Benzoxazine resin, a new type of phenolic resin, has many advantages, such as a strong molecular design, no small molecular release in the curing process, excellent thermal stability and mechanical properties, and a high residual carbon ratio. Thus, it is important for electronic communication industry matrix material. To meet the needs of high-frequency and high-speed communication technology for low-dielectric polymer resin, the low-dielectric modification of benzoxazine resin is of great significance to the high frequency and high-speed propagation of the signal, which attracts a wide range of materials researchers’ attention. In this paper, we review a series of studies on the low dielectric modification of benzoxazine resin in recent years, including the synthesis of new monomers, inorganic - organic hybridization, copolymerization with other resins, and low molecular weight benzoxazine resin research trends.

1. Rimdusit S, Ishida H. Development of new class of electronic Packaging materials based on ternary systems of benzoxazine, epoxy, and phenolic resins. Polymer 2000; 22: 7941-7949.

2. Rimdusit S, Ishida H. Gelation study of high processability and High reliability ternary systems based on benzoxazine, epoxy and Phenolic resins for application electronic packaging materials. Rheologica Acta 2000; 41: 1-9.

3. Ogura I. Handbook of low and high dielectric constant materials and their applications. Academic Press, 1999. 213-219.

4. Hamerton I, Howlin B J, Mitchelll A L, et al. Systematic Examination of thermal, mechanical and dielectrical properties of Aromatic polybenzoxazines. Reactive and Functional Polymers 2012; 72: 736-744.

5. Sua YC, Chen WC, Ou KL, et al. Study of the morphologies and dielectric constants of nanoporous materials derived from benzoxazine-terminated poly (3 caprolactone)/polybenzoxazine stocks. Polymer 2005; 46: 3758-3766.

6. Kumar RS, Padmanathanbc N, Alagar M. Design of hydrophobic Polydimethylsiloxane and polybenzoxazine hybrids for interlayer Low k dielectrics. New Journal of Chemistry 2015; 39: 3995-4008.

7. Zhang K, Zhuang QX, Liu XY, et al. Preparation and properties of novel low dielectric constant benzoxazole-based polybenzoxazine. Polymer Chemistry 2012; 50: 5115-5123.

8. Zhang K, Zhuang QX, Cai RL, et al. Synthesis and Copolymerization of benzoxazines with low-solar constants and High thermal stability. RSC Advances 2013; 3: 5261-5270.

9. Herrera PV, Doyama K, Abe H, et al. Synthesis and Characterization of highly fluorinated polymer with the benzoxazine moiety in the main chain. Macromolecules 2008; 41: 9704-9714.

10. Herrera PV, Ishida H. Synthesis and characterization of highly Fluorinated diamines and benzoxazines derived therefrom. Journal of Fluorine Chemistry 2009; 130: 573-580.

11. Parveen AS, Thirukumaran P, Sarojadevi M. Low dielectric Materials from fluorinated polybenzoxazines. Polymers for Advanced Technologies 2014; 25: 1538-1545.

12. Su YC, Chang FC. Synthesis and characterization of fluorinated polybenzoxazine material with low dielectric constant. Polymer 2003; 44: 7989-7996.

13. Shieh J Y, Lin C Y, Huang C L, et al. Synthesis and characterization of novel dihydrobenzoxazineous. Journal of Applied Polymer Science 2006; 101: 342-347.

14. Hwang HJ, Lin CY, Wang CS Flame retardancy and dielectric properties of dicyclopentadiene-based benzoxazine cured with a phosphorus-containing phenolic resin. Journal of Applied Polymer Science 2008; 110: 2413-2423.

15. Liu Z, Yuan C, Huang F. Benzoxazine blend resin and its glass fiber cloth preparation and properties of reinforced composites. Polymer Materials Science and Engineering 2013; 30(4): 13-21.

16. Xiao L, Yu R, Zhao W, et al. Benzoxazine resin based aromatic sulfonamide fiber and glass study on the properties of fiber composites. FRP/Composites 2010; 6: 21-24.

17. Wang YQ, Kou KC, Zhuo LH, et al. Preparation of Boz/glass fibers/cyanate ester resins Lamin composites. Polymer Composites 2015; 1-5.

18. Li GZ, Wang LC, Ni HL, et al. Polyhedral oligomeric silsesquioxane (POSS) polymers and copolymers: A review. Journal of Inorganic and Organometallic Polymers 2001; 3: 123-154.

19. Tseng MC, Liu YL. Preparation, morphology, and ultra-low Natural constants of benzoxazine-based polymers/polyhedral oligomeric silsesquioxane (POSS) nanocomposites. Polymer 2010; 51: 5567-5575.

20. Vengatesan MR, Devaraju S, Kumar AA, et al. Studies on thermal and dielectric properties of octa (maleimido phenyl) silsesquioxane (OMPS) Polybenzoxazine (PBZ) hybrid nanocomposites. High Performance Polymers 2011; 23: 441-456.

21. Vengatesan M R, Devaraju S, Dinakaran K, et al. Studies on Thermal and dielectric properties of organo clay and octakis (dim ethylsiloxypropylglycidylether) Silsesquioxane filled polybenzoxazine Hybrid nanocomposites. Polymer Composites 2011; 11: 1701-1711.

22. Kumar RS, Alagar M. Dielectric and thermal behaviors of POSS terms polyurethane based polybenzoxazine nanocomposites. RSC Advances 2015; 42: 33008-33015.

23. Sethuraman K, Vengatesan MR, Lakshmikandhan T, et al. Thermal and dielectric properties of ‘thiolene’ photocured hybrid Composite materials from allylterminated benzoxazine and SH-POSS. High Performance Polymers 2015; 27: 1-12.

24. Thirukumaran P, Parveen AS, Sarojadevi M. Synthesis of Eugenol-based polybenzoxazine-poss nanocomposites for low dielectric applications. Polymer Composites 2015; 11: 1973-1982.

25. Chandramohan A, Chozhan CK, Alagar M. Polysilsesquioxanere inforced phosphorous containing bis (4-maleimidophenyl) benzoxazine hybrid nanocomposites. High Performance Polymers 2013; 25: 744-758.

26. Liu HC, Su WC, Liu YL. Self-assembled benzoxazine-bridged polysilsesquioxanes exhibiting ultralow-host constants and yellow-light photoluminescent emission. Journal of Materials Chemistry 2011; 21: 7182-7187.

27. Kumar R S, Ariraman M, Alagar M. Design of lamellar structured POSS / BPZ polybenzoxazine nanocomposites as the novel class of ultra low k dielectric material. RSC Advances 2014, 4: 19127-19136.

28. Zhang K, Zhuang QZ, Liu XY, et al. A new benzoxazine Containing benzoxazole-functionalized polyhedral oligomeric silsesquioxane and the corresponding polybenzoxazine nanocomposites. Macromolecules 2013; 46: 2696-2704.

29. Kumar R S, Ariraman M, Alagar M. Studies on MCM-41/PDMS based hybrid polybenzoxazine nanocomposites for interlayer low k dielectrics. RSC Advances 2015; 5: 40798-40806.

30. Vengatesan MR, Devaraju S, Dinakaran K, et al. SBA-15 filled Polybenzoxazine nanocomposites for low-k dielectric applications. Journal of Materials Chemistry 2012; 22: 7559-7566.

31. Selvaraj V, Jayanthi KP, Lakshmikandhanc T, et al. Development of a polybenzoxazine/TSBA-15composite from the Renewable resource cardanol for low-k applications. RSC Advances 2015, 5: 48898-48907.

32. Geim A K. Graphene: Status and prospects. Science 2009; 324: 1530-1534.

33. Stankovich S, Dikin DA, Dommett GHB, et al. Graphenebased composite materials. Nature 2006; 442: 282-286.

34. Novoselov KS, Falko VI, Colombo L, et al. A roadmap for graphene. Nature 2012; 490: 192-200.

35. Zeng M, Wang J, Li RR, et al. The curing behavior and thermal property of graphene oxide/benzoxazine nanocomposites. Polymer 2013; 54: 3107-3116.

36. Xu QY, Zeng M, Feng ZJ, et al. Understanding the effects of carboxylated groups of functionalized graphene oxide on the curing behavior and intermolecular interactions of benzoxazine nanocomposites. RSC Advances 2016; 6: 31484-31496.

37. Kumar RS, Ariraman M, Alagar M. Studies on dielectric properties of GO reinforced bisphenol-Z polybenzoxazine hybrids. RSC Advances 2015; 5: 23787-23797.

38. Lin CH, Huang SJ, Wang PJ, et al. Miscibility, microstructure, and thermal and dielectric properties of reactive blends of dicyanate ester and diamine-based benzoxazine. Macromolecules 2012; 45: 7461-7466.

39. Yan HX, Li TT, Feng S, et al. Mechanical and dielectric properties of blends of dicyanate ester and bisphenol a-based benzoxazine. High Performance Polymers 2014; 26: 618-625.

40. Li X, Luo X, Xia Y, et al. Benzoxazine/cyanate ester copolymer and performance. Polymer Materials Science and Engineering 2015; 31(8): 96-101.

41. Lin CH, Huang CM, Wong TI, et al. High-Tg and lowdielectric epoxy hotosets based on a propargyl ether-containing phosphinated benzoxazine. Polymer Chemistry 2014; 52: 1359-1367.

42. Krishnadevi K, Selvaraj V. Development of halogen-free flame retardant phosphazene and rice husk ash incorporated benzoxazine blended epoxy composites for microelectronic applications. New Journal of Chemistry 2015; 39: 6555-6567.

43. Krishnadevi K, Grace AN, Alagar M, et al. Development of hexa (aminophenyl) cyclotriphosphazene-modified cyanate ester composites for high temperature applications. High Performance Polymers 2014; 26: 89-96.

44. Krishnadevi K, Selvaraj V, Prasanna D. Thermal, mechanical and antibacterial properties of cyclophosphazined incorporated benzoxazine blended bismaleimide composites. RSC Advances 2015; 5: 913-921.

45. Wang CF, Su YC, Kuo SW, et al. Low-surface-free-energy Materials based on polybenzoxazines. Angewandte Chemie International Edition 2006; 45: 2248-2251.

46. Li XD, Xia YQ, Xu WL, et al. The curing procedure for a Benzoxazine-cyanate-epoxy system and the properties of the terpolymer. Polymer Chemistry 2012; 3: 1629-1633.

47. Jamshidi S, Yeganeh H, Ataei S M. Preparation and properties of one-pack polybenzoxazine-modified polyurethanes with improved thermal stability and electrical insulating properties. Polymer International 2011; 60: 126-135.

48. Gaina C, Ursache O, Gaina V, et al. Poly (urethane-benzoxazine)s. Journal of Polymer Research 2014; 21: 586-596.

49. Wang YQ, Kou KC, Zhuo LH, et al. Thermal, mechanical and dielectric properties of BMI modified by the bis allyl benzoxazine. Journal of Polymer Research 2015, 22: 51-59.

50. Wang YQ, Kou KC, Zhao W, et al. The effect of functionalized benzoxazine with allyl groups on the dielectric, mechanical and thermal properties of BMI/BADCy composites. RSC Advances 2015; 5: 99313-99321.

51. Wang YQ, Kou KC, Wu GL, et al. The effect of bis allyl benzoxazine on the thermal, mechanical and dielectric properties of bismaleimide-cyanate blend polymers. RSC Advances 2015; 5: 58821-58831.

52. Zhang CX, Luo XX, Zhu RQ, et al. Thermal and dielectric properties of epoxy/DDS/CTBN adhesive modified by cardanol based benzoxazine. Journal of Adhesion Science and Technology 2015; 29: 767-777.