分散聚合法制备粉末涂料用丙烯酸酯树脂

以偶氮二异丁腈为引发剂、聚乙烯吡咯烷酮为分散剂、乙醇-水混合溶剂为分散介质,采用甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯和丙烯酸丁酯为共聚单体,合成了含有环氧基的丙烯酸酯树脂;考察了丙烯酸丁酯量对共聚物微球形态的影响、反应时间与转化率的关系、丙烯酸酯树脂的玻璃化温度和环氧值等物性;利用合成的丙烯酸酯树脂,配合适当的助剂,制备出加工性能优异的丙烯酸酯粉末涂料。     

AIM 核壳增韧剂/ PVC 树脂共混体系性能

采用自制的丙烯酸丁酯接枝甲基丙烯酸甲酯核壳结构增韧剂( PBA-g-PMMA, AIM) 与聚氯乙烯( PVC) 树脂熔融共混, 制备了AIM/ PVC 共混物。研究了增韧剂粒子在PVC 中的分散和空洞化、AIM/ PVC 共混物的断裂与脆韧转变。结果表明, 球形的增韧剂粒子能够在PVC 树脂中均匀分散并对PVC 有很好的增韧作用, 在PVC 树脂中加入质量分数为615 %AIM 时, 冲击样条以韧性方式断裂; 样条冲击断面周围应力发白区域内产生了空洞。提出AIM 增韧PVC 的机理是橡胶粒子的空洞化与塑料基体剪切屈服协同作用。      

Effect of hybridization of liquid rubber and nanosilica particles on the morphology, mechanical properties, and fracture toughness of epoxy composites

A liquid carboxyl-terminated butadiene–acrylonitrile copolymer (CTBN) and SiO₂ particles in nanosize were used to modify epoxy, and binary CTBN/epoxy composites and ternary CTBN/SiO₂/epoxy composites were prepared using piperidine as curing agent. The morphologies of the composites were observed by scanning electron microscope (SEM) and transmission electron microscope (TEM), and it is indicated that the size of CTBN particles increases with CTBN content in the binary composites, however, the CTBN particle size decreases with the content of nanosilica in the ternary composites. The effects of CTBN and nanosilica particles on the mechanical and fracture toughness of the composites were also investigated, it is shown that the tensile mechanical properties of the binary CTBN-modified epoxy composites can be further improved by addition of nanosilica particles, moreover, obvious improvement in fracture toughness of epoxy can be achieved by hybridization of liquid CTBN rubber and nanosilica particles. The morphologies of the fractured surface of the composites in compact tension tests were explored attentively by field emission SEM (FE-SEM), it is found that different zones (pre-crack, stable crack propagation, and fast crack zones) on the fractured surface can be obviously discriminated, and the toughening mechanism is mainly related to the stable crack propagation zone. The cavitation of the rubber particles and subsequent void growth by matrix shear deformation are the main toughening mechanisms in both binary and ternary composites.     

Enhancement of fracture toughness,mechanical and thermal properties of rubber/epoxy composites by incorporation of graphene nanoplatelets

Carboxyl terminated butadiene acrylonitrile (CTBN) was added to epoxy resins to improve the fracture toughness, and then two different lateral dimensions of graphene nanoplatelets (GnPs), nominally <1 μm (GnP-C750) and 5 μm (GnP-5) in diameter, were individually incorporated into the CTBN/epoxy to fabricate multi-phase composites. The study showed that GnP-5 is more favorable for enhancing the properties of CTBN/epoxy. GnPs/CTBN/epoxy ternary composites with significant toughness and thermal conductivity enhancements combined with comparable stiffness to that of the neat resin were successfully achieved by incorporating 3 wt.% GnP-5 into 10 wt.% CTBN modified epoxy resins. According to the SEM investigations, GnP-5 debonding from the matrix is suppressed due to the presence of CTBN. Nevertheless, apart from rubber cavitation and matrix shear banding, additional active toughening mechanisms induced by GnP-5, such as crack deflection, layer breakage and separation/delamination of GnP-5 layers contributed to the enhanced fracture toughness of the hybrid composites.     

Role of rigid nanoparticles and CTBN rubber in the toughening of epoxies with different cross-linking densities

Experimental investigations were conducted to characterize the fracture behaviours of Bisphenol A diglycidyl ether (DGEBA) epoxies modified with rigid nanoparticles (nanosilica or halloysite) and a reactive liquid carboxylterminated butadiene–acrylonitrile (CTBN) liquid rubber to identify toughening mechanisms and toughenability in the cured epoxies with different cross-linking densities. The epoxy was cured using three different hardeners, a heterocyclic amine (piperidine), a cycloaliphatic polyamine (Aradur 2954) and an aromatic amine [4,4′-Diaminodiphenyl sulfone (DDS)] to form nanocomposites with different cross-linking densities. It was found that both the hybrid particles, nanosilica with CTBN rubber and halloysite with CTBN rubber, were effective additives that clearly increased the fracture toughness of the three epoxy composites. In particular, the use of halloysite nanoparticles as additives for the epoxies showed greater potential than nanosilica to increase strength and modulus due to the reinforcing effect of the halloysite nanotubes (HNTs). The epoxy systems cured with the hardeners (Aradur 2954 and DDS), which generated relatively high cross-linking densities, evidenced inferior toughenability of the hybrid particles, compared with the epoxy systems cured using the hardener (piperidine), which produced lower cross-linking densities. The CTBN rubber formed dissimilar domains in different epoxy systems, features which were attributed to the different toughenability of the hybrid particles in the systems due to variations in the dominant toughening mechanisms involved.     

相容剂对长玻纤增强热塑性聚氨酯弹性体/聚乳酸复合材料性能的影响

采用熔体浸渍工艺制备长玻纤增强热塑性聚氨酯弹性体(TPU)/聚乳酸(PLA)复合材料;以苯乙烯-丙烯腈接枝甲基丙烯酸缩水甘油酯(SAG)作为相容剂,热塑性弹性体聚氨酯作为增韧剂,聚乳酸为基体树脂,考察苯乙烯-丙烯腈接枝甲基丙烯酸缩水甘油酯用量对长玻璃纤维增强聚TPU/PLA复合材料性能的影响。结果表明,加入苯乙烯-丙烯腈接枝甲基丙烯酸缩水甘油酯能改善长玻璃纤维增强聚TPU/PLA复合材料的相容性;长玻璃纤维增强聚TPU/PLA复合材料的拉伸强度、缺口冲击强度、弯曲强度和模量等力学性能及储能模量随着苯乙烯-丙烯腈接枝甲基丙烯酸缩水甘油酯用量的增加呈先增加后降低的趋势,而长玻璃纤维增强聚TPU/PLA复合材料的损耗因子则随苯乙烯-丙烯腈接枝甲基丙烯酸缩水甘油酯含量的增加呈现降低后增加的趋势;通过复合材料的形态分析表明,加入相容剂的复合材料中玻璃纤维与基体树脂界面强度增加,且玻璃纤维表面有一层包覆的树脂基体;通过分析得出,当相容剂添加量为6%时,长玻璃纤维增强聚TPU/PLA复合材料的拉伸强度、弯曲强度和模量、缺口冲击强度等力学性能最优。     

端羧基丁腈橡胶改性环氧树脂的结构与性能

用液体端羧基丁腈橡胶(CTBN)对环氧树脂(EP)进行改性,合成了CTBN/EP预聚物,FT-IR分析表明,在反应中EP的环氧基开环后与CTBN的羧基反应生成了酯键。研究了CTBN/EP/聚醚胺(PEA)体系的力学性能,结果表明,随着CTBN含量的增大,其弯曲强度、拉伸强度降低,冲击强度、断裂伸长率增大,说明CTBN通过化学预聚改性的EP具有良好的韧性。SEM分析表明,固化过程中析出了橡胶相并均匀分散在环氧树脂基体中。     

环氧树脂复合材料的制备及力学性能

通过配方设计,以硅烷偶联剂改性的空心玻璃微珠(HGB)为填料,端羧基液体丁腈橡胶(CTBN)为增稠剂和增韧剂,环氧树脂(EP)为基体,经变温分段固化技术制备环氧树脂/端羧基丁腈橡胶/空心玻璃微珠(EP/CTBN/HGB)三元泡沫复合材料并研究其力学和流变性能。结果表明,CTBN使得复合材料由脆性断裂变为韧性断裂;CTBN劣化了复合材料模量而HGB弥补了复合材料模量;当CTBN、HGB含量分别为12%(质量分数)和30%(体积分数)时,三元复合材料的冲击、弯曲、拉伸强度及弯曲模量均优于纯EP。另外,纯环氧树脂和EP/CTBN共混物的黏度呈现出牛顿流体的流变行为,而三元共混物的黏度表现出明显的剪切变稀现象。     

共聚法改性苯并(口恶)嗪/环氧树脂体系的性能

通过力学性能、热失重、动态粘弹谱和扫描电子显微镜研究了增韧剂对苯并(口恶)嗪/环氧树脂体系性能的影响.研究表明,液体聚硫橡胶通过共聚法改性苯并(口恶)嗪/环氧树脂体系,不仅可以提高树脂体系的耐热性能,还可以显著提高树脂体系的冲击强度和拉伸强度;而且明显好于共混法改性以及其它增韧剂改性.     

Possible phase transformation toughening of thermoset polymers by poly(butylene terephthalate)

Mechanisms were explored by which particles of poly(butylene terephthalate) (PBT) are able to toughen a brittle epoxy. The epoxy studied was an aromatic amine-cured diglycidyl ether of bisphenol-A, which was toughened at about twice the rate with particles of poly(butylene terephthalate) as with particles of nylon 6, poly(vinylidene fluoride), or CTBN rubber. Many of the mechanisms of toughening are visible on the fracture surface of the PBT-epoxy blend, but a mechanism suggested to account for perhaps half of the increased toughness with PBT, phase transformation toughening, is not. The two types of experiment performed to detect phase transformation toughening were: (1) measurements of the rubber cavitation zone in PBT-CTBN rubber-epoxy ternary blends, which would detect an expansion of the PBT particles during fracture if it occurred, and (2) measurements of the fracture energy in PBT-epoxy blends in which the various mechanisms of toughening were selectively suppressed. Both types of experiment indicated the occurrence of phase transformation toughening in these PBT-epoxy blends.     

Rubber modified vinyl ester resins of different molecular weights

The morphology, as well as the related fracture and mechanical behavior of vinyl ester resins (DVER) of different molecular weights cured with styrene (S) and modified with two different liquid rubbers are presented and discussed. The liquid rubbers are: carboxyl terminated poly(butadiene-co-acrylonitrile) (CTBN), a common toughening agent for epoxy resins, and an almost unreactive rubber with the DVER and S comonomers, and a reactive rubber (vinyl terminated poly(butadiene-co-acrylonitrile), (VTBN). The initial miscibility of the modified systems and the reactivity of the rubber determine the final morphology of the material. This morphology will correspond to a continuous main phase (rich in the DVER-S copolymer) with simple rubber rich inclusions (as in the epoxy-rubber systems) or with inclusions with a complex internal structure, where phase separation occurs as in the low profile modified unsaturated polyester resins. The morphologies developed are strongly dependent on the resin molecular weight as well as on the elastomer added. In spite of the initially higher compatibility of the S-DVER-CTBN system with respect to the S-DVER-VTBN system, the reactivity of the vinyl-ended elastomer leads to a much finer distribution of the elastomeric phase. In particular, the low molecular weight resin cured with S and modified with 10% of CTBN leads to a cocontinuous structure with microvoids that generates a material of low density and poor mechanical and fracture properties. On the other hand, the use of VTBN as additive leads to a more compact morphology, with gradual reduction of the mechanical performance of the modified resins and improved fracture behavior.     

端羧基液体丁腈橡胶改性海因环氧树脂性能研究

目的 采用端羧基液体丁腈橡胶(CTBN)对海因环氧树脂进行增韧改性。方法 通过热熔法将不同份数的CTBN添加到海因环氧树脂中，以4,4''–二氨基二苯甲烷为固化剂制备了改性环氧树脂，通过固化动力学研究确定了其固化工艺，考察CTBN用量对改性树脂体系的反应活性、力学性能、热性能以及断面微观形貌的影响。结果 随着CTBN的加入，改性树脂的固化放热峰向高温方向偏移。CTBN可显著提高树脂体系的断裂伸长率和冲击强度，其热性能基本保持不变。改性树脂的断面呈现两相“海岛”结构。结论 CTBN对海因环氧树脂有明显的增韧作用，制备的改性树脂体系可用于金属防腐涂料和胶黏剂等材料。     

水性环氧交联丙烯酸树脂乳液的结构及性能表征

以过硫酸钾和亚硫酸氢钠为引发剂,聚乙烯醇为保护胶体,采用种子无皂乳液聚合方法制备了丙烯酸丁酯、苯乙烯、α-甲基丙烯酸和丙烯酸-2-羟乙酯共聚的丙烯酸树脂乳液;添加钾离子、钙离子等金属阳离子催化了阴离子丙烯酸树脂乳液和水性环氧树脂的交联,形成了空间网状结构;在单晶硅基底上铺展了共聚物超薄膜,用激光纳米粒度及电位仪、流变仪、原子力显微镜表征了粒度、Zeta电位、流变性能和膜的形貌,分析了金属阳离子对丙烯酸树脂乳液交联的影响,发现阳粒子的加入使得粒径、Zeta电位减小,流变性能变化,可以催化共价交联的进行。     

Toughening of thermoset polymers by rigid crystalline particles

The toughening of an aromatic amine-cured diglycidyl ether of bisphenol-A epoxy with particles of crystalline polymers was studied. The crystalline polymers were poly (butylene terephthalate), nylon 6, and poly(vinylidene fluoride). Nylon 6 and poly(vinylidene fluoride) were found to toughen the epoxy about as well as did an equivalent amount of CTBN rubber. Poly(butylene terephthalate) was found to toughen the epoxy about twice as well as did the rubber. The toughness of poly(butylene terephthalate)-epoxy blends was independent of particle size for sizes in the range of tens of micrometres, but the toughness of the nylon 6-epoxy blends decreased with increasing particle size for sizes smaller than about 40 μm. There was no loss of either Young's modulus or yield strength of the epoxy with the inclusion of either nylon 6 or poly(butylene terephthalate) and less loss of these with the inclusion of poly(vinylidene fluoride) than with the inclusion of rubber. Toughness seems to have arisen from a combination of mechanisms. The poly(butylene terephthalate)-epoxy blends alone seem to have gained toughness from phase-transformation toughening. Crack path alteration and the formation of steps and welts and secondary crack bridging seem to have accounted for an especially large part of the fracture energy of the poly(vinylidene fluoride)-epoxy blends. Secondary crack nucleation contributed to the toughness of the nylon 6-epoxy blends.     

Low-temperature behaviour of epoxy-rubber particulate composites

Toughness and mechanical property data are presented for a carboxyl-terminated acrylonitrile butadiene (CTBN) rubber-modified epoxy resin in the temperature range 20 to – 110° C. A toughening model based on ultimate strain capability and tear energy dissipation of the rubber, present as dispersed microscopic particles in an epoxy matrix, is used to explain the suppression of composite toughness (G _Ic ) below – 20° C. The toughness loss is attributed to a glass transition in the rubber particles, and to a secondary transition in the epoxy resin, both occurring in the range – 40 to – 80° C. Strain-tofailure and modulus measurements on bulk rubber-epoxy compounds, formulated to simulate rubber particle compositions, confirm a decrease in rubber ductility coincident with the onset of composite toughness loss. An increase in rubber tear energy associated with its transition to a rigid state can explain the observation that even at low temperatures composite toughness generally remains significantly higher than that of pure epoxy. Although the low-temperature epoxy transition reduces molecular mobility in the matrix phase, residual ductility in, and energy dissipation by, the rubber particles determine the extent of composite toughness suppression. The low-temperature data bear out the particle stretching-tearing model for toughening.     

聚合反应条件对甲基丙烯酸缩水甘油酯/丙烯酸丁酯乳液共聚体系凝胶的影响

将丙烯酸丁酯（BA）与甲基丙烯酸缩水甘油酯（GMA）进行乳液共聚合以制备环氧型聚丙烯酸酯橡胶（ACM）,通过对ACM中凝胶含量及环氧基开环率的对比研究,探讨了不同反应条件对凝胶含量的影响。结果表明,在反应体系中加入20%的第二单体丙烯酸乙酯（EA）、选择复合引发体系、反应温度控制在30℃以及在反应体系对单体需求处于饥饿...     

Toughening of epoxy using core–shell particles

An epoxy resin, cured using an anhydride hardener, has been modified by the addition of preformed core–shell rubber (CSR) particles which were approximately 100 or 300 nm in diameter. The glass transition temperature, T _g, of the cured epoxy polymer was 145 °C. Microscopy showed that the CSR particles were well dispersed through the epoxy matrix. The Young’s modulus and tensile strength were reduced, and the glass transition temperature of the epoxy was unchanged by the addition of the CSR particles. The fracture energy increased from 77 J/m² for the unmodified epoxy to 840 J/m² for the epoxy with 15 wt% of 100-nm diameter CSR particles. The measured fracture energies were compared to those using a similar amount of carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber. The CTBN particles provided a larger toughening effect when compared to CSR particles, but reduced the glass transition temperature of the epoxy. For the CSR-modified epoxies, the toughening mechanisms were identified using scanning electron microscopy of the fracture surfaces. Debonding of the cores of the CSR particles from the shells was observed, accompanied by plastic void growth of the epoxy and shell. The observed mechanisms of shear band yielding and plastic void growth were modelled using the Hsieh et al. approach (J Mater Sci 45:1193–1210). Excellent agreement between the experimental and the predicted fracture energies was found. This analysis showed that the major toughening mechanism, responsible for 80–90% of the increase in fracture energy, was the plastic void growth.     

带有环氧基的反应型聚丙烯酸酯乳液的合成及表征

以甲基丙烯酸甲酯、丙烯酸-2-乙基己酯和甲基丙烯酸缩水甘油酯等为单体,制备了以PMMA-BA为"核"、PEHA-GMA为"壳"的微相复合乳液.利用透射电镜和激光动态光散射对乳胶粒子的形态和粒径分布进行了表征.研究了乳液聚合物和乳液与水溶性脲醛树脂共混物经不同温度热处理后的物理性能.结果表明,合成乳液的乳胶粒子具有预期的核-壳结构,粒度分布窄,平均粒径为132 nm;乳液聚合物和乳液与脲醛树脂共混物均随着热处理温度的升高,玻璃化转变温度升高,拉伸强度增大,断裂伸长率变小,吸水率降低.     

Interlayer self-healing and toughening of carbon fibre/epoxy composites using copolymer films

This paper presents an investigation of the combined self-healing and toughening performance of two copolymers: thermoplastic poly(ethylene-co-methyl acrylate) (EMA) and poly(ethylene-co-methacrylic acid) (EMAA). Carbon fibre composites were manufactured from unidirectional prepregs with rectangular-shaped patches being placed between composite plies. Results from double-cantilever-beam and short-beam-shear testing show that the incorporation of mendable polymers improves interlaminar fracture toughness but causes a reduction in interlaminar shear strength. The healing efficiency in terms of restoration of the interlaminate fracture energy scales linearly with the areal percentage of self-healing material. Microstructure study revealed distinct difference in the fracture surfaces of composites with EMA and EMAA, with EMA displaying extensive nano-scale porous structures in contrast to the more homogenous single phase structure from EMAA.     

The microstructure and fracture performance of styrene–butadiene–methylmethacrylate block copolymer-modified epoxy polymers

The microstructure and fracture performance of an anhydride-cured epoxy polymer modified with two poly(styrene)-b-1,4-poly(butadiene)-b-poly(methyl methacrylate) (SBM) block copolymers were investigated in bulk form, and when used as the matrix material in carbon fibre reinforced composites. The ‘E21’ SBM block copolymer has a higher butadiene content and molecular weight than the ‘E41’. A network of aggregated spherical micelles was observed for the E21 SBM modified epoxy, which became increasingly interconnected as the SBM content was increased. A steady increase in the fracture energy was measured with increasing E21 content, from 96 to 511 J/m² for 15 wt% of E21. Well-dispersed ‘raspberry’-like SBM particles, with a sphere-on-sphere morphology of a poly(styrene) core covered with poly(butadiene) particles, in an epoxy matrix were obtained for loadings up to 7.5 wt% of E41 SBM. This changed to a partially phase-inverted structure at higher E41 contents, accompanied by a significant jump in the measured fracture energy to 1032 J/m² at 15 wt% of E41. The glass transition temperatures remained unchanged with the addition of SBM, indicating a complete phase separation. Electron microscopy and cross polarised transmission optical microscopy revealed localised shear band yielding, debonding and void growth as the main toughening mechanisms. Significant improvements in fracture energy were not observed in the fibre composites, indicating poor toughness transfer from the bulk to the composite. The fibre bridging observed for the unmodified epoxy matrix was reduced due to better fibre–matrix adhesion. The size of the crack tip deformation zone in the composites was restricted by the fibres, hence reducing the measured fracture energy compared to the bulk for the toughest matrix materials.