新型补强固结灌浆材料 丙烯酸环氧酯灌浆材料的研究

一、引言丙烯酸环氧酯树脂(Epoxy-Acylate Resins)是环氧树脂和不饱和一元酸的加成物,有时又称乙烯基酯树脂(Vinyl Esters),是六十年代出现的一种新型热固性树脂。它结合了环氧树脂和不饱和聚酯树脂的优点,成为一种有发展前途的新型树脂。环氧树脂具有粘结力强,机械、电绝缘和耐腐蚀性能好等一系列优点,但也存在一些缺点,如树脂本身粘度大,不易操作;当加入稀释剂后其性能明显降低,树脂的固化     

聚酯纤维布混杂增强环氧树脂可钻复合材料的制备与性能研究

采用聚酯纤维布与碳纤维、Kevlar纤维分别混杂增强环氧树脂,制备满足油田开发的可钻桥塞用高性能复合材料。分别采用液体芳胺(DETDA)与固体芳胺(DDM)作为固化剂,两种材料有着相近的玻璃化转变温度和力学强度。以DETDA固化的树脂基体中,活性环氧稀释剂用量增加,拉伸强度变化不大,但材料的弹性模量在10%稀释剂用量时,达到最大值;树脂交联密度1000/Mc为2.35时,材料的模量和拉伸强度都处于相对较大值。聚酯纤维/Kevlar纤维和聚酯纤维/碳纤维混杂增强环氧树脂复合材料的模量和强度,分别随着Kevlar纤维和碳纤维含量的增加而增加,有碳纤维的复合材料拉伸强度增加较大,断裂伸长率相对较小。实验显示:聚酯纤维混杂增强复合材料具有较好的可钻性,在钻压为1.5吨,钻速为32转/分的条件下,磨铣速度为4 mm·min~(-1)。     

丙烯酸环氧酯树脂灌浆材料的研究

丙烯酸环氧酯树脂(Epoxy-acrylate resins)是六十年代出现的一种新型热固性树脂,它结合了环氧树脂和不饱和聚酯树脂的优点,成为一种很有发展前途的新型树脂。环氧树脂具有粘结力强,机械性能好,电绝缘性能和耐腐蚀性能好等一系列优点,但也存在一些缺点,如树脂本身粘度大,不易操作,加入稀释剂则其性能明显下降;树脂的固化过程不易控制,一般固化时间较长等。不饱和聚酯树脂虽然性能不如环氧树脂,但它却有很好的操作性能和固化性能。丙烯酸环氧酯树脂就是一种既保持环氧树脂的优良性能,并使之具有不饱和聚酯的优良操作性能和固化性能的新型树脂。最常用的丙烯酸环氧酯树脂是双酚A型环氧树脂的丙烯酸酯,具有下式结构:     

活性稀释剂苄基缩水甘油醚丙烯酸酯的合成及性能表征

本文以苄基缩水甘油醚和丙烯酸为原料合成活性稀释剂苄基缩水甘油醚丙烯酸酯(BGEA),研究了反应温度、催化剂和阻聚剂用量对反应的影响.结果表明最佳的反应条件为:反应温度110℃左右,催化剂N,N’-二甲基苄胺质量分数为0.9%,阻聚剂对甲氧基苯酚质量分数为0.2%.后将BGEA作为稀释剂加入到双酚A型环氧丙烯酸树脂中配制成光固化涂料,利用TG、AFM等表征手段对光固化膜的热性能、表面形貌及物理机械性能进行研究.     

紫外光固化脂环族环氧丙烯酸酯涂料的制备及性能

通过丙烯酸（AA）与脂环族环氧树脂的开环反应合成了可紫外光（UV）固化的脂环族环氧丙烯酸酯树脂（CEA）。采用红外光谱（FT-IR）对树脂结构进行了表征,研究了反应温度、反应时间对产率的影响。用活性稀释剂与CEA制备了涂料预聚物,用转板黏度计测定了预聚物的黏度,采用差示扫描量热（DSC）仪、综合热分析仪和铅笔硬度计对树脂固化膜进行了分析。结果表明：当丙烯酸与环氧基团摩尔比为1.03,120°C下反应25.8 h时,反应转化率可达96.58%。CEA固化膜的玻璃化转变温度为64°C,初始分解温度为314°C,活性稀释剂的加入增强了固化膜的耐热性,固化膜铅笔硬度可达6H。     

原位法制备纳米银修饰碳纳米管环氧导电复合材料

将碳纳米管(CNTs)和乙酸银同时引入到环氧树脂-咪唑固化体系中,在固化过程中原位热降解银-咪唑复合物生成纳米银修饰碳纳米管,差示扫描量热仪(DSC)表明改性碳纳米管对环氧固化有一定的促进作用.采用X-射线衍射(XRD)表征了乙酸银和咪唑配合物[Ag(2E4MZ)2]Ac的结构,并提出了原位降解生成纳米银的机理.XRD结果表明,单独的乙酸银-咪唑配合物热降解生成的纳米银粒径为21-24nm,而配合物在环氧基体中生成的纳米银粒径为11-13nm.添加80%(质量分数)片状微米银粉制备的纳米银/碳纳米管环氧导电复合材料其体积电阻率低达9×10-5Ω·cm.当纳米银和碳纳米管质量比为80:20时,复合材料导电性和剪切强度达到最佳;采用扫描电镜(SEM)表征了复合材料的形貌结构.     

苯并噁嗪改性液体成型环氧树脂的研究

采用具有低固化收缩特性的苯并噁嗪树脂(benzoxazine,BOZ)对液体成型环氧树脂进行改性,以期在不改变液体成型树脂耐热性、工艺性及力学性能的前提下,大幅度降低树脂的固化收缩率.对比研究了不同BOZ含量改性树脂的固化收缩特性、固化反应特性、液体成型工艺性及力学性能.并采用真空辅助树脂浸渗(vacuum assisted resin infusion,VARI)工艺制备了单向碳纤维织物增强复合材料,研究了复合材料的力学性能.结果表明,加入BOZ对液体成型树脂的反应性、工艺性及耐热性影响不大,改性树脂的固化收缩随BOZ含量的提高逐渐减小,其中BOZ质量分数为15 wt%的改性树脂,较未改性树脂的固化收缩减小约80%,拉伸强度提高约19%,冲击强度提高约148%.以此改性树脂作为基体的复合材料相对于未改性树脂复合材料的拉伸强度提高约23%,层间剪切强度提高约9%,具有良好的力学性能和界面结合性能.     

双官能团液体脂环族环氧化合物的合成与性能

脂环族烯烃类化合物经过环氧化反应制备了三种液体脂环族环氧化合物 ,即 3,4 环氧环己基甲基 2′ ,3′ 环氧环己醚 (Ⅰe ) ,双 (2 ,3 环氧环己基 )醚 (Ⅱe )和双 (2 ,3 环氧环己烷 ) (Ⅲe ) .反应收率大于 80 % .用红外光谱、核磁共振谱、元素分析、环氧当量测定等方法证实了它们的结构 .三种环氧化合物在固化前都具有很低的粘度 (<10 0mPa·s ,2 5℃ ) ,用酸酐类固化剂热固化后得到的交联聚合物具有高的玻璃化转变温度 (Tg=15 0～ 180℃ )、低的线性热膨胀系数 (α1 =6 .0× 10 - 5 ～ 7.6× 10 - 5 ℃ ,α2 =14.5× 10 - 5 ～ 17.0× 10 - 5 ℃ )和较高的储存模量 (E′1 =2 .1～ 3.0GPa ,E′2 =0 .0 2 0～ 0 .0 33GPa) ,它们的总体性能好于国外同类产品ERL 42 2 1.在涂料、电子封装料等方面具有良好的应用前景     

氨酯键扩链改性的669稀释剂对环氧树脂力学性能影响研究

制备了氨酯键扩链改性的669稀释剂UE6M,考察了加入不同用量的UE6M对环氧树脂进行稀释后环氧树脂混合体系的粘度变化。使用氰乙基化三乙烯四胺作为固化剂对环氧树脂混合体系进行固化,研究了UE6M的用量对环氧树脂混合体系固化物性能的影响。研究结果表明,UE6M对E51环氧树脂具有较好的稀释效果,且混合体系固化产物的韧性较纯环氧树脂固化物明显增强:UE6M用量为30%和40%的混合体系粘度仅为纯E51环氧树脂粘度的6.35%和1.43%,但其固化物的拉伸强度均在60MPa以上,分别为纯E51环氧树脂固化物的87.9%和80.9%。断裂伸长率均为纯环氧树脂固化物的8倍以上,弯曲应变为纯环氧树脂固化物2倍以上,弯曲强度及弯曲模量等未出现大幅下降,UE6M稀释剂加入环氧树脂后固化产物的韧性得到明显增强。     

4-苯乙炔基苯胺封端聚酰亚胺树脂的合成与性能研究

使用4-苯乙炔基苯胺(4-PEA)作为反应性封端剂,和3,3′,4,4′-二苯醚四酸二酐(ODPA),3,3′,4,4′-联苯四酸二酐(BPDA),1,4-双(4′-氨基-2′-三氟甲基苯氧基)苯(BTPB)和3,4′-二氨基二苯醚(3,4-′ODA)反应合成了系列4-苯乙炔基苯基封端的聚酰亚胺低聚物,对低聚物的化学结构、热性能和熔体粘度以及固化后树脂的热性能等进行了研究.实验结果表明,低聚物均具有一定的结晶性,含有ODPA的聚酰亚胺低聚物较之含有BPDA的低聚物具有更低的熔体粘度,且出现最低熔体粘度的温度更低;固化后的树脂表现出良好的热性能,含有BPDA的树脂具有更高的玻璃化转变温度;系列低聚物中二胺单体的比例对于低聚物的熔体粘度和固化后树脂的热稳定性有一定影响.     

Preparation and characterization of bismaleimide/1,3-dicyanatobenzene modified epoxy intercrosslinked matrices

An intercrosslinked network of cyanate ester (CE)-bismaleimide (BMI) modified epoxy matrix system was made by using epoxy resin, 1,3-dicyanatobenzene and bismaleimide (N,N^′-bismaleimido-4,4^′-diphenyl methane) with diaminodiphenylmethane as curing agent. BMI-CE-epoxy matrices were characterised using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and heat deflection temperature (HDT) analysis. The matrices, in the form of castings, were characterised for their mechanical properties such as tensile strength, flexural strength and unnotched Izod impact test as per ASTM methods. Mechanical studies indicated that the introduction of cyanate ester into epoxy resin improves the toughness and flexural strength with reduction in tensile strength and glass transition temperature, whereas the incorporation of bismaleimide into epoxy resin influences the mechanical and thermal properties according to its percentage content. DSC thermograms of cyanate ester as well as BMI modified epoxy resin show an unimodal reaction exotherm. Electrical properties were studied as per ASTM method and the morphology of the BMI modified epoxy and CE-epoxy systems were studied by scanning electron microscope.     

Effect of new nonionic curing agent on curing kinetics and mechanical properties of epoxy resin

The current research work presents a novel nonionic curing agent (AEDA) synthesized by utilizing ethylene glycol diglycidyl ether (EGDE), 3,4-dimethoxyaniline (DI), and triethylenetetramine (TETA). Infrared spectroscopy and nuclear magnetic resonance spectroscopy were used to characterize the structure of AEDA curing agent. Non-isothermal scanning calorimetry was used to determine the activation energy and curing conditions of epoxy resin in the curing process. An impact testing machine, a tensile testing machine and a scanning electron microscope (SEM) were used to analyze the impact strength, tensile strength, bending strength, and micromorphology of the AEDA/E-51 system with different mass ratios. The results show that AEDA is an effective high-temperature curing agent. For the AEDA/E-51 system with the optimal mass ratio of 10:100, the best curing temperature is 92.15°C, and the post-curing temperature is 135.65°C. Furthermore, the apparent activation energy (E_a) of 1670 J/mol, the pre-exponential factor (A) of 3.7 × 10^?4, and the reaction series (n) value of 0.76 are obtained for the AEDA/E-51 system. The impact strength of AEDA/E-51 epoxy resin polymer is 7.82 kJ/m², tensile strength is 14.2 MPa, and bending strength is 18.92 MPa. The micromorphological results of the AEDA/E-51 system are consistent with the results of DSC test and mechanical properties test. Hence, this study provides theoretical support for the practical applications of AEDA as curing agent.     

Effect of Epoxy Resin on the Thermal,Mechanical and Rheological Properties of Polybutylene Terephthalate/Glycidyl Methacrylate Functionalized Methyl Methacrylate-butadiene Blend

Epoxy resin was used to modify polybutylene terephthalate(PBT) and glycidyl methacrylate functionalized methyl methacrylate-butadiene(MB-g-GMA) blend. Results show that MB-g-GMA dispersed in PBT matrix uniformly and PBT/MB-g-GMA/epoxy blends reveal good compatibility. However, the added epoxy resin restricted the mobility of PBT macromolecular chains during the growth process of the crystal, which reduced the final crystallinity of PBT. The PBT/MB-g-GMA blend containing 1%(mass fraction) epoxy resin exhibited good mechanical properties. For example, the notched impact strength of the PBT/MB-g-GMA blend with 1%(mass fraction) epoxy resin was about 2 times that of PBT/MB-g-GMA blend. Sanning electron microscope(SEM) results show that the shear yielding of the PBT matrix and the cavitations of rubber particles were the major toughening mechanisms. The chemical reaction between PBT and epoxy resin induced the high complex viscosity and storage modulus of PBT/MB-g-GMA blend.     

Development of toughened bio‐based epoxy with epoxidized linseed oil as reactive diluent and cured with bio‐renewable crosslinker

In the current work, renewable resourced toughened epoxy blend has been developed using epoxidized linseed oil (ELO) and bio‐based crosslinker. Epoxidation of linseed oil was confirmed through FTIR and ¹H NMR spectra. The ELO bio‐resin was blended at different compositions (10, 20, and 30 phr) with a petroleum‐based epoxy (DGEBA) as reactive diluent to reduce the viscosity for better processibility and cured with cardanol‐derived phenalkamine to overcome the brittleness. The flow behavior of the neat epoxy and modified bio‐epoxy resin blend systems was analyzed by Cross model at low and high shear rates. The tensile and impact behavior studies revealed that the toughened bio‐epoxy blend with 20 to 30 phr of ELO showed moderate stiffness with much higher elongation at break 7% to 13%. Incorporation of higher amount of ELO (20 to 30 phr) increases enthalpy of curing without affecting peak temperature of curing. The thermal degradation behavior of the ELO based blends exhibits similar trend as neat epoxy. The higher intensity or broadened loss tangent curve of bio‐epoxy blends revealed higher damping ability. FE‐SEM analysis showed a rough and rippled surface of bio‐based epoxy blends ensuring effective toughening. Reduced viscosity of resin due to maximum possible incorporation of bio‐resin and use of phenalkamine as curing agent leads to an eco‐friendly toughened epoxy and can be useful for specific coating and structural application.     

Thermal,mechanical, and morphological properties of soybean oil-based polyurethane/epoxy resin interpenetrating polymer networks (IPNs)

A series of interpenetrating polymer networks (IPNs) based on epoxy (EP) resin and polyurethane (PU) prepolymer derived from soybean oil-based polyols with different mass ratios were synthesized. The structure, thermal properties, damping properties, tensile properties, and morphology of soybean oil-based PU/EP IPNs were characterized by Fourier-transform infrared spectroscopy, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), universal test machine, and scanning electron microscopy (SEM). DSC and DMA results show that the glass transition temperature of the soybean oil-based PU/EP IPN decreases with the increase of PU prepolymer contents. Soybean oil-based PU/EP IPNs have better damping properties than that of the pure epoxy resin. The tensile strength and modulus of PU/EP IPNs decrease, while elongation at break increases with the increase of PU prepolymer contents. SEM observations reveal that phase separation appears in PU/EP IPNs with higher PU prepolymer contents.     

The curing kinetics and mechanical properties of epoxy resin composites reinforced by PEEK microparticles

In this paper, a polyether-ether-ketone (PEEK)/epoxy composite was prepared by using PEEK microparticles as the reinforcement. The nonisothermal differential scanning calorimetry (DSC) test was used to evaluate the curing reaction of PEEK/epoxy resin system. The curing kinetics of this system were examined utilizing nonisothermal kinetic analyses (Kissinger and Ozawa), isoconversional methods (Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose) and an autocatalytic reaction model. During these analyses, the kinetic parameters and models were obtained, the curing behavior of PEEK/epoxy resin system under dynamic conditions was predicted. The results show that isoconversional methods can adequately interpret the curing behavior of PEEK/epoxy resin system and that the theoretical DSC curves calculated by the autocatalytic reaction model are in good agreement with experimental data. Furthermore, the tensile elongation at break, tensile strength, flexural strength, compression strength and compression modulus increased by 81.6%, 33.66%, 36.53%, 10.98% and 15.14%, respectively, when PEEK microparticles were added in epoxy resin composites.     

Kinetics of curing and thermal degradation of hyperbranched epoxy (HTDE)/diglycidyl ether of bisphenol-A epoxy hybrid resin

Hyperbranched epoxy resin (HTDE) has relatively low viscosity and high molecular mass and holds great promise as a functional additive for enhancing the strength and toughness of thermosetting resins. In this work, the curing and thermal degradation kinetics of HTDE/diglycidyl ether of bisphenol-A epoxy (DGEBA) hybrid resin were studied in detail using differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) techniques by Coats–Redfern model. The effect of molecular mass or generation and content of HTME on the activation energy, reaction order, and curing time were discussed; the results indicated that HTDE could accelerate the curing speed and reduce the activation energy and reaction order of the curing reaction.     

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.     

端羟基丁腈橡胶增韧环氧树脂研究

本文研究了端羟基丁腈橡胶(HTBN)对环氧树脂的增韧作用。加入10—20phr的HTBN,环氧树脂性能可以大幅度提高,粘接碳钢剪切强度30MPa,冲击强度9×10~(-2)J/cm~2,浇注试样抗张强度61MPa,伸长10％,玻璃化温度115℃;不加HTBN的环氧树脂固化物,剪切强度24MPa,冲击强度34×10~(-2)J/cm~2,抗张强度30MPa,伸长5％,玻璃化温度124℃。 本文还通过DSC、SEM研究观察到增韧环氧树脂的两相结构。     

Application of Modified Natural Oils as Reactive Diluents for Epoxy Resins

Bisphenol A based low-molecular-weight epoxy resin was modified with epoxidized soybean oil, which exhibit viscosity reducing ability comparable to commercial grade active diluents. The studied compositions showed a non-Newtonian rheological behavior, typical for Bingham liquids. The values of the flow index (n) and the consistency index (k) for the compositions tested in the temperature range 25–65 °C were calculated from the Ostwald-de Waele rheological model and were used to calculate the flow-activation energy (E_a) using the Arhenius equation. Studies of co-crosslinking of mixed oil-resin compositions using isophorone diamine showed essential decrease of the reaction heat and peak maximum temperature. Mechanical properties, thermal stability, water absorption and chemical resistance of the epoxy resin modified with natural oil, were also investigated. Compositions of epoxy resin Ruetapox 0162, modified with the oil diluent, preserved very good mechanical properties of the epoxy resins and demonstrated relatively low water absorption as well as high chemical resistance. The compositions displayed even higher impact strength than pure epoxy resin due to plasticizing effect of the built-in oil. Compositions with the high contents (up to 60 weight %) of the oil were flexible materials with fast elastic recovery.