含金刚烷结构新型环氧树脂的合成

以1,3-二(4-羟苯基)金刚烷(BPAD)和环氧氯丙烷(ECH)为原料,采用一步法合成了1,3-二(4-羟苯基)金刚烷二缩水甘油醚(DGEBAD),并优化了中间体BPAD的合成工艺。研究了原料配比,反应温度以及反应时间对DGEBAD的合成反应及产物的影响。结果表明,DGEBAD最优合成反应条件如下:BPAD与ECH物质的量比为1∶15,反应温度80℃,反应时间6 h,所得DGEBAD具有较高的环氧值和产率(分别为0.376 mol/100 g和147.1%)。     

新型含硼苯并噁嗪的合成及其与环氧树脂共混热性能

以乙醇胺、硼酸为原料合成硼酸乙醇胺酯（BAE）,再用所得硼酸乙醇胺酯与多聚甲醛、苯酚反应,合成含硼苯并噁嗪（BAE-BOZ）。将所得BAE-BOZ高温固化,BAE-BOZ和环氧树脂E-51按照不同的质量比进行熔融共混,并经高温固化。采用FT-IR,¹H NMR 和¹³C NMR等分析了BAE-BOZ的化学结构,证明了产物为目标产物;采用DSC对BAE-BOZ的固化特性进行研究;采用TG 分析了含硼乙醇胺型苯并噁嗪poly（BAE-BOZ）和BAE-BOZ/E-51共聚物的热稳定性。结果表明：BAE-BOZ在218℃出现了固化峰;BAE-BOZ的硼含量达到8.67%,在N₂条件下,poly（BAE-BOZ）的热分解温度为302℃,在426℃时热分解速率最快,800℃的残炭率为58.08%,与未经硼改性的乙醇胺型苯并噁嗪（E-BOZ）相比,热分解温度提高40℃,残炭率提高了16.28%;BAE-BOZ/E-51共聚物的热分解温度达到343℃,热性能得到进一步提高。     

含异氰脲酸酯基环氧树脂的合成

为了改善环氧树脂的耐热性与韧性 ,以三羟乙基异氰脲酸酯 (THEIC)为原料 ,与环氧氯丙烷 (ECH)合成了氯化聚醚多元醇 (CPP) ,CPP与氢氧化钠反应制备了一种新型的含异氰脲酸酯基和醚键的液体环氧树脂 (EP) ,并通过IR确定了结构。CPP与氢氧化钠的摩尔比为 1∶3.2 5,在 2 50ml乙醇 ( 0 .1molCPP)中 ,室温反应 3h ,产率 87.7% ,环氧值 0 .36 87。     

新型含磷酚醛树脂的合成与性能

通过亚膦酸酯与碳碳双键之间的亲电加成反应,合成了一种新型的含磷马来酰亚胺酚醛树脂。采用红外光谱(FTIR)和元素分析法对聚合物的结构进行了表征。并用此含磷酚醛树脂作为环氧树脂的固化剂制得了一含磷氮的环氧固化物。采用热分析法、极限氧指数法对相应环氧固化物的耐热性能和阻燃性能进行了表征。研究结果表明:以该含磷聚合物作为环氧树脂的固化剂,对稳定固化物骨架碳的结构和交联成炭能力的提高起到了增强作用;环氧固化物具有较高的玻璃化转变温度(145.4℃)和较高的热稳定性(T508℃),极限氧指数显示其具有较好的阻燃性能。     

Synthesis of a bifunctional epoxy monomer containing biphenyl moiety and properties of its cured polymer with phenol novolac

A new type of epoxy resin containing a 4,4′‐biphenylene moiety in the backbone (Bis‐EBP) is synthesized and confirmed by elemental analysis, infrared spectroscopy, and ¹H‐nuclear magnetic resonance spectroscopy. In addition, to evaluate the influence of the 4,4′‐biphenylene group in the structure, an epoxy resin having a 1,4‐phenylene group in place of the 4,4′‐biphenylene moiety (Bis‐EP) is synthesized. The cured polymer obtained through the curing reaction between the new biphenyl‐containing epoxy resin and phenol novolac is used for making a comparison of its thermal and physical properties with those obtained from Bis‐EP and bisphenol‐A (4,4′‐isopropylidenediphenyl)‐type epoxy resin (Bis‐EA). The cured polymer obtained from Bis‐EBP shows markedly higher fracture toughness of 1.32 MPa m^1/2, higher glass transition temperature, lower moisture absorption, and higher thermal decomposition temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 690–698, 1999     

Preparation,characterization, and polymerization of novel maleimidobenzoxazine containing carboxylic moiety and its cocuring behaviors with epoxy resin

A novel benzoxazine containing maleimide and carboxylic moieties, 1‐[3‐(4‐carboxylphenyl)‐3,4‐dihydro‐2H‐benzo[e][1,3]‐oxazin‐6‐yl]maleimide (Mal‐Bz‐Co), was synthesized and the structure was identified by ¹H‐NMR and FTIR. Mal‐Bz‐Co exhibited good solubility in common organic solvents. The cure behavior of Mal‐Bz‐Co and cocure behavior of Mal‐Bz‐Co with o‐cresol formaldehyde epoxy resin were investigated by differential scanning calorimetry. Results indicated that Mal‐Bz‐Co showed a single curing exothermic peak at about 238.3°C. However, the maximum curing temperature (T_p) decreased to 146.1°C when Mal‐Bz‐Co cocured with o‐cresol formaldehyde epoxy resin in the molar ratio of 1 : 1. The T_p was about 92°C lower than that of Mal‐Bz‐Co. Thermogravimetric analysis showed that high‐decomposition temperature and char yield were observed for the cured resins of Mal‐Bz‐Co and Mal‐Bz‐Co/o‐CFER. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of a novel epoxy resin containing pyrene moiety and thermal properties of its cured polymer with phenol novolac

A new epoxy resin containing the pyrene moiety in the backbone (3) was synthesized and confirmed by gel permeation chromatography and field‐desorption mass spectroscopy and infrared spectroscopy. In addition, to evaluate the influence of the pyrene moiety on the structure, epoxy resins having an anthrylene moiety (5) and having a phenylene moiety (7) were synthesized. The cured polymer obtained through the curing reaction between 3 and phenol novolac was used for making a comparison of its thermal properties with those obtained from 5, 7, and bisphenol‐A (4,4′‐isopropylidenediphenyl)‐type epoxy resin (Bis‐EA). The cured polymer obtained from 3 showed a higher glass transition temperature, lower coefficient of linear thermal expansion, lower moisture absorption, and markedly higher anaerobic char yield at 700°C of 37.6 wt %, which might be attributed to the higher aromaticity of 3 containing the pyrene moiety. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 528–535, 2000     

含有联萘基团的环氧树脂的合成与固化

合成了一种具有联萘结构的环氧树脂(BEBN)。通过红外光谱、核磁共振氢谱以及元素分析对其结构进行了表征。以双酚A型环氧树脂(E-51)作为参照,采用二氨基二苯基甲烷为固化剂,通过差示扫描量热法(DSC)研究了BEBN,E-51的固化反应性;采用DSC,热重分析对固化物的热学性能进行测试,比较了固化物的力学性能、热性能以及吸水率;探讨了BEBN的结构与性能之间的关系。结果表明,同E-51相比,BEBN的固化反应平缓：BEBN固化物的玻璃化转变温度升高29℃,吸水率降低0．31％,热失重5％和50％的温度分别升高15℃和13℃。     

Synthesis and characterization of a liquid crystalline epoxy containing azomethine mesogen for modification of epoxy resin

A novel liquid crystalline epoxy monomer, 1,1′‐bis [4‐(2,3‐epoxypropoxyphenyleneininomethyl)]‐2,2′‐dimethylbiphenylene (BMPE) was synthesized and characterized by infrared (IR) and Nuclear magnetic resonance (NMR) spectroscopy. The effect of BMPE content on mechanical and thermal properties of its blends with Diglycidyl Ether of Biphenol A (DGEBA) was investigated. BMPE presented a Schlieren texture in the range of 150 to 215°C as observed by differential scanning calorimeter (DSC) and polarizing optical microscope (POM). The improvement of mechanical properties of DGEBA modified with BMPE was achieved without sacrificing thermal resistance. Scanning electronic microscopy (SEM) graphs of fracture surfaces of the cured blends showed that microfiber‐like structure formed in the cured blends, which would be a result of self‐oriented alignment of azomethine mesogen component. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis,characterization, and mechanical properties of a novel terphenyl liquid crystalline epoxy resin

A novel terphenyl liquid crystalline (LC) epoxy resin was synthesized and characterized by ¹H‐NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry (DSC), and polarizing optical microscopy. Depending on the curing temperature, the synthesized resin formed both smectic and nematic LC phases. A time‐temperature‐transformation diagram was constructed to optimize the curing process, which helped in the preparation of LC and isotropic system. The terphenyl epoxy resin obtained exhibited higher acid resistance than a comparable Schiff‐base epoxy resin, and also displayed excellent fracture toughness. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41296.     

Synthesis and properties of phosphorus and nitrogen containing intumescent flame-retardant curing agent for epoxy resin

A kind of intumescent ?ame-retardant curing agent (PCDSPB) was synthesised by using pentaerythritol, phosphorus oxycholoride, cyclohexane-1,3-diyldimethanamine (1,3- BAC) as raw materials and the structure was characterised by FTIR and MS. The composite materials were investigated by using TG, TG-FTIR, LOI, UL-94, SEM, and CCT. The results show that the ?lling of PCDSPB can improve the ?ame resistance of EP composites. When the phosphorus content of the composite system was 1.74 wt-%, the initial weight loss temperature was 299°C and the char yield was 26.3% at 600°C. Tensile strength was 35.4 MPa, impact strength was4.3 kJ m?2, LOI was 27.9, and the UL94 passed V-0 level. In the CCT, the peak heat release rate reduced to 276.0 kW m?2(EP-2) from 622.8 kW m?2 (EP-0), the total heat release decreased from 121.8 MJ m?2 (EP-0) to 89.5 MJ m?2 (EP-2). Therefore, the PCDSPB is a good intumescent ?ame-retardant curing agent for EP.     

Synthesis of a novel lignin-based epoxy resin curing agent and study of cure kinetics,thermal, and mechanical properties

In this contribution, first of all, the methoxy groups of organic solvent lignin (OSL) was converted to phenolic hydroxyl groups through demethylation reaction for the purpose of fabricating demethylated organic solvent lignin (DOSL). In addition, the resulting DOSL was utilized as a renewable material to synthesize a novel esterified lignin (EDOSL) by reacting with isobutyryl chloride for curing of epoxy resin. Finally, commercial liquid diglycidyl ether of bisphenol A was cured by EDOSL in the presence of 4-dimethylaminopyridine (DMAP) used as a catalyst based on dual-curing mechanism. Dual curing is a processing methodology based upon the alliance of two diverse and compatible polymerization reactions occurring sequentially or simultaneously. According to the FTIR spectra and ¹H-NMR analyses, the demethylation of OSL, esterification of DOSL, and the curing reaction of epoxy resin with EDOSL were successfully conducted. The value of the phenolic hydrogen in the DOSL was approximately 4.89 mmol/g, which increased by 12.64% after demethylation. The thermal and mechanical performances of these cured epoxy samples were measured by DSC, DMA, TGA, and tensile testing. The epoxy system cured by 10%wt esterified lignin with 1%wt DMAP possessed the tensile strength of 71.54 ± 7.50 MPa and the initial degradation temperature (T_5%) of 370°C, which can compete fairly with commercial aromatic curing agents or other lignin-based agents studied currently for the curing of epoxy systems.     

Synthesis and characterization of a novel epoxy resin containing naphthyl/dicyclopentadiene moieties and its cured polymer

A new epoxy resin containing both naphthalene and dicyclopentadiene (DCPD) groups was synthesized to produce a highly heat-resistant network, and the curing behavior was investigated using diaminodiphenylsulfone (DDS) as curing agent. The chemical structures were characterized with FTIR spectroscopy, NMR, MS, and GPC analyses. Dynamic curing behavior was investigated using differential scanning calorimetry (DSC). The physical properties of the resulting polymers were evaluated with dynamic thermal mechanical analyses (DMTA) and thermogravimetric analyses (TGA). The cured polymer showed great improvement in heat-resistant property including remarkably higher glass transition temperature (T_g) and thermal stability. Such properties make this new epoxy resin highly promising for heat-resistant applications.     

Polydimethylsiloxane containing isocyanate group-modified epoxy resin: Curing,characterization, and properties

A synthesized polydimethylsiloxane containing an isocyanate group was used to improve the flexibility and to reduce the internal stress of epoxy resin cured with MDA (4,4′-methylene dianiline). The effect of polysiloxane content on the curing kinetics of a novolac-type epoxy modified with an isocyanate group was investigated. It was found that the modified epoxy resin showed significant improvement in impact strength. The polysiloxane containing isocyanate groups effectively depressed the internal stress of cured epoxy resins by reducing the flexural modulus and the coefficient of thermal expansion, while the glass transition temperature was increased. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2739–2747, 1999     

Synthesis, characterization, and properties of novel novolac epoxy resin containing naphthalene moiety

A series of novel novolac epoxy resins containing naphthalene moiety with different molecular weights were synthesized via condensation of bisphenol A and 1-naphthaldehyde, followed by epoxidation with epichlorohydrin. The chemical structure of the naphthalene epoxy thus obtained was characterized using FTIR, ¹H NMR spectra and GPC analyses. The naphthalene epoxy was cured with 4,4′-diaminodiphenyl sulfone (DDS) and the cured products were characterized with thermogravimetric analysis, dynamic mechanical analysis, and X-ray diffraction. Compared with the diglycidyl ether of bisphenol A (DGEBA), the cured naphthalene epoxy resin showed remarkably higher glass transition temperatures (T_gs), enhanced thermal stability and better moisture resistance. When the molar ratio of 1-naphthaldehyde to bisphenol A was 0.67, the optimal thermal resistance was observed.     

Synthesis of a bifunctional epoxy monomer containing anthracene moiety and properties of its cured polymer with phenol novolac

A new type of epoxy resin containing anthracene moiety in the backbone was synthesized and was confirmed by elemental analysis, infrared spectroscopy, and ¹H nuclear magnetic resonance spectroscopy. Thermal properties of its cured polymer with phenol novolac were examined by thermomechanical, dynamic mechanical, and thermogravimetric analyses. The cured polymer with phenol novolac showed higher glass transition temperature (T_g), lower thermal expansion, lower moisture absorption, and higher anaerobic char yield at 700°C than a cured polymer having a phenylene group in place of anthracene moiety. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 953–959, 1999     

多面齐聚倍半硅氧烷改性环氧的制备及表征

以八苯基多面齐聚倍半硅氧烷为原料通过溴代,格氏试剂与丙酮加成等反应制备了八多羟基苯基多面齐聚倍半硅氧烷,并对产物进行了FTIR表征。采用该产物改性环氧树脂,并通过热失重分析仪、示差扫描量热仪对其固化物的热性能进行了研究。结果表明:该合成具有活性官能团的多面齐聚倍半硅氧烷的方法可行。在环氧树脂中加入八多羟基苯基多面齐聚倍半硅氧烷对其固化物热稳定性影响不大,但可以显著提高材料的玻璃化转变温度,当其质量分数为5.13%时,Tg可达183.2℃。     

新型含氟环氧树脂的结构及其表征

首先自行合成了含氟的双酚单体：(3—三氟甲基苯)对苯二酚，并以此为基础，使其与环氧氯丙烷反应合成了一种新型含氟环氧树脂。采用红外光谱、质谱和核磁共振光谱对环氧树脂的结构进行表征。初步确定所合成的产物为我们所设计的目标产物。对于这种含氟环氧树脂的性能，我们将在以后的工作中进一步研究。     

新型含磷阻燃环氧树脂的合成与表征

以2-(5,5-二甲基-4-苯基-2-氧代-1,3,2-二氧磷杂环已烷膦酸酯基)-对苯二酚和双酚A 二缩水甘油酯合成了一新型的含环状膦酸酯结构的阻燃环氧树脂(DPODB-EP).采用元素分析、红外光谱(FTIR)和凝胶渗透色谱(GPC)对该含磷环氧树脂的结构和相对分子质量分布进行了表征.采用示差扫描量热法(DSC))和热失重法(TG)对DPODB-EP/PN固化物热性能进行了测试,发现该固化物具有较高的玻璃化转变温度(165℃)和较高的燃烧残炭率(700℃,31%).阻燃性能测试表明该固化物具有较好的阻燃效果,在磷的质量分数为2.25%时其极限氧指数可达29.5%.     

氯甲基笼型倍半硅氧烷改性双酚A环氧树脂性能

引言双酚A环氧树脂是目前应用最广、用量最大的环氧树脂,具有良好的化学稳定性、电气绝缘性被广泛应用于涂料和电子电器等领域;然而,双酚A环氧树脂存在耐热性较差和固化后脆性大等缺点,因此如何提高环氧树脂的耐热性及力学性能等是目前改性研究的热点之一[1-5]。而笼型多面体倍半硅氧烷(POSS)是一类具有(RSiO1.5)n通式的纳米材料,因其特殊的分子组成结构使得POSS具