Mechanical behavior and structure of rubber modified vinyl ester resins

Vinyl esters are used widely as thermoset matrix materials for reinforced composites; however, they suffer from low‐impact resistance. Substantial enhancement of the toughness of brittle polymers may be achieved by dispersing elastomeric inclusions or rubber particles in the polymer matrix, inducing multiple crazing and shear yielding of the matrix. The main objectives of this work are morphological characterization of vinyl ester/reactive rubber systems and investigation of the mechanical and fracture behavior of these systems. Additional studies focused on rubber endcapped vinyl ester in the absence and presence of added reactive rubber. The initial compatibility of the liquid rubber with the liquid resin was studied. This is a key factor, along with cure conditions, in determination of the possible morphologies, namely, the degree of phase separation and particle size. The initial rubber/resin compatibility was found poor and all attempts to improve it by means of surfactants or ultrasonic treatment have not been successful. The flexure mechanical and fracture behavior of the cured resin/rubber systems was investigated. Three basic types of crack propagation behavior, stable, unstable, and stick‐slip, were observed. Fracture toughness of various resin/rubber systems was evaluated and was found to increase with increased content of rubbery second‐phase material. However, there is some payoff in stiffness and flexural strength of the cured resins. The addition of rubber does not affect the resin toughness at impact conditions. Analysis and interpretation of fractures morphology show that both multiple crazing and external cavitation play an important role in the fracture mechanism of the rubber modified specimens. No shear yielding is evident. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 647–657, 1999     

超声波对乳液聚合丁腈胶的影响研究

研究了超声波作用时间对乳液聚合丁腈胶固含量、转化率的影响,对丁腈胶的微观结构进行了红外测试分析。结果表明,随着超声波作用时间的延长,聚合物的固含量和转化率增加,超声波作用的反应体系所得聚合物的微观结构与传统乳液聚合所得聚合物的微观结构一致。     

耐腐蚀性乙烯基酯树脂的研究与应用

论述了乙烯基酯树脂优异的耐腐蚀性能、耐腐蚀原理及目前国内外耐腐蚀性乙烯基酯树脂的研究进展和在一些领城的典型应用。     

N,N-二乙基苯胺作为VE合成催化剂的研究

在环氧丙烯酸酯（VE）的合成过程中采用N，N－二乙基苯胺（DEAn)作为催化剂，成功地合成了预期产物VE树脂，合成产物色泽浅，粘度低，凝胶时间长。利和化学滴定、红外光谱（FTIR）等分析方法对VE的合成过程进行了跟踪、表征，讨论了DEAn用量对VE树脂及其固化产物性能的影响。     

Toughening of epoxy resin systems using low‐viscosity additives

This study has evaluated three low‐viscosity epoxy additives as potential tougheners for two epoxy resin systems. The systems used were a lower‐reactive resin based upon the diglycidyl ether of bisphenol A (DGEBA) and the amine hardener diethyltoluene diamine, while the second epoxy resin was based upon tetraglycidyl methylene dianiline (TGDDM) and a cycloaliphatic diamine hardener. The additives evaluated as potential tougheners were an epoxy‐terminated aliphatic polyester hyperbranched polymer, a carboxy‐terminated butadiene rubber and an aminopropyl‐terminated siloxane. This work has shown that epoxy‐terminated hyperbranched polyesters can be used effectively to toughen the lower cross‐linked epoxy resins, i.e. the DGEBA‐based systems, with the main advantage being that they have minimal effect upon processing parameters such as viscosity and the gel time, while improving the fracture properties by about 54 % at a level of 15 wt% of additive and little effect upon the T_g. This result was attributed to the phase‐separation process producing a multi‐phase particulate morphology able to initiate particle cavitation with little residual epoxy resin dissolved in the continuous epoxy matrix remaining after cure. The rubber additive was found to impart similar levels of toughness improvement but was achieved with a 10–20 °C decrease in the T_g and a 30 % increase in initial viscosity. The siloxane additive was found not to improve toughness at all for the DGEBA‐based resin system due to the poor dispersion within the epoxy matrix. The TGDDM‐based resin systems were found not to be toughened by any of the additives due to the lack of plastic deformation of the highly cross‐linked epoxy network Copyright © 2003 Society of Chemical Industry     

双酚A及端羧基丁腈橡胶对环氧树脂的增韧作用

以2-乙基-4-甲基咪唑为固化剂,分别以端羧基丁腈橡胶(CTBN)、CTBN/双酚A(BPA)或BPA为增韧剂增韧环氧树脂,研究了环氧树脂增韧体系的微观形貌和力学性能,考察了不同混料方式对CTBN增韧环氧树脂性能的影响。结果表明:CTBN增韧环氧树脂能使其固化物的冲击韧性有所提高,但其他力学性能降低;采用环氧树脂先与其进行预聚反应再经固化剂固化的方法能提高CTBN对环氧树脂的增韧效果;用CTBN/BPA为增韧剂不仅可以大幅度提高材料的冲击强度和扯断伸长率,而且可以提高弯曲强度与模量,克服了CTBN单一增韧导致材料强度下降的不足。BPA的加入可使环氧树脂固化物体系的弯曲强度、冲击强度和扯断伸长率有较大幅度的提高。     

Toughening of crosslinked polystyrene with liquid rubber

The optimum conditions for preparing poly(styrene‐co‐divinylbenzene) were determined and the variation of the mechanical properties of the networks with the crosslinking density was evaluated. The molecular weight between crosslinks was in the 800–12,000 range. The flexural modulus and flexural strength were 5000 and 110 MPa, respectively, for the more crosslinked materials. When liquid rubber (hydroxyl‐terminated polybutadiene) was incorporated into the glassy matrix, these values dropped to 2500 and 70 MPa, respectively, but the impact resistance increased to 70 J/m. These values were comparable to some commercial grade high impact polystyrene resins. The particle size of the dispersed rubber phase was on the nanometer scale, and attempts to increase its dimensions should provide further improvement in the impact properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2098–2105, 2001     

叔碳酸乙烯酯改性醋酸乙烯酯乳液的制备

合成了叔碳酸乙烯酯(VeoVa10)改性醋酸乙烯酯乳液，着重研究了保护胶用量、乳化荆用量、VeoVa10用量对涂膜耐水性的影响。研究结果表明，在保护胶质量分数为0．2％，乳化剂质量分数为3％，VeoVa10质量分数为15％—20％时，乳液具有耐碱性、耐水性好及低成本的优点。     

Toughening mechanisms in core-shell rubber modified polycarbonate

We have conducted a study of toughening mechanisms in rubber modified polycarbonate systems in order to evaluate the sequence of deformation events which improve fracture toughness. We conclude that cavitation of the rubber particles occurs first, followed by massive shear yielding of the matrix material. The size and shape of the deformation zone created in front of the crack is governed by the mechanical properties of the rubber particles and the stress state at the crack tip. The importance of using a variety of analytical techniques to characterize deformation mechanism is also illustrated.     

Synthesis and characterization of vinyl ester networks containing phthalonitrile moieties

A new styrenic monomer, 4-vinylphenoxyphthalonitrile, was synthesized by nucleophilic aromatic substitution of 4-vinylphenolate onto 4-nitrophthalonitrile. The new monomer was reacted with dimethacrylate-styrene resins (so-called vinyl esters) via free radical copolymerization at 90, then 120 °C with benzoyl peroxide as the initiator to form networks. The networks were further post-cured at 220, 240, or 260 °C for 4 h to convert the last portion of the methacrylates, and to partially cross-link the pendent phthalonitrile groups. A dimethacrylate-styrene network containing 30 wt% of the phthalonitrile-functional monomer exhibited a 70% reduction in peak heat release rate by cone calorimetry measured at an incident heat flux of 50 kW m⁻² relative to control vinyl ester networks. This still remains somewhat higher than peak heat release rates exhibited by brominated vinyl ester networks, but the CO/CO₂ ratio in the smoke is much lower for these non-halogenated materials.     

纳米CaCO_3对CE及CE/EP基体的改性研究

通过力学性能测试和扫描电镜、热重分析以及红外光谱测试研究了纳米CaCO3的加入量对氰酸酯(CE)及CE/环氧(EP)基体力学性能及热性能的影响。结果表明,适量的纳米CaCO3的加入,可有效地改善CE或CE/EP基体的韧性和强度。当纳米CaCO3的质量分数为3%时,两改性体系的冲击强度和拉伸模量均达到最大值,CE/EP/CaCO3体系较CE/CaCO3体系具有更高的冲击强度(7.8kJ/m2)和较低的拉伸模量(100.5GPa)。纳米CaCO3的加入有利提高基体的热稳定性,但CE/EP/CaCO3三元体系的热稳定性仍明显低于纯CE或CE/CaCO3二元体系。     

丁腈橡胶增韧环氧树脂研究进展

综述了近年来丁腈类橡胶增韧环氧树脂的研究进展,其中包括固体丁腈橡胶,液体丁腈橡胶(丁腈-40液体橡胶,无规端羧基液体丁腈橡胶(CRBN),端羧基液体丁腈橡胶(CTBN),改性端羟基丁腈橡胶(HTBN),改性端氨基液体丁腈橡胶(ATBN))以及改性液体丁腈橡胶与纳米SiO2共同增韧环氧树脂。     

Toughening epoxy resins with solid acrylonitrile–butadiene rubber

The feasibility of using solid acrylonitrile–butadiene rubbers (NBR) with 19 and 33% w/w acrylonitrile to toughen diglycidyl ether of bisphenol A (DGEBA) epoxy resins has been investigated. Thermal analysis experiments revealed a two‐phase morphology of these rubber‐modified epoxies. However, the higher content of acrylonitrile in the rubber caused better compatibility between NBR and the epoxy resin. The rubber with 33% acrylonitrile was found to be an effective toughening agent for DGEBA epoxy resins. Fracture surface studies and also the high tensile strength of crosslinked high molecular weight NBR suggest that the toughening effect should arise from rubber bridging and tearing mechanisms. © 2000 Society of Chemical Industry     

天然橡胶增韧聚氯乙烯的研究

采用未改性的标准天然橡胶(NR)作增韧剂,通过机械共混法制备增韧聚氯乙烯(PVC)复合材料,考察了NR和增容剂用量对PVC增韧效果以及力学性能的影响.结果表明:当NR用量为10份时,材料的冲击强度最高为24.87 kJ/m2;加入增容剂环氧化天然橡胶(ENR)后,材料的冲击强度随其用量的增加而增大,在ENR为5份时其冲击强度为69.86 kJ/m2;氯化聚乙烯(CPE)作增容剂时,其冲击强度先升后降,在4份时达到峰值103.93 kJ/m2;氯化橡胶(CNR)作增容剂在3份时,其冲击强度达到最佳值35.37 kJ/m2;增容增韧后共混物的拉伸强度普遍降低.     

Photo-DSC cure kinetics of vinyl ester resins II: influence of diluent concentration

The photopolymerization kinetics of two commercial vinyl ester resins (VERs) and a model VER photoinitiated by the camphorquinone/amine photoinitiator system were monitored using isothermal DSC. A decrease in styrene concentration in model VERs was found to raise the rate of photopolymerization. In contrast, when the styrene was replaced by a monomethacrylate diluent, the photopolymerization rate passed through a maximum near 70 wt% diluent monomer. This difference in the variation of the rate of polymerization with decreased monomer concentration was attributed to the competition of the effects of the higher reactivity of the methacrylyl radical relative to the styryl radical and the lower termination rate for divinyl-rich systems (both of which tend to raise the maximum polymerization rate) and the effects of the reduction in the initiation efficiency and decrease in k_p due to increased fraction of pendant double bonds (which lower the polymerization rate) when the concentration of diluent monomer was reduced. Subsequent dark polymerization was observed during a temperature ramp and the onset of polymerization was independent of resin composition due to vitrification effects during the isothermal photocuring stage. The kinetics during the dark polymerization stage was discussed in terms of the radical concentration and the propagation rate constant. Increases in the concentration of either diluent monomer raised the extent of isothermal cure during the isothermal polymerization because vitrification was delayed by the lower crosslink density and the plasticizing effect of the diluent. Higher levels of diluent also raised the maximally attainable conversion due to reduced topological restrictions for reaction in networks of lower crosslink density.     

Curing studies on vinyl ester resin using acrylates as reactive diluents

The curing behavior of bis(methacryloxy) derivatives of diglycidyl ether of bisphenol A (vinyl ester resin) containing acrylates (methyl, ethyl and butyl acrylate) as the reactive diluents (40% w/w) were studied by DSC analysis. Data found in this study indicated that an appreciable curing rate is obtained at lower temperature with increased concentrations of initiator. The acid value, activation energy, Arrhenius factor and specific heat are discussed.     

用凝聚法制备粉末丁腈橡胶

以非交联或交联剂的丁腈－４０胶浆为原料，用正凝聚法使橡胶杨粉得到粉末橡胶淤浆，再加入隔离剂防粘结，经过滤，洗洗，过滤，干燥而掉得粒烃大于１．２５ｍｍ，橡胶含量大于９０％的粉末丁腈橡胶。研究了凝聚方式，隔离剂，凝聚剂，胶浆稳定性，凝聚条件，凝聚设备的结构等对成粉率的影响，成粉率达９０％以上，并所制产品与国外同类产品进行了比较。     

Toughening of vinyl ester resins by two-dimensional MXene nanosheets

Two-dimensional nanosheets are highly effective tougheners for vinyl ester resins. The toughening effect is related to the high specific surface area and unique two-dimensional planar structure of the nanosheets. In this study, a coupling agent γ-(2,3-epoxypropoxy) propytrimethoxysilane (Kh-560) was used to modify MXene nanosheets (M-MXene) for use in toughening vinyl ester resin. The mechanical properties, including the tensile strength, flexural strength, Young’s modulus and elongation, of neat vinyl ester resin and vinyl ester resin modified with MXene and M-MXene were investigated. The results showed that modification significantly improved the mechanical properties of the vinyl ester resin. The tensile and flexural strengths of the MXene-nanosheet-modified vinyl ester resin were 27.20% and 25.32% higher, respectively, than those of the neat vinyl ester resin. The coupling agent improved the interfacial compatibility between the MXene nanosheets and vinyl ester resin, which resulted in the tensile and flexural strengths of the M-MXene-nanosheet-modified vinyl ester resin being 52.57% and 54.60% higher, respectively, than those of the neat vinyl ester resin for a loading quantity of nanosheets of only 0.04 wt %, which is economically viable. The main mechanisms by which the nanosheets toughen the resin are crack deflection and crack pinning.     

有机硅改性酚醛──丁腈胶粘剂的研制

］本文介绍了一种有机硅改性酚醛——丁腈胶粘剂，该胶具有优异的耐热老化性能，预热处固化温度低，时间短，高温强度高，可广泛用于各种耐热老化部件的粘接。     

耐腐蚀性乙烯基酯树脂的研究与应用

论述了乙烯基酯树脂优异的耐腐蚀性能,耐腐蚀原理及目前国内外耐腐蚀性乙烯基酯树脂的研究进展和在一些领域的典型应用。