Recent research has shed light on the importance of four-phonon scattering processes in the thermal conductivity (k) of 2D materials. The inclusion of 4 phonon scattering processes from first-principles has been shown to lead to a thermal conductivity of ∼1290 W m-1 K-1 in graphene at 300 K, significantly lower than the values predicted to be in excess of 4000 W m-1 K-1 based only on 3 phonon scattering processes. Four phonon processes are shown to be most significant for flexural ZA phonon modes, where the reflection symmetry selection rule (RSSR) is less restrictive for 4-phonon than 3-phonon scattering processes. This combined with the low frequencies of ZA phonon modes, leading to high populations, leads to higher 4-phonon than 3-phonon scattering of low frequency ZA phonon modes in graphene at 300 K. In this review, the role of parameters such as atomic structure, phonon dispersion and temperature on 4-phonon scattering processes in a wide range of 2D materials is reviewed. Materials such as graphene nanoplatelets (GnPs) have been extensively investigated for enhancement of the thermal conductivity of polymer composites. However, such enhancement is limited by the poor interfacial thermal conductance between the polymer and filler material. Interconnected filler networks overcome this issue through highly efficient continuous percolative heat transfer paths throughout the composite. Such 3D networks have been shown to enable ultra-high polymer thermal conductivities, approaching ∼100 W m-1 K-1, and even exceeding those of several metals. In this review, different techniques used to achieve such interconnected 3D filler networks, namely, aerogels, foams, ice-templating, expanded graphite, hot pressing of filler coated polymer particles, the synergistic effect between multiple fillers, and the stitching of filler sheets, are discussed and their impact on thermal conductivity enhancement are presented.