Synthesis, Properties and Application of a Novel Epoxidized Soybean Oil-toughened Phenolic Resin

A novel epoxidized soybean oil-toughened-phenolic resin(ESO-T-PR)has been synthesized by etheri- fication graft and multi-amine curing ESO.Fourier transform infrared spectroscopy(FTIR)was adopted to investi- gate its molecular structure and scan electron microscope(SEM)was used to observe the micro morphology of its impact fracture surface.This ESO-T-PR was adopted as the matrix resin to prepare paper copper clad laminate (P-CCL)and the properties of resulting P-CCL are found superior to the related Chinese National Standard.The toughing mechanism was investigated by comparing the impact strength,solderleaching resistance,flexural strength, peeling strength and morphology of this ESO-T-PR with those of other two ESO modified phenolic resins.It is demonstrated that during the synthesizing process of ESO-T-PR,the phenol hydroxyl is etherified by ESO or ESO epoxy resin prepolymer(ESO chain extension polymer)and the long ESO epoxy resin chain segments enhance the crosslink density of ESO-T-PR and consequently improve the impact toughness and solderleaching resistance of P-CCL made of ESO-T-PR.The ESO-T-PR is a cheap matrix resin with excellent properties to make P-CCL(elec- tric guide board).

MODIFICATION OF EPOXY RESINS WITH PHENOLIC HYDROXYL-TERMINATED POLYSILOXANE

Phenolic hydroxyl-terminated polysiloxanes were incorporated into epoxy resins to reduce the internal stress owing to the mismatch in coefficient of thermal expansion (CTE). Polysiloxane-epoxy resin block copolymers were made by a pre-reaction step prior to the curing. In the cured resin, the domain size of the polysiloxane phase depended on the structure of the phenolic hydroxyl-terminated polysiloxane. It was found that the modulus of the cured resin depended largely on the level of the modifier, while the CTE was affected greatly by the structure of the polysiloxane. By means of incorporating a few percent of methylphenylsiloxane unit into the polydimethylsiloxane chain, or by introducing; more compatible end-capping groups, the compounds of more effective low stress modifiers were synthesized.

Synthesis and Properties of Novel Epoxidized Soybean Oil-modified Phenolic Resin /Montmorillonite Nanocomposites

The novel epoxidized soybean oil-modified-phenolic resin/clay nanocomposites（ESO-M-PR/ CN） was prepared. The coupling agent-benzyldimethylphenylammonium chloride [C6H5CH2N^＋（CH3）2C6H5Cl^- , B2MP] was adopted to modify the interface between the organic and inorganic phases. The effect of the nanocomposite structure on its physical and chemical properties was discussed. During the synthesizing process of ESO-M-PR/CN, the phenol hydroxyl was etherified by ESO or ESO epoxy resin prepolymer to provide long ESO epoxy segments. Long ESO epoxy resin chain segments enhanced the crosslink density of ESO-M- PR/CN. The thermal and mechanical properties exhibit a significant improvement. The temperature at which a weight loss of 5% occurs increases from 287.1 ℃ to 402.3 ℃. The flexural strength increases by 25%, while the flexural modulus increases by 39%. Moreover, the properties of resin were enhanced by the effect of the inorganic nanoparticles, while the size of the nanomontmorillonites in the phenolic resin was characterized with a scanning electron microscope. The particle size of inorganic montmorillonites in the modified system is less than 100 nm.

A Study on a Magnesium-Based Layered Composite Used as a Flame Retardant for Phenolic Epoxy Resins

The effects of a magnesium-based layered composite on the flammability of a phenolic epoxy resin(EP)are studied.In order to produce the required composite material,first,magnesium hydroxide,aluminum salt and deionized water are mixed into a reactor according to a certain proportion to induce a hydrothermal reaction;then,the feed liquid is filtered out using a solid-liquid separation procedure;finally,the material is dried and crushed.In order to evaluate its effects on the flammability of the EP,first,m-phenylenediamine is added to EP and vacuum defoamation is performed;then,EP is poured into a polytetrafluoroethylene mold,cooled to room temperature and demoulded;finally,the magnesium-based layered composite is added to EP,and its flame retardance is characterized by thermogravimetric analysis,limiting oxygen index and cone calorimetry.The X-ray diffraction patterns show that the baseline of magnesium-based layered composite is stable and the front shape is sharp and symmetrical when the molar ratio of magnesium to aluminium is 3.2:1;with the addition of magnesium-based layered composite,the initial pyrolysis temperature of EP of 10%,15%and 30%magnesium-based layered composite decreases to 318.2°C,317.9°C and 357.1°C,respectively.After the reaction,the amount of residual carbon increases to 0.1%,3.45%and 8.3%,and the limiting oxygen index increases by 28.3%,29.1%and 29.6%,respectively.The maximum heat release rate of cone calorimeter decreases gradually.The optimum molar ratio of Mg:Al for green synthesis is 3.2:1,and the NO_(3)-intercalated magnesium-based layered composite has the best flame retardance properties.

In-situ reactive compatibilization of HDPE/GTR blends by dicumyl peroxide and phenolic resin without catalyst

In-situ reactive compatibilization of high-density polyethylene （HDPE）/ground tire rubber （GTR） blends by dicumyl peroxide （DCP） and HY-2045 - a kind of thermoplastic phenolic resin without catalyst was investigated by studying the mor-phology, stress and strain behavior, dynamic mechanical properties and crystallization performance of the blends. Scanning e-lectron microscopy （SEM） results show that there are a lot of fibrous materials distributing in the interface, which connects the dispersed phase with the matrix and obtains better interfacial strength for prominent mechanical properties. The addition of compatibilizers results in the decrease of crystallinity of the blends and the disappearance of an obvious yield phenomenon, which was proved by the differential scanning calorimeter （DSC） test and X-ray diffraction （XRD） characterization Although the crystallinity of the blends decreases,the tensile strength and tensile strain of the blends significantly increases, especially for the HDPE/GTR/DCP/HY-2045 blends, which is possibly attributed to the good compatibility of the blends owing to the in-situ interface crosslinking. In addition, it is found that the compatibilizing HDPE/GTR blends shows a higher tan^ peak temperature and a broaden transition peak for GTR phase.

Preparation and Properties of Phenolic Resin/Montmorillonite Intercalation Nanocomposites

Phenolic resin/montmorillonite intercalation composites were prepared by using the methods of pressing intercalation and melt intercalation.Properties and structure of the composites were investigated by using XRD,TG and test of softening point.It is indicated that both the pressing intercalation and melt intercalation can be used to prepare the phenolic resin/organo-montmorillonite intercalation nanocomposites.Compared with phenolic resin,the intercalation nanocomposites have better heat-resistance,higher decomposition temperatures and less thermal weight-loss.However,these two intercalation methods have different effects on the softening point of the intercalation nanocomposites.Pressing intercalation almost does not affect the softening point of the intercalation nanocomposites,while melt intercalation significantly increases the softening point of the intercalation nanocomposites, probably due to the chemical actions happening in the process of melt intercalation.

Synthesis of benzoxazine-based phenolic resin containing furan groups

A novel benzoxazine-based phenolic resin containing furan groups（PFB） was synthesized via simple two-step reactions and the structure of PFB was confirmed by FTIR and ~1H NMR spectra.Differential scanning calorimetry（DSC） showed that the polybenzoxazine cured from PFB had good heat resistance and lower polymerization temperature compared with that of benzoxazine-based phenolic resins.

Structural Characteristics of Mesophase Spheres Prepared from Coal Tar Pitch Modified by Phenolic Resin

Mesocarbon microbeads （MCMB） were prepared from coal tar pitch modified by phenolic resin and from the same pitch modified by phenolic resin and hexamethylenetetramine at 440℃ for lh. By investigating the morphology of mesophase spheres and the structure of the MCMB carbonized at 1000℃ for lh using scanning electron microscope （SEM） and XRD, it was found that phenolic resin accelerated the formation and coalescence of mesophase spheres. Some of the obtained MCMB were hi- or tri-spheres with the distorted microtextural carbon layers. Hexamethylenetetramine in the pitch modified by phenolic resin accelerated the condensation of phenolic resin and consequently expedited the combination of mesophase spheres, which was proved by the formation of some tetra-spheres. Owing to the cross-linkage of the additives, MCMB with complex structure were obtained.

STUDY ON THE THERMODYNAMIC PROPERTIES OF ADSORPTION OF ETHYL BENZOATE AND DIETHYL PHTHALATE BY PHENOLIC RESIN ADSORBENTS

This paper presents experimental observations on the adsorption of individual solutes by a simple thermodynamic framework, and the equilibrium adsorption of ethyl benzoate and diethyl phthalate on phenolic resin adsorbent in hexane solutions within the temperature range of 293-313 K. The experimental results show that the Freundlich adsorption law is applicable to the adsorption of ethyl benzoate and diethyl phthalate on the adsorbent, since all the correlative factors R' are larger than 0.99. The negative values of all the isosteric adsorption enthalpies for ethyl benzoate and diethyl phthalate indicate that they undergo exothermic processes, while their magnitudes (19-28 kJ/mol) manifest a hydrogen bonding sorption process. Other thermodynamic properties: the free energy changes and the entropy change associated with the adsorption have been calculated from the Gibbs adsorption equation and the Gibbs-Helmholtz equation

PREPARATION AND PHOTOSENSITIVITY OF WATER SOLUBLE PHENOLIC RESINS CONTAINING ACRYLOYL AND QUATERNARY AMMONIUM CHLORIDE GROUPS

New water soluble and photocrosslinkable prepolymers containing acrylate and quaternary ammonium salt groups were synthesized from epoxy phenolic resin via ring-opening reaction with acrylic acid and with aqueous solution of triethylamine hydrochloride successively. The second reaction needs no phase transfer catalyst to accelerate, since the product formed can act as a phase transfer catalyst. The prepolymer obtained contains both photocrosslinkable acrylate groups and hydrophilic quaternary ammonium salt groups. Optimum conditions for these reactions were studied. The photosensitivity of the prepolymer was also investigated. The effects of different photoinitiators, different crosslinkable diluent monomers and amine accelerator on the photosensitivity of the prepolymer were compared. The photoinitiator of hydrogen abstraction type is still effective without using amine or alcohol as accelerator, because the prepolymer contains a H beside the OH groups formed in the ring-opening reactions.

Cardo poly (ether sulfone) toughened E51/DETDA epoxy resin and its carbon fiber composites

A toughener that can effectively improve the interlaminar toughness in carbon fiber composites is crucial for various applications.We investigated,the toughening effects of phenolphthalein-based cardo poly(ether sulfone)(PES-C)on E51/DETDA epoxy and its carbon fiber composites(CFCs).Scanning electron microscopy showed that the phase structures of PES-C/epoxy blends change from island(of dispersed phase)structures to bi-continuous structures(of the matrix)as the PES-C content increased,which is associated with reaction-induced phase separation.After adding 15 phr PES-C,the glass transition temperature(T_(g))of the blends increased by 51.5℃,and the flexural strength,impact strength and fracture toughness of the blends were improved by 41.1%,186.2%and 42.7%,respectively.These improvements could be attributed to the phase separation structure of the PES-C/epoxy sys-tem.A PES-C film was used to improve the mode-II fracture toughness(G_(IIC))of CFCs.The G_(IIC) value of the 7μm PES-C film toughened laminate was improved by 80.3%compared to that of the control laminate.The increase in G_(IIC) was attributed to cohesive failure and plastic deformation in the interleaving region.

Effect of Epoxy Resin on the Properties of Recycled Asphalt

To promote the recycling of reclaimed asphalt pavement(RAP),epoxy resin was used to prepare the epoxy-recycled asphalt mixtures.The effect of epoxy resin on the properties of aged asphalt binder was investigated based on the tensile test,flexural creep test,and laser scanning confocal microscopy.The curing characteristics and the mechanical performance of recycled asphalt with different epoxy contents were explored.The results show that the low-temperature performance,ductility,and strength of the aged asphalt binder were significantly improved when the epoxy content reached 40%.The curing time of epoxy-recycled asphalt should be at least 4 d to ensure the formation of good internal spatial network structure.

Enhanced corrosion resistance of epoxy resin coating via addition of CeO_(2) and benzotriazole

The use of fillers to enhance the corrosion protection of epoxy resins has been widely applied.In this work,cerium dioxide(CeO_(2))and benzotriazole(BTA)were introduced into an epoxy resin to enhance the corrosion resistance of Q235 carbon steel.Scanning electron microscopy results indicated that the CeO_(2) grains were rod-like and ellipsoidal in shape,and the distribution pattern of BTA was analyzed by energy dispersive spectroscope.The dynamic potential polarization curve proved the excellent corrosion resistance of the composite epoxy resin with CeO_(2) and BTA co-addition,and electrochemical impedance spectroscopy test analysis indicated the significantly enhanced long-term corrosion protection performance of the composite coating.And the optimal protective performance was provided by the coating containing 0.3%(mass)CeO_(2) and 20%(mass)BTA,which was attributed to the barrier performance of CeO_(2) particles and the chemical barrier effect of BTA.The formation of corrosion products was analyzed using X-ray diffraction.In addition,the corrosion resistance mechanism of the coating was also discussed in detail.

Optimization Mechanism of Mechanical Properties of Basalt Fiber-Epoxy Resin Composites by Interfacially Enriched Distribution of Nano-Starch Crystals

Fibre reinforced polymer composites have become a new generation of structural materials due to their unique advantages such as high specific strength,designability,good dimensional stability and ease of large-area monolithic forming.However,the problem of interfacial bonding between the resin matrix and the fibres limits the direct use of reinforcing fibres and has become a central difficulty in the development of basalt fibre-epoxy composites.This paper proposes a solution for enhancing the strength of the fibre-resin interface using maize starch nanocrystals,which are highly yield and eco-friendly.Firstly,in this paper,corn starch nanocrystals(SNC)were prepared by hydrolysis,and were deposited on the surface of basalt fibers by electrostatic adsorption.After that,in order to maximize the modification effect of nano-starch crystals on the interface,the basalt fiber-epoxy resin composite samples were prepared by mixing in a pressureless molding method.The test results shown that the addition of basalt fibers alone led to a reduction in the strength of the sample.Deposition of 0.1 wt%SNC on the surface of basalt fibers can make the strength consistent with pure epoxy resin.When the adsorption amount of SNC reached 0.5 wt%,the tensile strength of the samples was 23.7%higher than that of pure epoxy resin.This is due to the formation of ether bond homopolymers between the SNC at the fibre-epoxy interface and the epoxy resin,which distorts the originally smooth interface,leading to increased stress concentration and the development of cracks.This enhances the binding of basalt fibers.The conclusions of this paper can provide an effective,simple,low-cost and non-polluting method of interfacial enhancement modification.

Evaluation of the injection and plugging ability of a novel epoxy resin in cement cracks

Sustained casing pressure(SCP)is a crucial issue in the oil and gas production lifecycle.Epoxy resins,exhibiting exceptional compressive strength,ductility,and shear bonding strength,have the potential to form reliable barriers.The injectivity and sealing capacity of the epoxy resin is crucial parameters for the success of shallow remediation operations.This study aimed to develop and assess a novel solid-free resin sealant as an alternative to Portland cement for mitigating fluid leakage.The investigation evaluated the viscosity,compressive strength,and brittleness index of the epoxy resin sealant,as well as its tangential and normal shear strengths in conjunction with casing steel.The flow characteristics and sealing abilities of conventional cement and epoxy resin were comparatively analyzed in cracks.The results showed that the application of a viscosity reducer facilitated control over the curing time of the epoxy resin,ranging from 1.5 to 6 h,and reduced the initial viscosity from 865.53 to 118.71 m Pa,s.The mechanical properties of the epoxy resin initially increased with a rise in curing agent content before experiencing a minor decrease.The epoxy resin containing 30%curing agent exhibited optimal mechanical properties.After a 14-day curing period,the epoxy resin's compressive strength reached81.37 MPa,2.12 times higher than that of cement,whereas the elastic modulus of cement was 2.99 times greater than that of the epoxy resin.The brittleness index of epoxy resin is only 3.42,demonstrating high flexibility and toughness.The tangential and normal shear strengths of the epoxy resin exceeded those of cement by 3.17 and 2.82 times,respectively.In a 0.5 mm-wide crack,the injection pressure of the epoxy resin remained below 0.075 MPa,indicating superior injection and flow capabilities.Conversely,the injection pressure of cement surged dramatically to 2.61 MPa within 5 min.The breakthrough pressure of0.5 PV epoxy resin reached 7.53 MPa,decreasing the crack's permeability to 0.02 D,a mere 9.49%of the permeability observed following cement plugging.Upon sealing a 2 mm-wide crack using epoxy resin,the maximum breakthrough pressure attained 5.47 MPa,3.48 times of cement.These results suggest that epoxy resin sealant can be employed safely and effectively to seal cracks in the cement.

Curing mechanism of alkaline phenolic resin with organic ester

To study the curing mechanism of alkaline phenolic resin with organic ester, three esters were chosen to react with three systems - alkaline phenolic resin, potassium hydroxide aqueous solution containing phenol, and potassium hydroxide aqueous solution. The variations of pH, heat release and gel pH during the reactions were monitored and measured. Infrared spectroscopy （IR） and thermal gravity analysis （TG） techniques were used to characterize the curing reaction. It was found that organic ester is only partial y hydrolyzed and resin can be cured through organic ester hydrolysis process as wel as the reaction with redundant organic ester. The sequential curing mechanism of alkaline phenolic resin cured by organic ester was identified as fol ows： a portion of organic ester is firstly hydrolyzed owing to the effect of the strong alkaline; the gel is then formed after the pH decreases to about 10.8-10.88, meanwhile, the redundant organic ester （i.e. non-hydrolysis ester） starts the curing reaction with the resin. It has also been found that the curing rate depends on the hydrolysis velocity of organic ester. The faster the hydrolysis speed of the ester, the faster the curing rate of the resin.

Application conditions for ester cured alkaline phenolic resin sand

Five organic esters with different curing speeds:propylene carbonate(i.e.high-speed ester A);1,4-butyrolactone;glycerol triacetate(i.e.medium-speed ester B);glycerol diacetate;dibasic ester(DBE)(i.e.lowspeed ester C),were chosen to react with alkaline phenolic resin to analyze the application conditions of ester cured alkaline phenolic resin.The relationships between the curing performances of the resin(including pH value,gel pH value,gel time of resin solution,heat release rate of the curing reaction and tensile strength of the resin sand)and the amount of added organic ester and curing temperature were investigated.The results indicated the following:(1)The optimal added amount of organic ester should be 25 wt.%-30 wt.%of alkaline phenolic resin and it must be above 20 wt.%-50 wt.%of the organic ester hydrolysis amount.(2)High-speed ester A(propylene carbonate)has a higher curing speed than 1,4-butyrolactone,and they were both used as high-speed esters.Glycerol diacetate is not a high-speed ester in alkaline phenolic resin although it was used as a high-speed ester in ester cured sodium silicate sand;glycerol diacetate and glycerol triacetate can be used as medium-speed esters in alkaline phenolic resin.(3)High-speed ester A,medium-speed ester B(glycerol triacetate)and low-speed ester C(dibasic ester,i.e.,DBE)should be used below 15°C,35°C and 50°C,respectively.High-speed ester A or lowspeed ester C should not be used alone but mixed with medium-speed ester B to improve the strength of the resin sand.(4)There should be a suitable solid content(generally 45 wt.%-65 wt.%of resin),alkali content(generally 10 wt.%-15 wt.%of resin)and viscosity of alkaline phenolic resin(generally 50-300 mPa·s)in the preparation of alkaline phenolic resin.Finally,the technique conditions of alkaline phenolic resin preparation and the application principles of organic ester were discussed.

PREPARATION OF BISPHENOL A EPOXY RESIN WATERBORNE DISPERSIONS BY THE PHASE INVERSION EMULSIFICATION TECHNIQUE

The phase inversion emulsification technique (PIET) is an effective physical method for preparing waterborne dispersions of polymer resins. Some results concerning the preparation of bisphenol A epoxy resin waterborne dispersions by PIET in our laboratory were summarized. Electrical properties, rheological behavior and morphological evolution during phase inversion progress were systematically characterized. The effects of the emulsifier concentration and emulsification temperature on phase inversion progress and the structural features of the waterborne particles were studied as well. The deformation and break up of water drops in a shear field were analyzed in terms of micro-theology, while the interaction and coalescence dynamics of water drops were discussed in terms of DLVO theory and Smoluchowski effective collision theory, respectively. Based on the experimental results and theoretical analysis, a physical model of phase inversion progress was suggested, by which the effects of the parameters on phase inversion progress and the structural features of the waterborne particles were interpreted and predicted.

Preparation of Phenolic Resin/Silver Nanocomposites via in-situ Reduction

Resol type phenolic resin/silver nanocomposite was prepared by in-situ reduction method, in which the curing of phenolic resin and the formation of silver nano-particles took place simultaneously. The silver ions were reduced completely to silver nanoparticles, which were dispersed homogeneously in the resin matrix with narrow size distribution.

Ceramification of Composites of MgO-Al_(2)O_(3)-SiO_(2)/Boron Phenolic Resin with Different Calcine Time

The ceramifiable polymer composite of MgO-Al_(2)O_(3)-SiO_(2)/boron phenolic resin(MAS/BPF)with 40wt%of inorganic fillers was calcined at 1200℃for different time to promote ceramification of ceramifiable composite and improve heat resistance.The effects of different calcine time on the macroscopical morphology,mass loss,phase evolution,microstructure and chemical bond evolution of MAS/BPF composites were characterized by XRD,XPS,and SEM analyses.The experimental results reveal that the increase of calcine time result in the fewer holes,relatively denser and smoother top layer of MAS/BPF composites and protect the interior from deeper decomposition.The final residues of composites are amorphous carbon and C-O-Si-Al-Mg ceramic.And MAS/BPF composites show excellent mass stability,low shrinkage and self-supporting features after 2 h holding compared with BPF composites without 40wt%of inorganic fillers.