新型金属-树脂间粘接性单体的合成与应用

甲基丙烯酰氧癸基硫脲嘧啶羧酸酯;粘接性单体;复合树脂;牙用合金;粘接性能     

丙烯酰胺/甲基丙烯酰氧乙基二甲基丙磺酸铵共聚物的合成及其性能

以二甲氨基乙醇和丙烯酰氯为原料,制得丙烯酸二甲胺乙酯（DMAEA）; DMAEA与1,3-丙磺内酯反应制得甜菜碱型乙烯基两性离子单体--甲基丙烯酰氧乙基二甲基丙磺酸铵（MSBM）; MSBM与50%丙烯酰胺水溶液共聚合成了两性聚合物丙烯酰胺/甲基丙烯酰氧乙基二甲基丙磺酸铵(AM/MSBM),其结构经¹H NMR和IR确证。研究了矿化度,剪切作用和温度对AM/MSBM粘度的影响。结果表明：AM/MSBM具有反聚电解质溶液行为。在实验条件（盐水矿化度1 075.9 mg·L^-1,温度45~75 ℃,剪切速率2 000 rpm）下,AM/MSBM的粘度保持率＞90%。模拟驱油实验结果表明,AM/MSBM可提高采收率13.2%。     

(2-甲基丙烯酰氧乙基)三甲基氯化铵-丙烯酰胺反相微乳液共聚合特性研究

选用SPAN80与OP10复合乳化剂、K₂S₂O₈-Na₂SO₃氧化还原引发剂,进行(2-甲基丙烯酰氧乙基)三甲基氯化铵-丙烯酰胺反相微乳液共聚合反应.研究了单体配比、电解质浓度和乳化体系的油水比对共聚物分子量及离子度的影响,考察了该共聚合体系的反应特性.     

双网络结构冻胶堵剂在高温高盐下的性能研究

针对塔河油田高温、高盐等缝洞油藏堵水困难的技术难题,构建了双网络结构的冻胶堵剂体系。以N-(3-二甲胺丙基)甲基丙烯酰胺(DMAPMA)和氯乙酸钠(ClCH₂COONa)为原料合成甜菜碱单体TCJ,与单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)和N-(3-二甲氨基丙基)甲基丙烯酰胺(DMAPMA)共聚合成疏水缔合聚合物CDD。采用矿化度为22×10⁴ mg/L的实际地层水,以0.8%(AM/AMPS)聚合物FZ、1.2%酚醛交联剂、0.15%CDD和0.05%特种交联剂CN-10在130℃条件构建互穿双网络结构冻胶CDD-FZ。冻胶性能测试结果表明,双网络冻胶CDD-FZ,仅3 h就能成胶并且成胶强度为H级,最大屈服应力为326.42 Pa,突破压力为88.19MPa/m,30天脱水率1.14%,较传统单层网络结构冻胶具有更高的强度、耐盐性、耐温性和耐稀释性。该研究填补了塔河油田耐温抗盐高强度堵水冻胶的技术的空白,具备较好的实际应用前景。     

紫外光固化聚多氟烷氧丙基甲基硅氧烷的研究

本文报道几种紫外光敏有机硅单体:(γ-甲基丙烯酰氧)丙基甲基二甲氧基硅烷,1,3,5,7-四(γ-甲基丙烯酰氧丙基)四甲基环四硅氧烷和1,3-双(甲基丙烯酰氧甲基)-1,1,3,3-四甲基二硅氧烷的合成,以及它们与αH,αH,ωH-全氟烷氧丙基甲基环四硅氧烷的开环共聚反应,制备了一系列新型光敏聚多氟烷氧丙基甲基硅氧烷.并初步研究了在紫外光辐照下,这类光敏聚多氟烷氧丙基甲基硅氧烷的化学结构对固化速度的影响.     

有机磷化合物的研究(Ⅳ)——S-烷基S-(N-取代氨基羰甲基)乙基三硫代磷酸酯的合成

应用乙基二硫化磷可制取O-烷基乙基二硫代膦酸酯^[1];从而可以进行此类杀虫剂的合成^[2].G.Schrader先后合成S,S-(3,4二氯苯基)三硫代乙基膦酸酯及S-乙基S-乙硫乙基三硫代甲基膦酸酯,生物试验证明它们是很好的杀虫剂,且对温血动物毒性低^[3].我们对乙基三硫代膦酸酯的制备进行了一些试验,最后以乙基三硫代膦酸铵和N-取代α-氯代乙酰胺反应,制取S-烷基S-(N-取代氨基羰甲基)乙基三硫代膦酸酯.     

一种两性三元共聚物的合成

选用聚乙二醇二丙烯酸酯(PEGDA)为扩链剂,以丙烯酰胺(AM)、2-甲基-2-丙烯酰胺基丙磺酸(AMPS)、甲基丙烯酰氧乙基三甲基氯化铵(DMC)为主单体,采用水溶液聚合方法合成了两性三元共聚物AM/AMPS/DMC;测定了共聚物的性能,并利用红外光谱研究了其分子结构.结果表明,所合成的共聚物具有良好的耐酸和高温稳定性,以及高抗剪切率.     

6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪及其共聚物的合成

以6-甲基-3-羟乙基-3,4-2H-1,3-苯并噁嗪(MB-OH)和甲基丙烯酰氯为原料, 通过酯化反应合成了6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪(MBEM). 采用自由基溶液聚合法, 以偶氮二异丁腈(AIBN)为引发剂, 以甲苯为溶剂, 以MBEM与N-苯基马来酰亚胺(NPMI)为单体, 合成了6-甲基-3-甲基丙烯酰氧乙基-3,4-2H-1,3-苯并噁嗪-co-N-苯基马来酰亚胺共聚物[P(MBEM-co-NPMI)]. 分别对MB-OH, MBEM, P(MBEM-co-NPMI)进行加热固化, 得到相应的交联聚合物PMB-OH, PMBEM和P[P(MBEM-co-NPMI)]. 对其结构、分子量和热性能进行了表征. 结果表明, PMB-OH, PMBEM, P[P(MBEM-co-NPMI)]的最大损耗因子tanδ_max对应的玻璃化转变温度(T_g)分别为92, 129和181℃, 最大损耗模量G"_max对应的T_g分别为56, 91和156℃. 在N₂气氛围下, PMB-OH, PMBEM, P[P(MBEM-co-NPMI)]失重5%的温度分别为257, 244和260℃; 失重10%的温度分别为280, 266和284℃; 800℃的残炭率分别为23.2%, 17.8%和14.0%. 表明P[P(MBEM-co-NPMI)]具有优异的耐热性能.     

直接氟化表面处理超高分子量聚乙烯粘接性能研究

采用直接氟化处理新技术对板材进行了表面处理,明显增强其可粘性,与环氧黏合剂粘接的剪切强度可达4.72 MPa,且氟化处理后样品在室温环境放置1个月后,与环氧粘接的剪切强度基本保持不变.扫描电镜结果显示,氟化后UHMWPE板材表面形貌结构并未发生明显变化.接触角测试发现氟化后UHMWPE表面极性部分明显增加,表面能由30...     

N-羟基-1,6-亚甲基桥[10]轮烯-3,4-酰亚胺/乙酸钴液相催化氧化3-甲基吡啶制备烟酸

以1,6-亚甲基桥[10]轮烯-3,4-二甲酸酐为原料,与羟胺基盐酸盐经酰化和脱水反应制得N-羟基-1,6-亚甲基桥[10]轮烯-3,4-酰亚胺(2);构建了2/乙酸钴催化体系,以氧分子为氧源,乙腈为溶剂,在1 MPa氧气压力下于120℃反应20 h,氧化3-甲基吡啶制备烟酸,产率70%,其结构经~1H NMR和IR确证。     

Effect of micro-arc oxidation treatment on laser joint microstructures of Ti-6Al-4V alloy/CFRP

Resin-based carbon fibre reinforced composite (CFRP) with excellent properties has been widely applied in aerospace industry. In this study, polyether ether ketone enforced composite (PEEK-CFRP) and Ti-6V-4V titanium alloy had been joined by laser welding process. Micro-arc oxidation (MAO) process was conducted on the surface of titanium alloy to improve the joint property. Fractures and mechanical properties of joints were analysed. Interfacial microstructures of the joints had been investigated, and the formation mechanism of joint had been figured out. The results showed that after MAO treatment, the joint strength had been greatly improved and the shear strength reached to 42.3 MPa compared with pretreated sample. The wettability of CFRP on titanium alloy was rising with the contact angle of 68.8°. Fracture showed that cohesive failure contributed to the main fracture mode. As joints were formed by both mechanical bonding and chemical bonding, ‘anchor-shaped’ structures were found in the joint to enhance the mechanical bonding effects due to the flowing of the melted resin. (−OH) bonds were identified at the surface of MAO-treated titanium alloy that provided conditions for hydrogen bond interaction. TiO₂, TiO and Ti–V–C phase were found at interface, whereas Ti–F and Ti–O–F bonds were generated during the welding process, which made great contribution to the chemical bonds between titanium alloy and CFRP.     

含磷有机硅杂化环氧树脂固化体系性能研究

通过磷酸与γ-环氧丙氧基三甲氧基硅烷反应得到含磷有机硅氧烷,并加入到环氧树脂/4,4'-二氨基二苯基甲烷体系中混合,通过溶胶-凝胶的方法制备了含磷有机硅杂化环氧树脂固化物.对固化体系进行了玻璃化转变温度、热失重、阻燃、拉伸强度、冲击强度测试分析.结果表明,该固化体系的阻燃性得到提高,极限氧指数在25.8～29.3,玻璃化转变温度得到提高,在161～179℃;虽然初始分解温度比纯环氧树脂固化物低,但800℃残炭率可以达到26.5%,提高了36%;拉伸强度得到提高,在71～94 MPa,冲击强度可以达到14.36 kJ/m2,提高了14%.该固化体系具有较好的阻燃性能和热性能,同时具有较好的力学性能.     

五种植物纤维粉填充不饱和聚酯树脂复合材料的性能对比

以芝麻秸秆粉、水稻秸秆粉、玉米芯秆粉、菠萝叶粉、甘蔗渣粉五种不同植物纤维粉为填充体、不饱和聚酯树脂(UPR)为基体制作植物纤维粉/UPR复合材料,对比研究了秸秆种类对复合材料密度、力学性能及吸水性能的影响。结果表明,植物纤维粉粒径为100目、添加量为UPR用量的10%时,芝麻秸秆粉/UPR复合材料的综合力学性能最好,拉伸强度、弯曲强度和冲击强度分别为41.320 MPa、67.467 MPa和2.815 KJ/m^2,且每一浸泡阶段吸水率均最低。     

Ethylene Oligomerization to Low Carbon Olefins by a Zirconium Complex Incorporating 8—Quinolinolato Ligands at a Low Al／Zr Ratio

Bis (8-quinolinolato) zirconium dichloride (Ox)2ZrCl2(Ox^-=8-quinolinolato) was found active for ethylene oligomerization with a high selectivity of 84-94% to C4-C10 olefins at 70-100℃ under the pressure of 1.8MPa using Et2AlCl as a co-catalyst (Al/Zr=60).     

钇,铈对低铪镍基K444返回合金组织与力学性能的影响

研究了Y,Ce对含铪(Hf)镍基铸造高温合金K444返回料(添加50%返回料)合金的力学性能和组织的影响.研究结果表明:适量Y,Ce(Y<0.03%,Ce<0.015%(质量分数))添加到返回料合金后,一方面,Y,Ce具有去除N,O等有害杂质的作用,使O含量由15×10~(-6)降低到8×10~(-6),N含量由35×10~(-6)降低到18×10~(-6),从而使返回料合金得到净化.另一方面,Y,Ce细化了枝晶组织,减少了共晶和大块状碳化物数量,并且强化了晶界.和未加Y,Ce的返回料合金相比.添加Y,Ce使返回料合金室温拉伸强度提高约100 MPa,塑性提高近一倍;使900℃的高温瞬时拉伸性能波动较为平稳,塑性提高近一倍.添加Y,Ce还可以提高返回合金900℃/274 MPa条件下的持久性能,达到新料水平;可以明显延长K444返回合金900℃/274 MPa条件下的蠕变第二阶段,提高蠕变寿命.     

Preparation and Characterization of Si3N4-TiN Nanocomposite via in situ Co-deposition in Liquid Ammonia

"A new method of TiN/Si3N4 nanocomposite synthesis was described and tested. TiCl4 and SiCl4 used as the starting materials and sodium as the reduction agent were conducted in liquid ammonia respectively. TiCl4 and SiCl4 were reduced simultaneously and titanium nitride/silicon nitride nanocomposite powderswere obtained by in situ co-deposition at temperatures around ~ 45 oC. X-ray diffraction patterns indicate that the product was amorphous and the by-product was sodium chloride. The product powders were heated up to 1600 oC and crystallization to TiN and fi-Si3N4 happened. Due to presence of TiN, the crystallization of silicon nitride in the mixture was later than that of pure silicon nitride. Transmission electron microscopy images show the average size of powders range from 10 nm to 40 nm and scanning electron microscopy images conformed that Ti and Si elements were dispersed uniformly. A green bulk nitride composite containing 20%TiN with the mean grain size of 100-300 nm and fracture toughness of 10.1§1.1 m1=2MPa , was obtained by spark plasma sintering at 1500-1600 oC. The effect of TiN additiven microstructure and mechanical properties of composite bulk was discussed."     

Highly Efficient Degradation of Thiophosphate Pesticides Catalyzed by Cyclopalladated Ferrocenylketimines

Thiophosphoric acid esters pesticides such as parathion, methyl parathion, with an annual world production of hundred thousands of tons, are powerful pollution sources and their remains in the environment is a recognized ecological threat1. Creation of 揼reen拻 catalytic processes for degradation of thiophosphoric acid esters is therefore an urgent task of contemporary chemical technology and biotechnology. Significant progress has been made by the use of organophosphate hydrolases (OPH), a…     

Syntheses of biodegradable polymer networks based on polycaprolactone and glutamic acid

Biodegradable trifunctional oligomer was synthesized from polycaprolactone and glutamic acid and characterized by Fourier‐transform infrared (FTIR) and proton nuclear magnetic resonance (¹H NMR) spectroscopies. Injectable and in situ crosslinkable polymer networks were fabricated by the copolymerization of oligomer with triethylene glycol dimethacrylate (TEGDMA) and used to evaluate the initial compressive strengths, viscosities, shrinkages, thermal stabilities, and biodegradabilities in the forms of polymer network neat resin and their composites with β‐tricalcium phosphate. The initial compressive strengths (CS) values of neat resins ranged from 9.54 to 187.6 MPa. Both neat resins and composites had polymerization shrinkage ranging from 0% to 11.7%, which increased with increasing of TEGDMA contents in resin. Moreover, in polymer composite resins, shrinkage values decreased with increasing filler level from 0% to 4.6%, and exothermic evolution values decreased from 33.5°C to 29.7°C as increasing filler level. The composite with the formulation of (polycaprolactone)‐glutamate triacrylate (PCLGTA)/TEGDMA (25/75) and powder/liquid (P/L) ratio of 1.0 exhibited the highest exothermal and lowest shrinkage values. The increase of oligomer in the formulation led to an increase in viscosity.     

Syntheses and evaluation of novel biodegradable amino acid based anhydride polymer resins and composites

A novel synthetic biodegradable oligomer based upon methacrylated aminocaproyl maleamic acid (MACMA), was synthesized and characterized. Injectable and in situ crosslinkable polymer networks were formulated by copolymerization of MACMA with triethyleneglycol dimethacrylate (TEGDMA). In addition, composites composed of MACMA, TEGDMA and beta-tricalcium phosphate (β-TCP) were prepared. The networks and composites were initiated by photo- and redox-polymerization, respectively. The initial compressive (CS) and diametral tensile strengths (DTS) of these materials were determined and used to evaluate the effects of MACMA/TEGDMA ratios on the degradation behavior of the materials. The neat resin networks exhibited initial CS values ranging from 6.7 to 284.2 MPa and the composites demonstrated initial DTS values ranging from 2.8 to 20.8 MPa and CS values ranging from 19.1 to 119.5 MPa. During the course of degradation the polymer neat resins lost 51%, 69% and 61% of their initial CS after 3 weeks for the MACMA/TEGDMA ratios at 25/75, 50/50 and 75/25, respectively. The resin with the MACMA/TEGDMA ratio of 75/25 completely degraded after 6 months. The composite with the MACMA/TEGDMA ratio of 25/75 exhibited a significant increase in CS after an initial decrease for 7 days and then lost 57% of its initial CS after 3 months. The composite composed of poly(MACMA) homopolymer showed a complete degradation after 21 days.     

Surface modification of titanium alloy with the Ti3Al + TiB2/TiN composite coatings

Laser cladding of the Ti₃Al + TiB₂ pre‐placed alloy powder on the Ti–6Al–4 V alloy in nitrogen protective atmosphere can form the Ti₃Al + TiB₂/TiN composite coating, which can dramatically improve the wear resistance of the Ti–6Al–4 V alloy surface. In this study, the Ti₃Al + TiB₂/TiN composite coatings on the Ti–6Al–4 V alloy have been researched by means of X‐ray diffraction, SEM and energy dispersive spectrometry. It was found that there is a metallurgical combination between the Ti₃Al + TiB₂/TiN composite coating and the substrate. The microhardness of the Ti₃Al + TiB₂/TiN composite coatings were 3 ~ 4 times higher than that of the Ti–6Al–4 V alloy because of the actions of the Ti₃Al + TiB₂/TiN hard phases and the grain refinement strengthening. Moreover, the wear mass losses of the Ti₃Al + TiB₂/TiN composite coatings were much lower than that of the substrate. Copyright © 2011 John Wiley & Sons, Ltd.