测井钻杆用复合材料研制及应用

采用二烯丙基双酚A、F-51酚醛环氧树脂、甲基四氢苯酐、液体端羧基丁氰橡胶改性4,4'-双马来酰亚胺基二苯甲烷(BDM),采用热压罐工艺与玻璃纤维复合为复合材料.性能测试结果表明,该复合材料具有较高的玻璃化温度、极好的断裂延展性、与钢具有很高的粘接强度,很好地满足了测井钻杆的特殊使用要求.     

一种蒽醌基双马来酰亚胺及其胶粘剂的制备

以2，6—二胺蒽醌及顺丁烯二酸酐为原料合成了一种蒽醌基双马来酰亚胺(DEBMI)，以此双马来酰亚胺树脂为主体，以4，4′—双(对氨基苯酮)二苯醚为固化剂，以二烯丙基双酚A为增韧剂，合成耐热胶粘剂，该胶粘剂具有良好的工艺性能和耐热性能。     

双马来酰亚胺和有机硅改性环氧树脂制备与表征

为改善环氧树脂耐疲劳性、耐热性和抗冲击韧性,选用有机硅和双马来酰亚胺对环氧树脂改性。试验使用有机硅对环氧树脂改性,采用4,4'-二氨基二苯甲烷(DDM)对双马来酰亚胺(BMI)进行二元胺扩链改性,再将二者复合,确定了参考配方和技术指标。     

改性环氧树脂的制备及其性能研究

采用二苯甲烷型双马来酰亚胺(BDM)和二甲基二乙氧基硅烷(DMDES)共同改性双酚A型环氧树脂(EP/CYD-127)/芳香胺(DDM)固化体系,并对改性后的环氧树脂进行力学性能和热学性能分析。结果表明改性后的环氧树脂浇铸体具有优良的韧性和耐热性。当BDM质量分数为5%(DMDES质量分数为4%)时,改性后环氧树脂弯曲强度达到92.11 MPa,冲击强度达20.202k J/m;热失重率50%时温度到达399.992℃,残炭率为17.88%。     

双马来酰亚胺/烯丙基双酚A共聚树脂的改性研究

本文对典型的4，4’－二氨基二苯甲烷双马来酰亚胺／3，3’－二烯丙基双酚A（BMI／DP）共聚树脂进行改性。结果表明，使用热引发剂能有效地降低树脂固化反应温度，但所得固化物脆性变大；共混热塑性树脂的增韧效果优于软相橡胶增韧；加入少量的环氧树脂或低粘度活性单体改性剂有利于纤维预浸料工艺性的改善。     

硼酚醛改性BMI树脂的研究

在传统的4,4－双马来酰亚胺基二苯甲烷／二烯丙基双酚A体系中引入硼酚醛结构,以改善传统双马来酰亚胺（BM）树脂的燃烧性能,结果表明,在一定范围内随着硼酚醛结构含量的增加,明显提高了BMI体系在空气中的热分解温度,改善了BMI体系的燃烧性能,而原BMI体系的工艺性能及力学性能保不变。     

一种改性双马来酰亚胺共聚树脂体系及其粘接性能的研究

以二苯甲烷双马来酰亚胺和二烯丙基双酚A为共聚单体，在适当的催化剂等作用下，制备了一种改性双马来酰亚胺共聚树脂。本文对这种改性的双马来酰亚胺共聚树脂的溶解性能、固化反应动力学和固化机理进行了讨论；对体系固化物的机电热性能及其胶粘剂的高低温粘接性能也进行了研究。     

烯丙基双酚A改性双马来酰亚胺-三嗪树脂的热性能

以4,4′-二苯甲烷双马来酰亚胺、双酚A型氰酸酯和2,2-二烯丙基双酚A为基本原料制备了改性双马来酰亚胺-三嗪（BT）树脂。系统地研究了2,2-二烯丙基双酚A对BT树脂固化动力学、BT树脂的溶解性能和BT树脂固化物的热性能的影响。研究结果表明：烯丙基双酚A有效地降低了BT树脂的固化反应温度并提高了BT树脂的溶解性能。当烯丙基双酚A的加入量为20%（质量分数）时,BT树脂的固化反应峰值降至233.1 ℃;并且,其固化物的玻璃化转变温度仍然达到239.4 ℃,5%热失重温度为372.9 ℃,显示了良好的耐热性能。     

三元共聚双马来酰亚胺树脂的制备与性能

按照马来酰亚胺基团和烯丙基基团物质的量比为1∶0.87将寡聚双马来酰亚胺(PPCBMI)与o,o′-二烯丙基双酚A(DABPA)和二苯甲烷型双马来酰亚胺(BDM)反应合成了新型三元共聚双马来酰亚胺树脂。采用示差扫描量热分析、热重分析、动态机械分析及力学性能测试研究了PPCBMI含量对树脂的固化行为,固化物的耐热性、动态热机械性能和力学性能的影响。结果表明,PPCBMI可以有效地增韧BDM/DABPA体系,由于引入了大体积的Cardo结构,获得了耐热性与韧性兼具的理想树脂。     

聚醚酰亚胺对共聚双马来酰亚胺树脂的增韧作用

采用二烯丙基双酚A、烯丙基酚醛改性4,4'-二氨基二苯甲烷双马来酰亚胺共聚制备了一类新型的双马来酰亚胺树脂(简称ABD)。以ABD为基体,选用热塑性树脂聚醚酰亚胺(PEI)为增韧剂,采用共混法制备了共聚双马来酰亚胺/聚醚酰亚胺(PEI)树脂体系。采用DSC和流变仪对ABD树脂的固化行为进行了研究,结果表明,该树脂粘度较低,室温下为液态,树脂的冲击强度为8.99 kJ/m2。通过DMA、TGA和扫描电镜对PEI加入量对树脂热性能和微观形貌的影响表明,添加质量分数为15%聚醚酰亚胺时,树脂冲击强度达到16.9 kJ/m2,比基体树脂提高了88%。     

Modification of three‐component bismaleimide resin by poly(phthaloyl diphenyl ether) and related copolymers

A three‐component bismaleimide resin, composed of 4,4′‐bismaleimidodiphenyl methane (BDM), o,o′‐diallyl bisphenol A (DBA), and o,o′‐dimethallyl bisphenol A (1.0/0.3/0.7 eq ratio) was used as a parent bismaleimide resin. Modification of the three‐component bismaleimide resin was examined by blending it with poly(ether ketone ketone)s. Poly(ether ketone ketone)s include poly(phthaloyl diphenyl ether) (PPDE), poly(phthaloyl diphenyl ether‐co‐isophthaloyl diphenyl ether) (PPIDE), and poly(phthaloyl diphenyl ether‐co‐terephthaloyl diphenyl ether) (PPTDE). The PPIDE (51 mol % isophthaloyl) and PPTDE (44 mol % terephthaloyl) were more effective as modifiers for the bismaleimide resin than was PPDE. For example, the fracture toughness (K_IC) for the modified resin increased 30% with no deterioration in the flexural strength and modulus with a 15 wt % inclusion of PPTDE (MW 23,400) compared to the parent three‐component bismaleimide resin: the K_IC increased 95% compared to the value for the Matrimid 5292 resin composed of BDM and DBA. The morphologies of the modified resins changed from particulate to cocontinuous phase structures, depending on the modifier structure and concentration. Toughening of the cured bismaleimide resin could be achieved because of the cocontinuous phase structure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2991–3000, 2001     

蒙脱土/聚醚砜-双马来酰亚胺复合材料微观形貌及性能

采用十八烷基三甲基氯化铵（OTAC）作为改性剂、通过离子交换法制备了改性蒙脱土（OTAC-MMT）;以4,4'-二氨基二苯甲烷双马来酰亚胺（MBMI）、3,3'-二烯丙基双酚A（BBA）及双酚A双烯丙基醚（BBE）为原料制备了复合材料基体（MBAE）;利用原位聚合法将OTAC-MMT和聚醚砜（PES）掺杂基体中制备OTAC-MMT/PES-MBAE复合材料。XRD结果分析表明：OTAC-MMT层间距相对于Na-MMT有明显增大。SEM微观形貌显示：OTAC-MMT片层结构更加明显且分散均匀;复合材料的表面更加粗糙,改性蒙脱土分散均匀,PES与基体树脂呈两相结构,出现了向不同方向发展的银纹和微裂纹,呈韧性断裂。当OMMT质量分数为2%、PES为3%时,OTAC-MMT/PES-MBAE复合材料的冲击强度和弯曲强度分别为14.54 kJ·m^-2和149.12 MPa,较MBAE树脂分别提高了55.5%和47.2%。介电性能测试表明：OTAC-MMT/PES-MBAE复合材料介电常数和损耗略有上升,但仍满足材料的使用要求。     

改性聚酰亚胺树脂复合材料的研究

以4，4-二苯甲烷双马来酰亚胺、二氨基二苯甲烷、环氧树脂为主要原料合成性能优良的改性聚酰亚胺树脂体系；以此树脂为基体、玻璃纤维布为增强材料制作的复合材料具有玻璃化温度高、机械强度好、介电常数低等优异的综合性能，可用于制作耐高温、高强度绝缘材料。     

Modification of bismaleimide resin by poly(ethylene phthalate‐co‐ethylene terephthalate), poly(ethylene phthalate‐co‐ethylene 4,4′‐biphenyl dicarboxylate), and poly(ethylene phthalate‐co‐ethylene 2,6‐naphthalene dicarboxylate)

Aromatic polyesters were prepared and used to improve the brittleness of bismaleimide resin, composed of 4,4′‐bismaleimidodiphenyl methane and o,o′‐diallyl bisphenol A (Matrimid 5292 A/B resin). The aromatic polyesters included PEPT [poly(ethylene phthalate‐co‐ethylene terephthalate)], with 50 mol % of terephthalate, PEPB [poly(ethylene phthalate‐co‐ethylene 4,4′‐biphenyl dicarboxylate)], with 50 mol % of 4,4′‐biphenyl dicarboxylate, and PEPN [poly(ethylene phthalate‐co‐ethylene 2,6‐naphthalene dicarboxylate)], with 50 mol % 2,6‐naphthalene dicarboxylate unit. The polyesters were effective modifiers for improving the brittleness of the bismaleimide resin. For example, inclusion of 15 wt % PEPT (MW = 9300) led to a 75% increase in fracture toughness, with retention in flexural properties and a slight loss of the glass‐transition temperature, compared with the mechanical and thermal properties of the unmodified cured bismaleimide resin. Microstructures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The toughening mechanism was assessed as it related to the morphological and dynamic viscoelastic behaviors of the modified bismaleimide resin system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2352–2367, 2001     

Blended resins based on a new propargyl‐functional resin: Synthesis,cure, and thermal properties

A new propargyl‐functional resin, propargyl ether bisphenol A novolac (PBPN), was synthesized, and the structure of PBPN were characterized using ¹H NMR and FTIR spectra. The PBPN was blended with 4,4′‐bismaleimide diphenyl methane (BDM) at different molar ratio to obtain the blends. Differential scanning calorimetry (DSC) was used to characterize the cure behavior of PBPN and the blends. Thermal gravimetric analysis (TGA) and dynamic mechanical analysis (DMA) were performed, respectively, to evaluate thermal stability and dynamic mechanical properties of the cured resins. The results indicate that the PBPN presented better cure and thermal properties than do traditional propargyl resins; furthermore, the cure behavior and thermal properties of PBPN could be improved remarkably by blending with BDM. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4207–4212, 2006     

功能化石墨烯改性双马来酰亚胺复合材料的微观表征及性能

采用改进Hummers法制备氧化石墨烯（GO）,分别采用水合肼、壳聚糖、KOH还原得到了还原氧化石墨烯（rGO）并对三种还原方法做了对比,选择最佳方案;再通过离子液体（NH₂IL）对rGO功能化得到改性还原氧化石墨烯（NH₂IL-rGO）。以二烯丙基双酚A （BBA）和双酚A双烯丙基醚（BBE）为活性稀释剂,4,4'-二氨基二苯甲烷型双马来酰亚胺（MBMI）为反应单体,制备了MBMI-BBA-BBE （MBAE）树脂基体;同时以NH₂IL-rGO为增强体采用原位聚合法制备NH₂IL-rGO/MBAE复合材料。表征了石墨烯和复合材料的微观形貌并分析了石墨烯对复合材料性能的影响。结果表明：NH₂IL-rGO在树脂基体中以两相形式存在,结构完整,并赋予复合材料优异的性能。当NH₂IL-rGO含量为2%（质量）时,复合材料冲击强度和弯曲强度最大,分别为15.33 kJ/m²和142 MPa,热分解温度为435.73℃、当测试频率为100 Hz～10 kHz时介电常数发生突变达到84。     

Modification of bismaleimide resin by soluble poly(ester imide) containing trimellitimide moieties

Poly(ester imide)s containing trimellitimide moieties have been used to reduce the brittleness of the bismaleimide resin composed of 4,4′‐bismaleimidediphenyl methane and o,o′‐diallyl bisphenol A. The poly(ester imide)s include poly[ethylene phthalate‐co‐ethylene N‐(1,4‐phenylene)trimellitimide dicarboxylate]s containing 20–40 mol% trimellitimide (TI) unit, and poly[trimethylene phthalate‐co‐trimethylene N‐(1,4‐phenylene)trimellitimide dicarboxylate]s (PESIP) containing 20 mol% TI unit. The poly(ester imide)s are effective modifiers for reducing the brittleness of the bismaleimide resin. For example, when using 30 wt% of PESIP (20 mol% TI unit, M_w 13 500 g mol^?1), the fracture toughness (K_IC) for the modified resin is increased by 80% with retention in flexural properties and a slight loss of the glass transition temperature, compared with the values of the unmodified cured bismaleimide resin. Microstructures of the modified resins have been examined by scanning electron microscopy and dynamic viscoelastic analysis. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviour of the modified bismaleimide resin system. © 2004 Society of Chemical Industry     

双马来酰亚胺与链烯基酚醚共聚物及其粘接性研究

本文研究了由双马来酰亚胺、二元胺、双酚A双烯丙基醚和环氧树脂制备的单组分溶液共聚物及其固化物在不同条件下粘接性,为选择耐高温高粘接性和多种应用的热固性树脂提供了新的优良材料体系.     

3,3'-二叔丁基-4,4'-二氨基二苯甲烷的合成

以4,4'-二氨基二苯甲烷为原料,通过乙酰化反应、烷基化反应、去乙酰化反应,合成了3,3'-二叔丁基-4,4'-二氨基二苯甲烷,采用FTIR证实了其分子结构。通过产率测定研究了各反应阶段的影响因素,确定最佳反应条件:乙酰化反应中,在反应温度215℃下,乙酸过量200%,产率达97%;烷基化反应中,以N,N'-二甲基甲酰胺(DMF)为溶剂,无水三氯化铝为催化剂,在25℃反应温度下,产率达92%;去乙酰化反应中,采用浓盐酸加热,冰浴析出法,产率达98%。通过向4,4'-二氨基二苯甲烷的苯环上引入大体积的叔丁基,提高双马来酰亚胺树脂单体在普通溶剂中的溶解能力,降低预聚体粘度,以便于双马来酰亚胺树脂应用传递模塑成型工艺(RTM)加工。