乙烯基硅树脂改性EVA胶膜的制备

以混合氯硅烷及硅氧烷为单体,采用水解共缩聚的方法制备了乙烯基硅树脂,并研究了合成该树脂的影响因素;以乙烯基硅树脂为改性剂,以高乙酸乙烯含量的乙烯-乙酸乙烯共聚物(EVA)为基体,通过熔融混炼法添加各种助剂,得到改性的EVA胶膜,探讨了乙烯基硅树脂对EVA胶膜性能的影响。结果表明:乙烯基硅树脂改性的EVA胶膜热稳定性和老化性能得到了提高;含有苯基的乙烯基硅树脂改性EVA胶膜时,所得胶膜的热氧老化性能好,透光率高,且黄色指数增大速率较慢。因此,含苯基乙烯基硅树脂是EVA胶膜的理想改进剂。     

乙酸-乙酸乙烯酯橡胶/聚乳酸共混体系的发泡及阻尼性能

以乙烯-乙酸乙烯酯橡胶(EVM)/聚乳酸(PLA)共混物为基体材料,过氧化二异丙苯(DCP)为硫化剂、偶氮二甲酰胺(AC)为发泡剂,经模压发泡制备橡塑共混发泡材料,用扫描电子显微镜观察材料的泡孔结构及泡孔尺寸分布,采用动态黏弹谱仪对发泡材料的阻尼性能进行研究,考察了AC和DCP用量、发泡时间及白炭黑用量对EVM/PLA发泡材料泡孔结构及阻尼性能的影响。结果表明,随着AC用量的增加,材料的泡孔数目增多但孔径相差不大,阻尼性能也无明显变化,在AC用量为4份时材料的阻尼性能较好;随着DCP用量的增加,材料的泡孔尺寸略有减小,阻尼性能变化不大,DCP用量为5份时材料的阻尼性能较好;随着发泡时间的延长,泡孔尺寸逐渐减小,阻尼性能逐渐提高,发泡时间为5 min时,泡孔孔径与损耗因子均出现突变;填料用量增加,泡孔孔径减小,发泡材料整体损耗因子上升。     

高抗冲聚苯乙烯/乙烯-乙酸乙烯共聚物/丁苯橡胶热塑性硫化胶的黏弹行为

采用动态硫化法制备了高抗冲聚苯乙烯/乙烯-乙酸乙烯共聚物(EVA)/丁苯橡胶热塑性硫化胶(TPV),考察了EVA用量对TPV的动态硫化操作性、微观相态、力学性能、熔体表观黏度、动态黏弹行为及应力弛豫的影响。结果表明,在基质树脂相中加入EVA,可改善TPV动态硫化的操作性及制品的外观质量,且TPV的形变回复能力得到增强,但对TPV力学性能和表观黏度的影响不明显。随着TPV中EVA用量的增加,在频率扫描模式下,TPV的储能模量和损耗模量下降,损耗因子出现一定程度的波动;在温度扫描模式下,储能模量、损耗模量及损耗因子均下降。随着EVA用量的增加,TPV应力弛豫测试的残留应力降低。     

氢氧化镁阻燃剂填充EVA共聚物力学性能研究

研究了普通氢氧化镁、六角片状氢氧化镁和硬脂酸(SA)改性氢氧化镁分别填充到乙烯-乙酸乙烯共聚物(EVA)中制得的复合材料的力学性能。用红外光谱(FT-IR)、扫描电镜(SEM)对3种类型氢氧化镁及EVA/氢氧化镁复合材料的结构和形貌进行了分析。结果表明:相比普通氢氧化镁,六角片状氢氧化镁和SA改性的氢氧化镁有效地降低了表面极性,大大降低了对复合材料的力学性能的影响;4%(质量分数)SA改性氢氧化镁在EVA树脂中的分散性均匀,填料表面与树脂表面的界面黏结性较好;氢氧化镁(MH)粉体的加入增加了EVA/MH复合材料的拉伸强度,其中4%(质量分数)SA改性氢氧化镁粉体对复合材料拉伸强度的影响最大,六角片状氢氧化镁影响最小;氢氧化镁粉体填充量达到60质量份(60质量份氢氧化镁填充至100质量份EVA中)时,断裂伸长率降低到100%以下,复合材料力学性能急剧恶化。     

Thermal and physicomechanical properties of ethylene-vinyl acetate copolymer and layered double hydroxide composites

A series of ethylene-vinyl acetate (EVA) copolymer films have been prepared with different compositions viz. 2, 4, 6, and 8 wt % layered double hydroxide (LDH) nanoparticles by solution intercalation method. These solution-casted EVA/LDH nanocomposite films were dried and characterized by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. EVA/LDH films were further tested for tensile strength, density, moisture content, solubility resistance, flammability, and electrical properties. The DSC and FTIR analysis indicate strong interactions between the LDH layers and vinyl acetate groups in EVA. Further, EVA nanocomposite films show enhanced tensile strength, limiting oxygen index (LOI), and flammability rating for the addition of LDH without sacrificing the electrical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

撕裂模式下乙烯-丙烯酸共聚物/丁腈橡胶热塑性硫化胶的Mullins效应及其可逆回复

采用动态硫化法制备了乙烯-丙烯酸共聚物(EAA)/丁腈橡胶(NBR)热塑性硫化胶(TPV),对其撕裂强度、微观相结构、撕裂模式下的Mullins效应及热处理条件下的Mullins效应可逆回复行为进行了研究.结果表明,EAA/NBR TPV在EAA与NBR的质量比为40/60时的撕裂强度和应变较高.微观形貌观察可见,EA...     

基于乙烯-乙酸乙烯共聚物/丁腈橡胶热塑性硫化橡胶超亲水材料的制备与性能

采用动态硫化法制备了基于乙烯–乙酸乙烯酯共聚物/丁腈橡胶的热塑性硫化橡胶（EVA/NBR TPV）,以不同型号金相砂纸为模板,通过模压法在其表面构建具有微纳米结构的表面,研究了橡塑质量比对EVA/NBR TPV粗糙表面超亲水行为的影响及EVA/NBR TPV超亲水表面的微观结构和超亲水性能,并初步探讨了EVA/NBR TPV表面的亲水机制。结果表明,当EVA/NBR TPV的橡塑质量比为20/80时,采用模板法且以耐水砂纸为模板制得的EVA/NBR TPV表面亲水性较好。其中,当橡塑质量比为20/80时,以NO 1000砂纸为模板,模压温度为165 ℃,经过预热10 min、热压3 min、冷压5 min后制得的EVA/NER TPV薄膜表面的亲水性最佳。     

撕裂模式下乙烯-乙酸乙烯酯共聚物/氯丁橡胶热塑性硫化胶的Mullins效应及其可逆回复

采用动态硫化法制备了乙烯-乙酸乙烯酯共聚物（EVA）/氯丁橡胶（CR）热塑性硫化胶（TPV）,对其微观形貌、撕裂强度、撕裂模式下的Mullins效应、热处理后的可逆回复行为及其机制进行了研究。结果表明,EVA/CR TPV橡塑质量比为30/70时其撕裂模式下的应变和撕裂强度较高,橡胶相与树脂相呈“海-岛”结构;撕裂模式下EVA/CR TPV的单轴循环测试中表现出明显的Mullins效应,增大应变时,其最大撕裂强度、瞬时残余应变、内耗值和阻尼因子均增加,但应力软化因子趋于下降;随着热处理温度的上升,Mullins效应的可逆回复效果获得改善,且温度为70℃时其可逆回复行为最好。     

Effect of molecular structure on ethylene-vinyl alcohol copolymer thermal degradation and stability

To study the effect of molecular structure on ethylene-vinyl alcohol copolymer (EVOH) thermal stability during processing, EVOH samples with different molecular weights and comonomer distributions were prepared by solubility fractionation from two different commercial materials, and then, the structure features of samples were characterized by ¹H-NMR, viscometry, differential scanning calorimetry, and, especially, successive self-nucleation and annealing. Their thermal stabilities were further analyzed by isothermal oxygen treatment and thermogravimetry. Attenuated total internal reflectance Fourier transform infrared spectroscopy and UV were used to obverse the structural changes in samples (the formation of chromogenic groups: CO and  CC ). According to the results of isothermal oxygen treatment at 200°C, at the same ethylene content, low-molecular-weight samples have worse thermal stability, which were extremely easy to yellowing and form insoluble gel. To investigate the structure differences between the low-molecular-weight samples, it was found that long vinyl alcohol segments may not worsen the thermal stability in the conditions of the same ethylene content. But samples with a uniform distribution of ethylene segments and a certain length of ethylene segments will have better thermal stability, which makes it more difficult to form carbonyl even diketene conjugation structure.     

Adhesion properties and thermal degradation of silicone rubber

Silicone rubber is suitable for the thermal insulator of the rocket motors owing to its heat resisting properties as well as its excellent elasticity and restoring force. However, the adhesion properties of the silicone rubber should be improved greatly to be used as the thermal insulator because of its poor adhesiveness coming from the low surface tension. Functional groups were incorporated through copolymerization to the silicone rubber to induce chemical reaction with the functional groups in the propellant/liner components to enhance the adhesion properties. Peeling tests results disclosed that the incorporation of amine groups was the most efficient for the adhesiveness enhancement and that addition of carbon black improved the adhesiveness still more. Stability against thermal degradation of the silicone rubber was examined by measuring the activation energy through the thermogravimetric analysis. The results revealed that the compounding of the Cloisite® clays boosted up the thermal stability of the silicone rubber much more greatly than that of carbon black. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2782–2787, 2007     

Thermal stability and ablation properties of silicone rubber composites

Effects of incorporation of clay and carbon fiber (CF) into a high temperature vulcanized (HTV) silicone rubber, i.e., poly(dimethylsiloxane) (PDMS) containing vinyl groups, on its thermal stability and ablation properties were explored through thermogravimetric analyses (TGA) and oxy‐acetylene torch tests. Natural clay, sodium montmorillonite (MMT), was modified with a silane compound bearing tetra sulfide (TS) groups to prepare MMTS₄: the TS groups may react with the vinyl groups of HTV and enhance the interfacial interaction between the clay and HTV. MMTS₄ layers were better dispersed than MMT layers in the respective composites with exfoliated/intercalated coexisting morphology. According to TGA results and to the insulation index, the HTV/MMTS₄ composite was more thermally stable than HTV/MMT. However, addition of CF to the composites lowered their thermal stability, because of the high thermal conductivity of CF. The time elapsed for the composite specimen, loaded with a constant weight, to break off after the oxy‐acetylene flame bursts onto the surface of the specimen was employed as an index for an integrated assessment of the ablation properties, simultaneously taking into consideration the mechanical strength of the char and the rate of decomposition. The elapsed time increased in the order of: HTV < HTV/CF ≈ HTV/MMTS₄ < HTV/CF/MMTS₄ ≈ HTV/MMT < HTV/CF/MMT. This order was different from the increasing order of the thermal stability determined by TGA results and the insulation index. The decreased degree of crosslinking of the composites with MMTS₄ compared with that of the composite with MMT may be unfavorable for the formation of a mechanically strong char and could lead to early rupture of the HTV/MMTS₄ specimen. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

添加有机酸水热法制备碱式硫酸镁晶须的研究

以硫酸镁和氢氧化镁为原料水热反应制备碱式硫酸镁晶须[MgSO4.5Mg(OH)2.3H2O],通过正交实验得出制备条件,在此条件下添加有机酸,对不同的有机酸添加剂进行对比,对产物进行SEM,XRD,TG以及FT-IR分析。结果表明:控制硫酸镁浓度为0.70 mol/L,氢氧化镁浓度为0.32 mol/L,反应温度为160℃,搅拌速率600 r/m in,压强0.5 MPa,反应时间6 h,原料填充度大于60%,有机酸添加量为0.1%~1%(质量分数)。在此条件下可以制得长径比大于60的碱式硫酸镁晶须,产品为单晶纤维状结构。有机酸的加入,作为一种较好的表面处理剂,吸附在产品表面,阻止晶体的团聚,有利于产品的分散,通过小尺寸晶须的团聚,生成大尺寸的晶须产品。     

改性碱式氯化镁晶须/丁苯橡胶复合材料制备与性能研究

以工业活性轻烧氧化镁粉和盐酸为原料,采用水溶液法制备了碱式氯化镁晶须,继而采用硅烷偶联剂对碱式氯化镁晶须进行改性,然后将其与丁苯橡胶混炼得到改性碱式氯化镁晶须/丁苯橡胶复合材料,研究了改性碱式氯化镁晶须对丁苯橡胶力学性能及热学性能的影响。结果表明：采用水溶液法制备得到的碱式氯化镁晶须结构为Mg₂（OH）₃Cl·4H₂O,呈微细纤维状,分布较均匀,长径比大于20;改性碱式氯化镁晶须的加入,可以改善丁苯橡胶的机械强度和阻燃性能。     

Cure characteristics,morphology, mechanical properties,and aging characteristics of silicone rubber/ethylene vinyl acetate blends

Silicone rubber/ethylene vinyl acetate (SR/EVA) rubber mixes with different ratios were prepared by using dicumyl peroxide (DCP) and benzoyl peroxide (BP) as curing agents. The vulcanization characteristics such as cure kinetics, activation energy, and cure rate of the blends were analyzed. The effects of blend ratio and curing agents on the mechanical properties such as stress–strain behavior, tensile strength, elongation at break, tear strength, relative volume loss, hardness, flex crack resistance, and density of the cured blends have been investigated. Almost all the mechanical properties have been found to be increased with increase in EVA content in the blends particularly in DCP‐cured systems. The increment in mechanical properties of the blends with higher EVA content has been explained in terms of the morphology of the blends, attested by scanning electron micrographs. Attempts have been made to compare the experimental results, from the evaluation of mechanical properties, with relevant theoretical models. The aging characteristics of the cured blends were also investigated and found that both the DCP‐ and BP‐cured blends have excellent water and thermal resistance. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1069–1082, 2006     

Synthesis of a pyrene-functionalized hyperbranched polyethylene ternary copolymer for efficient graphite exfoliation in chloroform and formation of ethylene-vinyl acetate/graphene nanocomposites

A strategy for preparing ethylene-vinyl acetate (EVA)/graphene nanocomposites from liquid-phase exfoliated graphene has been explored with the use of a pyrene-functionalized hyperbranched polyethylene (HBPE) ternary copolymer, HBPE@Py@PMA, as stabilizer for graphite exfoliation. The HBPE@Py@PMA was synthesized by combining the Pd-diimine-catalyzed chain walking ternary ethylene copolymerization and atomic transfer radical polymerization techniques and has been confirmed to possess a HBPE core simultaneously bearing pyrene terminal groups and polymethacrylate side chains. As stabilizer, it is found to effectively promote graphite exfoliation in CHCl₃ to render high-quality few-layer graphene with an efficiency as high as 43%. Meanwhile, it can be steadily adsorbed on the exfoliated graphene surface to concurrently render functionalized graphene well dispersible in EVA matrix with strong interfacial interactions. This allows us to obtain EVA/graphene nanocomposites from resulting graphene dispersion through simple solution mixing process. By adding only 0.5 wt% of graphene, the dielectric constant of resulting composite increases by 55% compared to pure EVA, with a dielectric loss only 0.012. The role mechanism of the HBPE@Py@PMA for promoting graphite exfoliation in CHCl₃ and the formation of EVA/graphene nanocomposites from the resulting graphene has been proposed.     

硅橡胶隔热复合材料的制备及性能

采用空心玻璃微珠（HGB）和膨胀蛭石（EVMT）作为隔热填料,分别与高温硫化硅橡胶（HTV）共混制备HGB/HTV和EVMT/HTV隔热复合材料,并考察了隔热填料的种类和用量对隔热复合材料的隔热性能和力学性能的影响。结果表明,随着HGB和EVMT用量的增加,隔热复合材料的导热性能明显下降。相比于HTV试样,当HGB与HTV的质量比为20/100,EVMT与HTV的质量比为10/100时,隔热复合材料的导热系数分别下降了20.44%和12.34%。HGB和EVMT均能提高HTV隔热复合材料的100%定伸应力和邵尔A硬度,降低其拉伸强度与扯断伸长率。当HGB与HTV的质量比为20/100,EVMT与HTV的质量比为10/100时,隔热复合材料的拉伸强度分别为10.51 MPa和11.59 MPa,邵尔A硬度分别为71.6和59.1。     

Remarkable effects of silicone rubber on flame retardant property and mechanical properties of crosslinked high-density polyethylene/bio-based magnesium phosphate flame retardant (MHPA) composite

In this paper, a new bio-based flame retardant MHPA was prepared by the reaction of magnesium hydroxide (MH) and phytic acid (PA). Then the crosslinked high-density polyethylene (HDPE) flame-retardant composite was prepared by adding it and silicone rubber (SR) into HDPE and using electron beam irradiation. The test results of limiting oxygen index (LOI) and cone calorimeter test (CCT) show that the combination of MHPA and SR can increase the flame retardancy and smoke suppression performance of HDPE. The LOI of HDPE composite with 10 parts of SR is 28.3%, and its pHRR, THR and TSP values are reduced to 454.1 kW/m², 99.7 MJ/m² and 8.3 m², respectively, which is because MHPA and SR jointly promote the formation of continuous and high-density carbon slag in the combustion process of HDPE and inhibit the penetration of flame. In addition, the HDPE composite with 10 parts of SR has significant tensile strength, elongation breaking strength and tear strength, because SR can produce continuous stable structure with HDPE after irradiation and crosslinking. Therefore, this study verified that MHPA and SR together can effectively improve the flame retardancy, smoke suppression and mechanical properties of HDPE composite.     

Improving the transient thermal response and ablation properties of epoxy-modified silicone rubber composites by adding fluxing agent

In this work, transient thermal response and ablation behavior of liquid silicone rubber composites containing fluxing/ceramic forming fillers were investigated under different heat flows using an oxyacetylene flame. The results indicated that the introduction of zinc borate (ZB) and aluminum oxide (Al₂O₃) effectively reduced the temperature at various depths of the samples, and they improved the thermal insulation properties and lowered pyrolysis rates. The above finding was attributed to the heat absorption arising from water release and melt filling as well as the vitrified reaction of solid melt due to the decomposition of ZB. Besides, the melting and exfoliation of Al₂O₃ and the formation of aluminum silicate (Al₂SiO₅) caused heat absorption effect. Additionally, the mass ablation rates and line ablation rates increased with rising heat flows coupling with a decrease of compressive strength of the char layers. In a nutshell, the effect of adding ZB/Al₂O₃ on the thermal insulation behavior of epoxy-modified vinyl silicone rubber (EMVSR) composites under different heat flows was elucidtaed. This work served as a reference for the design and preparation of flexible ablative materials for thermal protection applications.     

纤维素醋酸酯与聚乳酸接枝共聚物的结构与性能表征

为改善纤维素醋酸酯的热加工性能,以辛酸亚锡为催化剂,通过丙交酯的开环接枝聚合反应,制备了纤维素醋酸酯和聚乳酸接枝共聚物(CDA-g-PLA),利用FTIR、1H NMR、DSC、XRD和TG对其结构和性能进行表征。结果表明,共聚物中存在聚乳酸支链,产物为纤维素醋酸酯与聚乳酸的接枝共聚物;柔性聚乳酸支链的引入,接枝共聚物的玻璃化温度大幅降低,热加工性能得到显著的改善。     

Mechanical and sorption properties of poly(ethylene-co-vinyl acetate)(EVA) compatibilized acrylonitrile butadiene rubber/natural rubber blend systems

Poly (ethylene-co-vinyl acetate) (EVA) has been used as a compatibilizer for heterogeneous natural rubber/acrylonitrile butadiene rubber (NR/NBR) blends. NR/NBR (50/50) blends were compatibilized with varying amounts, from 0 to 10 parts per hundred rubber (phr), of EVA. The compatibility of the blend components in presence of EVA has been evaluated in terms of mechanical and sorption characteristics. The mechanical properties were found to be improved by the addition of EVA upto 6 phr. The solvent resistance of the compatibilized samples has been observed to be higher compared to the uncompatibilized blends; attributed to the increased interfacial adhesion between the blend components. DSC studies showed a shift of glass transition temperatures of the blend components towards higher temperatures indicating increased rigidity of the matrix in presence of EVA.