响不是很明显,说明POM的热老化应该有一个相当长的过程;扫描电镜显示：105天热老化后,聚甲醛表面出现龟裂和粉化现象;X-射线光电子能谱显示：老化前后样品中C1s谱均含有C-C和C-02个峰,但老化后C-C含量降低,C-O含量增加,说明POM的热老化以C-C断裂降解为主,原始试样O1s／C1s为56．98％,105天老化后为72．92％。     

聚甲醛结晶性、分子量和工艺特性的热分析研究

聚甲醛是具有优良性能的工程塑料之一。它有较高的模量、热变形温度、韧性、耐湿热性和低功率损耗等,但聚甲醛也存在一定的缺点,如加工收缩率大,制品尺寸稳定性差,要得到性能优异的制品必须控制聚甲醛的分子排列、分子量及其分布、熔流特性和膨胀收缩特性。本文用热分析方法研究了共聚甲醛及其改性聚合物的结晶特性,并用DSC法导出聚甲醛分子量测定的方法。从TMA和DMA法可研究聚甲醛的膨胀和收缩特性,指出了收缩较小的树脂在热分析中的表征,可以作为聚甲醛制件质量控制的依据。聚甲醛是结晶型聚合物,结晶性能可决定制件性能的优劣。Hamme…     

助剂对聚甲醛常温颜色稳定性的影响研究

在聚甲醛中添加不同助剂体系,通过室温放置20 d和140 ℃烘箱加速老化7 d处理后,测定物料的黄色指数、熔体质量流动速率、拉伸强度、冲击强度变化,对助剂体系在聚甲醛中的应用进行了评价.结果表明,抗氧剂Irganox1010对聚甲醛的颜色变化有很大影响,引入金属减活化剂后,提高了聚甲醛在常温环境中的颜色稳定性,同时也较好地保持了聚甲醛的各项性能.     

Synthesis of a core–shell polyacrylate elastomer containing ultraviolet stabilizer and its application in polyoxymethylene

A core–shell polyacrylate elastomer containing ultraviolet (UV) stabilizer was synthesized via semicontinuous seeded emulsion polymerization from butyl acrylate (BA), methyl methacrylate (MMA), and a polymerizable UV stabilizer 2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylproroxy)benzophenone (BPMA). The core–shell poly(MMA‐BA‐BPMA) was investigated by Fourier transform infrared spectroscopy, gel permeation chromatography UV–visible (UV–vis) absorption spectroscopy, and transmission electron microscope. Furthermore, the obtained core–shell poly(MMA‐BA‐BPMA) elastomer was used as a modifier to enhance the UV resistance and impact resistance of polyoxymethylene (POM). As studied by scanning electron microscope, the core–shell poly(BA‐MMA‐BPMA) elastomer could be well dispersed in POM matrix, indicating that the elastomer had good compatibility with POM. In addition, the POM/poly(MMA‐BA‐BPMA) blend was examined by differential scanning calorimetry before and after UV irradiation. The results showed that the melting point decreased as the irradiation time increased; however, the crystallinity culminated at 500‐h UV irradiation slightly decreased and at last leveled off. The mechanical properties of POM/poly(BA‐MMA‐BPMA) before and after UV irradiation were also studied. It revealed that the photostabilizing fragments in the elastomer could provide long‐term UV resistance to POM. Besides, the impact strength was also improved when compared with pure POM. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Synthesis of an acrylate elastomer with UV stabilization and its application in polyoxymethylene

In this study, an acrylate elastomer with light‐stable functional groups was synthesized by methyl methacrylate (MMA), butyl acrylate (BA), and a polymerizable UV stabilizer 2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylproroxy) benzophenone (BPMA) via emulsion polymerization, and the product was poly[methyl methacrylate‐co‐butyl acrylate‐co‐2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylproroxy) benzophenone] [poly(MMA‐co‐BA‐co‐BPMA)]. The composition and characteristics of poly (MMA‐co‐BA‐co‐BPMA) were determined by using Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H‐NMR), and ultraviolet–visible absorption spectroscopy (UV–vis). Further, the obtained poly(MMA‐co‐BA‐co‐BPMA) was blended with polyoxymethylene (POM) to modify its photostabilization, as well as the mechanical properties of POM composite were tested before and after UV irradiation. The result showed that poly(MMA‐co‐BA‐co‐BPMA) can be dispersed well in the POM matrix, which could play a role of improving compatibility with and toughening for POM, and its light‐stable functional groups could increase the UV resistance of POM composite. Mechanical properties of modified POM were kept well with higher impact strength and elongation at break than pure POM after UV irradiation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanical properties and surface morphology of photodegraded polyoxymethylene modified by a core–shell acrylate elastomer with UV stabilization

In order to improve the photostability of polyoxymethylene (POM), a core‐shell acrylate elastomer with UV stabilization, i.e. poly[(methyl methacrylate)‐(butyl acrylate)‐2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxypropoxy)benzophenone] (core‐shell poly(MMA‐BA‐BPMA)), was added into the POM matrix using a melt‐mixing method. The effect of the modification with core‐shell poly(MMA‐BA‐BPMA) on POM was compared with that of poly(MMA‐ co ‐BA‐ co ‐BPMA) copolymer. Scanning electron microscopy, metallographic microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, X‐ray diffraction and X‐ray photoelectron spectroscopy were employed to characterize POM blends before and after UV irradiation, and the mechanical properties of the POM blends were investigated. The results showed that core‐shell poly(MMA‐BA‐BPMA) improved well the compatibility with and toughness of the POM matrix, and its light‐stable functional groups could increase the UV resistance of POM blends. During UV aging, the impact strength and elongation at break of POM/core‐shell poly(MMA‐BA‐BPMA) blends were retained, the growth rate of surface cracks of POM was inhibited effectively by core‐shell poly(MMA‐BA‐BPMA) and the degree of photo‐oxidation of POM blend surfaces was improved to a certain extent. Compared with poly(MMA‐ co ‐BA‐ co ‐BPMA), core‐shell poly(MMA‐BA‐BPMA) had a better UV stabilization effect on the POM matrix. Our results indicate that the core‐shell acrylate elastomer with toughening and UV stabilization functions can significantly improve the long‐term UV stability of POM. Copyright © 2012 Society of Chemical Industry     

Preparation of core–shell nanoparticle‐based hindered amine stabilizer and its application in polyoxymethylene

Core–shell nanoparticles chemically functionalized by hindered amine stabilizer (HAS), poly(BA‐MMA‐co‐PMPA) (PBMP), were prepared by two‐stage emulsion polymerization from butyl acrylate, methyl methacrylate, and 1,2,2,6,6‐pentamethylpiperidin‐4‐yl acrylate. The incorporation of HAS into the particles was confirmed by nuclear magnetic resonance (¹H‐NMR) and the core–shell microstructure of PBMP particles was revealed by transmission electron microscopy. Furthermore, PBMP capable of one‐step toughening and photostabilizing, was melt‐blended with polyoxymethylene (POM), and its dispersion in POM was investigated by scanning electron microscope. The results showed that the core–shell nanoparticles could be well dispersed in POM matrix, indicating its good compatibility with POM. The UV resistance and impact resistance of POM were obviously improved by the HAS‐functional core–shell nanoparticles simultaneously. In addition, the core–shell nanoparticles could confer excellent protection to the surface of POM from UV‐light damage, regardless of the adverse effects on the thermal‐oxidative stability of POM, as investigated by thermogravimetry analysis under aerobic condition. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

影响聚氨酯弹性体紫外线稳定性的因素

介绍了聚氨酯弹性体在紫外线照射下发生光老化的反应机理及其软段、硬段种类和结构对弹性体紫外线稳定性的影响,探讨了光稳定剂、光屏蔽剂对弹性体耐紫外线稳定性的影响。     

聚甲醛的光稳定化研究

采用了二苯甲酮类和苯并三唑类紫外线吸收剂(UVA)、位阻胺类光稳定剂(HALS)以及光屏蔽剂对聚甲醛进行光稳定化改性,对比了改性前后聚甲醛光降解后的物理力学性能及表面层分子量保持率。结果表明,0 5%的UVA可以显著提高POM的耐紫外光性能,苯并三唑类效果优于二苯甲酮类UVA。在酚类抗氧剂存在下,低含量的HALS(<0 25%)对聚甲醛没有光稳定化作用。     

端烷氧基有机硅改性聚醚的初步研究

将双烯丙基聚醚和端含氢硅氧烷共聚后,再用乙烯基三乙氧基硅烷封端的方法制备了有机硅改性聚醚共聚物：采用核磁共振谱和DSC进行表征,表明合成了目标产物,对合成共聚物的分子质量测试及制备硫化胶的性能研究表明,还需进一步提高共聚物的分子质量。     

热塑性丙烯酸酯树脂在紫外光固化涂料中的应用

在紫外光固化体系中引入非紫外光固化的热塑性丙烯酸酯树脂作为辅助成膜物.讨论了其对体系成膜附着力、柔韧性、硬度、光泽的影响.实验结果表明：选择合适相对分子质量的热塑性丙烯酸酯树脂可以改善紫外光固化涂料的附着力和柔韧性等漆膜性能.     

Toughened polyoxymethylene by polyolefin elastomer and glycidyl methacrylate grafted high‐density polyethylene

Ternary blends of polyoxymethylene (POM), polyolefin elastomer (POE), and glycidyl methacrylate grafted high density polyethylene (GMA‐g‐HDPE) with various component ratios were studied for their mechanical and thermal properties. The size of POE dispersed phase increased with increasing the elastomer content due to the observed agglomeration. The notched impact strength demonstrated a parabolic tendency with increasing the elastomer content and reached the peak value of 10.81 kJ/m² when the elastomer addition was 7.5 wt%. The disappearance of epoxy functional groups in the POM/POE/GMA‐g‐HDPE blends indicated that GMA‐g‐HDPE reacted with the terminal hydroxyl groups of POM and formed a new graft copolymer. Higher thermal stability was observed in the modified POM. Both storage modulus and loss modulus decreased from dynamic mechanical analysis tests while the loss factor increased with increasing the elastomer content. GMA‐g‐HDPE showed good compatibility between the POM matrix and the POE dispersed phase due to the reactive compatibilization of the epoxy groups of GMA and the terminal hydroxyl groups of POM. A POM/POE blend without compatibilizer was researched for comparison, it was found that the properties of P‐7.5(POM/POE 92.5 wt%/7.5 wt%) were worse than those of the blend with the GMA‐g‐HDPE compatibilizer. POLYM. ENG. SCI., 57:1119–1126, 2017. © 2017 Society of Plastics Engineers