Investigation of readily processable thermoplastic‐toughened thermosets. V. Epoxy resin toughened with hyperbranched polyester

This article describes the use of hyperbranched polyester oligomers (HBPs) as modifiers for epoxy thermosets. The effect of HBP molar mass, end group, and loading on prepolymer viscosity, thermoset fracture toughness, T_g, and high‐temperature dynamic storage modulus (E′) were measured. The HBP molar mass was systematically increased from nominal values of ∼ 1750 g mol (Generation 2, or G2) up to ∼ 14,000 g mol (Generation 5, or G5), which corresponds from a low of two layers of monomer up to a maximum of five layers of monomer around the central core. Toughness increased only modestly with the molar mass of the HBP. At 7% loading in the epoxy thermoset, the G5 HBP increased toughness by ∼ 60% over the untoughened control. Toughness increased to 82% above the untoughened control at a loading of 19% G5 HBP, but the toughness decreased at 28% HBP loading. The T_g and E′ were influenced by the HBP modifier, but the effect was not systematic and may have been due to competing effects of HBP molar mass and end group. The effect of the architecture of the thermoplastic modifier was investigated by introducing a linear aliphatic polyester (∼ 5400 g mol) with a repeat unit structure, which was similar to that of the HBP. At the molecular weight range investigated, neither the prepolymer viscosity nor the thermoset toughness of the HBP–epoxy was significantly different from that of the linear polyester in epoxy. Preliminary results are presented showing the effect of thermoplastic molecular weight and architecture on morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 151–163, 1999     

A morphological investigation of thermosets toughened with novel thermoplastics. I. Bismaleimide modified with hyperbranched polyester

The morphology of a bismaleimide (BMI) toughened with a thermoplastic hyperbranched aliphatic polyester (HBP) was studied by scanning electron microscopy (SEM). The effect of thermoplastic architecture, molecular weight, and end group on the size and arrangement of the dispersed phase was investigated and compared with the thermoset fracture toughness. SEM micrographs showed that higher molecular weight HBP formed roughly spherical dispersed domains of up to ∼ 60 μm, which contained BMI inclusions. Lower molecular weight HBP formed spherical dispersed thermoplastic domains, with diameters up to ∼ 10 μm with no BMI inclusions. A low molecular weight linear polyester with a repeat unit structure, which was similar to that of the HBP, was prepared and used as a control. Within error, BMI toughened with the linear control yielded the same fracture toughness as the best values obtained with HBP‐modified BMI, but the morphology differed. The linear polyester phase separated into particles with a larger average diameter and also possessed some phase‐inverted regions. End group effects were studied by modifying the hydroxy‐terminated HBP to unreactive nitrophenyl, phenyl, and acetyl end groups. The nitrophenyl‐terminated HBP did not phase separate from the thermoset, whereas the nonpolar phenyl‐ and acetyl‐terminated HBP phase separated to form small (≤1 μm and ∼ 2 μm, respectively) spherical domains. Some comparisons were made to other results with HBP thermoplastics in BMI and epoxy thermosets. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1065–1076, 1999     

One‐pot synthesis of hyperbranched poly(aryl ether ketone)s for the modification of bismaleimide resins

Hyperbranched poly(aryl ether ketone)s with hydroxyl end groups (HBP‐OH) and high degree of branching value (83%) were synthesized via an A₂ + B₃ approach. The polymerization conditions (e.g., polymerization temperature and time, monomer concentration, stoichiometric ratio of functional groups) were explored to avoid the gelation. Allyl‐terminated hyperbranched PAEKs (HBP‐AL) with low molecular weight (M_n = 3.4 × 10³) and narrow polydispersity (PDI = 1.65) were obtained via the etherification of HBP‐OH and it has been used for the modification of bismaleimide (BMI) resins. The prepolymers showed good processibilities with a viscosity below 0.6 Pa s at 110°C, though the viscosities slightly increased as the increase of HBP‐AL contents. The cured BMI resins showed high glass transition temperatures (T_g > 320°C) and good thermal stabilities (T_d > 400°C, both in nitrogen and air). It is inspiring to note that the incorporation of HBP‐AL into BMI matrix results in a significant enhancement of toughness without any noticeable loss in modulus, processibility, and T_g. POLYM. ENG. SCI., 54:1675–1685, 2014. © 2013 Society of Plastics Engineers     

Investigation of readily processable thermoplastic-toughened thermosets. III. Toughening BMIs and epoxy with a comb-shaped imide oligomer

This is the third in a five-part series describing the preparation of tough, high-performance thermosets from low viscosity, autoclave-processable prepolymers. The first 2 articles described toughening of bismaleimides (BMI) and epoxy with linear imide thermoplastics of ∼ 1000 g/mol. Highly processable prepolymers were obtained, which resulted in increases in fracture toughness for BMI of ∼ 75–100%, while the fracture toughness of epoxy was increased by up to 220%. This article describes the preparation of a low-molecular-weight comb-shaped imide oligomer (∼ 4100 g/mol) and the effect of the oligomer architecture and end-group on BMI and epoxy prepolymer viscosity and fracture toughness. When an unreactive comb-shaped oligomer was incorporated in a BMI prepolymer (10% thermoplastic loading in the thermoset), the fracture toughness increased by 67% over that of an untoughed control, while a reactive oligomer increased the fracture toughness by 150% over an untoughened control. At 55°C, the viscosity of the solution of the reactive comb-shaped imide in B was only 6.2 Pa · S. When the oligomer was dissolved in epoxy resin, the viscosity was less than 0.2 Pa · S at 90°C, and the fracture toughness increased by 110 and 133% (at ∼ 13% loading in the thermoset), relative to an untoughened control, depending on the reactivity of the end group. The T_g and high-temperature modulus of BMI and epoxy remained approximately the same relative to the untoughened controls. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 943–951, 1998     

Phenolic Hyperbranched Polymers as Additives in Cationic Photopolymerization of Epoxy Systems

Summary: A phenolic group containing hyperbranched polyester (HBP) was synthesized and employed as chain transfer agent in cationic photopolymerization of a biscycloaliphatic epoxy monomer ( CE ). The epoxy group conversion increases by increasing the amount of HBP in the photocurable resin, due to a chain transfer reaction involving the phenolic‐OH groups. HBP acts as a plasticizer inducing decrease of the T_g values together with an increase of the toughness properties. Meanwhile gel content increases together with the E′ values. By increasing the amount of HBP in the photocurable resin an increase of the density is evident indicating a decrease of free volume. Therefore an improvement of the gas barrier properties might be expected; at the same time an increase of the thermal stability is evident.

     

Investigation of readily processable thermoplastic-toughened thermosets. II. Epoxy toughened using a reactive solvent approach

The fracture toughness of epoxy thermosets was increased by up to 220% using very low-molecular-weight (∼ 1000 g/mol) imide thermoplastic. The objective was to produce a low-viscosity prepolymer that could be easily autoclave-processed to give a tough thermoset. Here, an homogenous epoxy prepolymer was prepared by first synthesizing very low-molecular-weight linear aromatic imide (∼ 1000 g/mol) directly in a liquid allyl phenol reactive solvent, followed by dissolution of the epoxy (Epon® 825) and the cure agent (DDS) directly in the thermoplastic solution. The allyl phenol both cures into the epoxy network, through phenol functional groups, and accelerates the cure. The viscosity of the pure epoxy was 1.4 Pa · S at 30°C. The prepolymer formulations ranged from ∼ 5–33 Pa · S at 30°C, but all reduced to less than 1 Pa · S at 90°C. The onset of cure is well above 90°C so the prepolymer viscosity is within the range for autoclave processing. The cured resin plaques were not transparent, but phase-separated domains were not found by scanning electron microscopy, indicating that the domain size is below the detection limit of the instrument. The reactive solvent causes a decrease in both the T_g and the high temperature modulus of the thermoset. Introduction of the thermoplastic results in partial recovery of the T_g and modulus. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 935–942, 1998     

Effect of colophony emulsion on the adhesive properties of vinyl acetate/n‐butyl acrylate copolymeric latex

We prepared a novel copolymeric latex of vinyl acetate and n‐butyl acrylate (V‐B) using a semibatch emulsion polymerization process. The glass‐transition temperature (T_g), steady viscosity, flow activation energy (E_f), dynamic moduli, and amphiphilic properties of the V‐B latex in the presence of colophony were systematically investigated. The experimental results demonstrate that excellent adhesive behaviors were achieved for the V‐B latex blended with 20 wt % colophony, whereas good adhesive performance was related to the moderate T_g, viscosity, E_f, storage modulus, and low contact angle on the adherent. The debonding mechanisms for V‐B and its colophony‐modified latexes were analyzed. A possible mechanism for the V‐B latex blended with colophony emulsion was determined. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Lignin valorization by forming toughened thermally stimulated shape memory copolymeric elastomers: Evaluation of different fractionated industrial lignins

Lignin‐based thermal responsive dual shape memory copolymeric elastomers were prepared with a highly branched prepolymer (HBP, A₂B₃ type) via a simple one‐pot bulk polycondensation reaction. The effect of fractionated lignin type (with good miscibility in the HBP) on copolymer properties was investigated. The thermal and mechanical properties of the copolymers were characterized by DMA, DSC, and TGA. Tensile properties were dominated by HBP <45% lignin content while lignin dominated >45% content. The copolymers glass transition temperature (T_g) increased with lignin content and lignin type did not play a significant role. Thermally stimulated dual shape memory effects (SME) of the copolymers were quantified by cyclic thermomechanical tests. All copolymers had shape fixity rate >95% and >90% shape recovery for all compositions. The copolymer shape memory transition temperature (T_trans) increased with lignin content and T_trans was 20°C higher than T_g. Lignin, a renewable resource, can be used as a netpoint segment in polymer systems with SME behavior. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41389.     

Advanced chemically induced phase separation in thermosets: Polybenzoxazines toughened with multifunctional thermoplastic main-chain benzoxazine prepolymers

Multifunctional thermoplastic main-chain benzoxazine prepolymers were synthesized and systematically varied in their structure in order to function as high-performance toughener additives. Their unique chemical composition allows multiple covalent crosslinking with many thermoset network systems including benzoxazines and epoxides in conjunction with a defined chemical induced phase separation (CIPS) upon curing. This was successfully shown using a benzoxazine-based thermoset resin matrix as an example. The corresponding morphologies were addressable in a predictable manner and brought into context with the obtained macroscopic mechanical and thermal properties. In this relationship the CIPS process was classified and compared with the literature in more general means for advanced morphology control by differentiating between covalently attached and so-called gradient domain structures. The prepolymers were characterized by ¹H NMR, FT-IR, DSC and TGA. The thermoset morphologies were investigated by TEM and AFM. The fracture toughness (K_Ic) and the elastic modulus (E) were measured by fracture and three point bending experiments. Thermal properties of the resulting films have been tested by DMA.     

Mechanical Behavior and Fracture Toughness of Poly(L‐lactic acid)‐Natural Fiber Composites Modified with Hyperbranched Polymers

Summary: The use of hyperbranched polymers (HBP) with hydroxy functionality as modifiers for poly(L ‐lactic acid) (PLLA)‐flax fiber composites is presented. HBP concentrations were varied from 0 to 50% v/v and the static and dynamic tensile properties were investigated along with interlaminar fracture toughness. Upon addition of HBP, the tensile modulus and dynamic storage modulus (E′) both diminished, although a greater decline was noticed in the static modulus. The elongation of the composites with HBP showed a pronounced increase as large as 314% at 50% v/v HBP. The loss factor (tan δ) indicated a lowering of the glass transition temperature (T_g) due to a change in crystal morphology from large, mixed perfection spherulites to finer, smaller spherulites. The change in T_g could have also resulted from some of the HBP being miscible in the amorphous phase, which caused a plasticizing effect of the PLLA. The interlaminar fracture toughness measured as the critical strain energy release rate (G_IC) was significantly influenced by HBP. At 10% v/v HBP, G_IC was at least double that of the unmodified composite and a rise as great as 250% was achieved with 50% v/v. The main factor contributing to high fracture toughness in this study was better wetting of the fibers by the matrix when the HBP was present. With improved ductility of the matrix, it caused ductile tearing along the fiber‐matrix interface during crack propagation.

ESEM photograph of propagation region of the interlaminar fracture toughness specimens with 30% v/v of HBP.     

Epoxy‐toughened,unsaturated polyester interpenetrating networks

A series of translucent interpenetrating polymer networks (IPNs) made of a reactive elastomer [linear (D) and branched (T) with varying molecular weights] (Jeffamine?), a commercially available epoxy (D.E.R. 331), and an unsaturated polyester (15:85 wt %) were prepared. DSC data indicated complete cure after 8 h at 90°C. DMTA data showed a single glass‐transition temperature (T_g) for all elastomer‐containing IPNs, an indication of homogeneity. As expected, all IPNs showed a decrease in T_g with incorporation of elastomer, from 16 to 114°C or lower, the largest decrease being with T‐5000. Izod impact strengths were increased by 28–44%, but with no apparent pattern among structure and molecular weight variations. In several cases the standard deviation of impact data increased significantly. Flexural data were measured using a three‐point bend test. The highest flexural modulus obtained was that which incorporated linear D‐2000 with a decrease of only 22% upon incorporation of the elastomer, whereas other compositions dropped up to 55% in flexural modulus. The strongest material obtained was that using D‐2000 with a flexural strength increase of 65% upon incorporation of the elastomer. Two of the three branched elastomer components showed flexural strength increases of about 53%, but one was only equal to the base polyester resin. TGA data were recorded for all IPNs and values compared well to that of the pure polyester resin, with the exception of T‐403, which showed a 20°C decrease, and D‐2000 with a 10°C decrease. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2283–2286, 2002     

Relationships between thermally induced residual stresses and architecture of epoxy‐amine model networks

The capability of epoxy‐amine resins to develop residual stresses was studied as a function of temperature and network architecture. These residual stresses were induced while cooling epoxy‐glass bilayers from temperatures higher than the network glass transition temperature, T_g. This behavior was the result of the marked differences (α_r − α_g), in linear thermal expansion coefficient of the two components, as evidenced by the measurement of α_r for the epoxy networks under study. Various network architectures were selected, resulting from variation of (1) the chemical nature of both epoxide and curing agent, (2) the nature and relative amount of the chain‐extensor agent, and (3) the stoichiometric ratio. Three ranges of cooling temperature were observed systematically: first, the range of temperatures above T_g, where no stress has been detected, then an intermediate temperature range (from T_g to T*), where stresses develop quite slowly, and finally, the low temperature range (T < T*), where a linear increase in stress accompanies the decrease of temperature. The two latter regimes were quantitatively characterized by the extent, T_g − T*, of the first one and by the slope, SDR, of the second one. T_g − T* values were shown to be governed by the T_g of the network: the higher the T_g, the larger the gap between T_g and T*. This result was interpreted by accounting for the variation of relaxation rate at T_g from one network to the other. It was also shown that a semiempirical relationship holds between SDR and T_g: SDR decreases monotonically as T_g increases. By inspecting the effects of network architecture in more details, it turned out that SDR is governed by the Young's moduli, E_r(T − T_g), of the epoxy resins in the glassy state: the lower E_r(T − T_g), the lower SDR in a series of homologous networks. As E_r(T − T_g) values are known to be related to the characteristics of the secondary relaxation β, which depends, in turn, on crosslink density, SDR values were finally connected to the amplitude of the β relaxation processes. This finding was corroborated by the measurements on an antiplasticized dense network. Finally, data relative to thermoplastic‐filled networks showed that the addition of thermoplastic reduces the development of residual stresses, whatever the system, is homogeneous or biphasic. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 638–650, 2000     

Structure–property correlation study of hyperbranched polyurethane–urea (HBPU) coatings

This paper deals with the structure–property relation of different HBPU coatings based on the variation of parameters like, NCO/OH ratio, generation number and type of diisocyanates used. For this, the NCO terminated HBPU prepolymers were synthesized first by reacting the different generation hyperbranched polyesters (HBPs) with excess diisocyanates. In the next step, these HBPU prepolymer coated films were completely moisture cured to get the desired HBPU coatings. The synthesized polymers were confirmed by ¹H, ¹³C NMR and FT-IR spectroscopy methods whereas structure–property relation was drawn from the FT-IR peak deconvolution technique. The degree of branching (DB) and percent composition of different structural units present in the HBPs were calculated from the ¹H and ¹³C NMR data by using Fretch equation. The melt viscosity study of different HBP samples suggests that most polyester sample showed Newtonian behavior. The coating film properties were studied by DMTA, TGA, UTM, and contact angle measurement instruments. DMTA and TGA data shows that the increase of NCO/OH ratio and generation number had a favorable impact on storage modulus (E′), glass transition temperature (T_g), onset degradation temperature (T_1ON) and char residue values of the coatings. The contact angle and UTM data suggest that the hydrophobicity and tensile strength increases but flexibility decreases with increasing the NCO/OH ratio.     

Polyester hot-melt adhesives. I. Factors affecting adhesion to epoxy resin coatings

The peel strength and tensile shear strength of polyester hot-melt adhesives on metals coated with epoxy resins are affected by four characteristics of the polyester: (1) inherent viscosity, (2) glass transition temperature (T_g), (3) degree of crystallinity, and (4) melting point. The inherent viscosity affects the strength, toughness, and crystallinity of the adhesive. The T_g and degree of crystallinity affect the low-temperature adhesive properties; the peel strength is relatively low when the T_g is appreciably above the use temperature. The T_g, degree of crystallinity, and melting point affect the high-temperature adhesive properties. A hot-melt adhesive with high peel and tensile shear strengths from 0° to 120°C is the polyester of 1,4-butanediol and trans-1,4-cyclohexanedicarboxylic acid.     

Biobased thermosetting resins composed of L‐lysine methyl ester and bismaleimide

Lysine methyl ester (LME), which was generated in situ by the reaction of lysine methyl ester dihydrochloride and triethylamine in dimethyl sulfoxide (DMSO), was prepolymerized with 4,4′‐bismaleimidodiphenylmethane (BMI) at 80°C for 2 h in DMSO. Then, the formed prepolymer was precipitated in water. The obtained LME/BMI prepolymers with molar ratios of 2:2, 2:3, and 2:4 were compression‐molded at a final temperature of 230°C for 2 h to produce cured lysine methyl ester/4,4′‐bismaleimidodiphenylmethane resins (cLBs; cLB22, cLB23, and cLB24, respectively). Fourier transform infrared (FTIR) analyses revealed that the Michael addition reaction of amino groups to the C?C bonds of the maleimide group occurred in addition to the homopolymerization of the maleimide group. The glass‐transition temperature (T_g) and 5% weight loss temperature (T₅) of the cured resin increased with increasing BMI feed content, and cLB24 showed the highest T_g (343°C) and T₅ (389°C). The flexural strengths (131–150 MPa) and moduli (3.0–3.6 GPa) of the cLBs were comparable to those of the conventionally cured resins of BMI and 4,4′‐diaminodiphenylmethane. Field emission scanning electron microscopy analysis revealed that there was no phase separation for all of the cured resins. Although cLB23 and cLB24 were not biodegradable, cLB22 had a biodegradability of 8.5% after 30 days in an aerobic aqueous medium containing activated sludge. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40379.     

Studies of the stability of thermoplastic-modified bismaleimide resin

The stability of bismaleimide—o,o′-diallyl bisphenol A (BMI—DABA) blends modified with high-performance amorphous thermoplastic bisphenol A polysulfone (PSF), polyether ketone (PEK-C), and polyether sulfone (PES-C) bearing a phthalidylidene group has been studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The extent of stability of thermoplastic components has been compared with the area of the endothermic peak that appears within the glass transition region for thermoplastic component in cured blends aged at temperature below the glass transition temperature (T_g). The stability of thermoplastic can be improved by the formation of semi-interpenetrating polymer networks (semi-IPNs). The stability of thermoplastic with higher T_g is more easily controlled. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1965–1970, 1997     

Synthesis and characterization of poly(urethane‐ester)s based on calcium salt of mono(hydroxybutyl)phthalate

Calcium‐containing poly(urethane‐ester)s (PUEs) were prepared by reacting diisocyanate (HMDI or TDI) with a mixture of calcium salt of mono(hydroxybutyl)phthalate [Ca(HBP)₂] and hydroxyl‐terminated poly(1,4‐butylene glutarate) [HTPBG₁₀₀₀], using di‐n‐butyltin‐dilaurate as catalyst. About six calcium‐containing PUEs having different composition were synthesized by taking the mole ratio of Ca(HBP)₂:HTPBG₁₀₀₀:diisocyanate (HMDI or TDI) as 3:1:4, 2:2:4, and 1:3:4. Two blank PUEs were synthesized by the reaction of HTPBG₁₀₀₀ with diisocyanate (HMDI or TDI). The polymers were characterized by IR, ¹H NMR, Solid state ¹³C‐CP‐MAS NMR, TGA, DSC, XRD, solubility, and viscosity studies. The T_g value of PUEs increases with increase in the calcium content and decreases with increase in soft segment content. The viscosity of the calcium‐containing PUEs increases with increase in the soft segment content and decreases with increase in the calcium content. X‐ray diffraction patterns of the polymers show that the HMDI‐based polymers are partially crystalline and TDI‐based polymers are amorphous in nature. The dynamic mechanical analysis of the calcium‐containing PUEs based on HMDI shows that with increase in the calcium content of polymer, modulus (g′ and g″) increases at any given temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1720–1727, 2006     

Properties of crosslinked polyurethanes synthesized from 4,4′‐diphenylmethane diisocyanate and polyester polyol

Polyurethanes were synthesized using the high functional 4,4′‐diphenylmethane diisocyanate (MDI), polyester polyol, and 1,4‐butane diol. The synthesized polyurethanes were analyzed using differential scanning calorimeter (DSC), dynamic mechanical thermal analysis (DMTA), Fourier transform infrared (FTIR) spectrometer, and swelling measurement using N,N′‐dimethylformamide. From the result of thermal analysis by DSC and DMTA, single T_gs were observed in the polyurethane samples at all the formulated compositions. From this result, it is suggested that the polyurethanes synthesized in this study have crosslinked structure rather than the phase‐separated segmented structure because of the high functionality (f = 2.9) of the MDI. By annealing the polyurethane samples using DSC, the T_gs were increased by 4.7∼16.0°C at the various annealing temperatures. From the results of FTIR and swelling measurement of polyurethanes, it is suggested that the increase of T_g of the polyurethanes by annealing is not due to increase of the hydrogen bond strength but mainly due to the increase of the crosslink density. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 624–630, 2000     

High glass transition temperature bismaleimide‐triazine resins based on soluble amorphous bismaleimide monomer

A novel bismaleimide (DOPO‐BMI) with unsymmetrical chemical structure and DOPO pendant group has been prepared. The particular molecular structure makes DOPO‐BMI show an intrinsic amorphous state with a T_g about 135°C and excellent solubility in most organic solvents, which is beneficial to the processability of bismaleimide composite materials. A series of bismaleimide‐triazine (BT) resins have been prepared based on DOPO‐BMI and 2,2‐bis(4‐cyanatophenyl)propane at various weight ratios. The prepared BT resins show outstanding solubility in organic solvent and low viscosity about 10–671 mPa s at 180°C. The cured BT resins exhibit high glass transition temperature (T_g) over 316°C. As the weight ratio of DOPO‐BMI increases to 80% (BT80), the T_g can rise to 369°C (tan δ). The cured BT resins also show good thermal stability with the 5% weight loss temperature over 400°C under both nitrogen and air atmosphere. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42882.     

Investigation of readily processable thermoplastic-toughened thermosets. I. BMIs toughened via a reactive solvent approach

Moderate increases (∼ 50–75%) in the toughness of bismaleimides (BMIs) were achieved with very low-molecular-weight (∼ 1000 g/mol) imide thermoplastics at low levels of thermoplastic loading (∼ 10–20%). The thermoplastic was introduced into the BMI using a simple, one-pot, reactive solvent approach. In this approach, the reactive diluent of a two-part BMI was used as the reaction solvent for the thermoplastic synthesis. The BMI monomer was then dissolved in the thermoplastic reaction solution to yield a low-viscosity homogenous prepolymer. The viscosity of the thermoplastic solution was ∼ 6 Pa S at 55°C. The effect of thermoplastic loading and molecular weight on viscosity was determined by rheology, and the fracture toughness of neat resin plaques was determined by compact tension. Increasing the thermoplastic loading increased prepolymer viscosity without improving toughness, while increasing the thermoplastic molecular weight increased the toughness by only 25% more than the lowest-molecular-weight thermoplastic, yet increased viscosity fivefold. Fracture surfaces showed no obvious phase separation by scanning electron microscopy. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 469–477, 1998