Polymers Beyond Chlorine

  • A. MuzafarovEmail author


Chlorine is an important catching reagent used in polymer chemistry, as well as various other areas of organic and inorganic chemistry. The abundance of simple methods to substantially alter polymer characteristics by adding chlorine has resulted in increasing interest in obtaining and utilizing new chlorine-containing polymers. Chlorine processes are used on a large scale not only to produce chlorine-containing polymer compounds but also in the intermediate stages of polymer synthesis. However, chlorine-containing solvents used for the production of polymers represent a dangerous and poorly controlled threat to the environment. Cheap, incombustible and volatile, these freons are close to being prohibited by law in many countries due to the degree of their negative environmental impact. A large sector of important polymer materials – silicones – is based on the so-called chloric cycle, which involves an addition of chlorine to a silicon atom at the first stage, and then removal of chlorine during the process of producing silicones. It has been shown that eliminating the need for chlorine-containing compounds in this sector is very challenging, but achievable.


Alkoxysilanes Polyorganosiloxanes Silicones Polycondensation Direct synthesis Chlorine-free process Composite polymer materials Environmental friendly materials 



This study was supported by the Russian Science Foundation (project # 14-23-00231).


  1. 1.
    Kirk RE, Othmer DF (1997) The Kirk-Othmer Encyclopedia of Chemical Technology, vol 24, 4th edn. Wiley, New York, pp 882–923Google Scholar
  2. 2.
    Felder RM, Ronald W (2004) Elementary principles of chemical processes. Wiley, New York, p 581; Donskoi AA, Shashkina MA, Zaikov GE (2003) Fire resistant and thermally stable materials derived from chlorinated polyethylene. VSR BV, NetherlandsGoogle Scholar
  3. 3.
    Harada M (2013) Method for producing chlorinated vinyl chloride resin. WO2013081133 2011-12-02Google Scholar
  4. 4.
    Ravve A (2000) Principles of polymer chemistry. Kluwer Academic/Plenum Publisher, New YorkCrossRefGoogle Scholar
  5. 5.
    Volynskii AL, Bakeev NF (1995) Solvent crazing of polymers. Elsevier, AmsterdamGoogle Scholar
  6. 6.
    Chojnowski J (1993) In: Clarson SJ, Semlyen JA (eds) Siloxane polymer. Prentice Hall, Englewood Cliffs, p 1Google Scholar
  7. 7.
    Panchenko BI, Gruber VN, Klebanskii AL (1969) Study of the hydrolytic polycondensation of dimethyldichlorosilane in concentrated hydrochloric acid. Polym.Sci USSR 11:496; Rubimsztajn S, Cypryk M, Chojnowski J (1989) Condensation of model linear siloxane oligomers possessing silanole and silyl chloride end groups. J Organomet Chem 367:27Google Scholar
  8. 8.
    Burger C, Kreuzer FH (1996) Chap 3: Polysiloxanes and polymers containing siloxane groups. In: Kricheldorf RH (ed) Silicon in polymer synthesis. Springer, Berlin, p 113CrossRefGoogle Scholar
  9. 9.
    Vaughn H (1964) Improvements in organopolysiloxane copolymers and a process for making them. GB 1,039,445; Pike R (1960) Zeolite catalyzed condensation process for producing organosilicon polymers. GB 943,841Google Scholar
  10. 10.
    Frances JM, Mutin HP (1998) Process for the preparation of optionally alkoxylatedpolyorganosiloxane resin by non-hydrolytic condensation. US 5,767,216; Koroleva TV, Zverev VV (2000) Method of preparing oligoalkyl siloxanes. RU2,268,902Google Scholar
  11. 11.
    Cho T et al. (1995) Process for preparing alkoxysilanes. US 5,103,034; Takashi O, Tadashi Y (2000) Production of alkoxysilane. JP 2000,178,282, Moody LG, Childress TE (1990) Trimethoxysilane preparation via the methanol-silicon reaction with recycle. EP 0,462,359
  12. 12.
    Gorshkov AS, Kopylov VM (2000) Method of preparing alkoxysilanes. RU2,157,375; Inaba Shinichi, Honda Shuichi (1988) Process for producing a tetraalkoxysilane. US,4,752,647Google Scholar
  13. 13.
    Lewis KM, Eng RN (2003) Nanosized copper catalyst precursors for the direct synthesis of trialkoxysilanes. US 2003,065,204Google Scholar
  14. 14.
    Roston WA, Cody RD (2008) Process for preparation of alkoxysilanes. US 7,582,788; Yang Se et al. In: Method for preparing trialkoxysilane. WO2013,035,956Google Scholar
  15. 15.
    Chunhui Y, Ji Li (2009) Method for directly synthesizing trialkoxysilane. CN 101,353,356Google Scholar
  16. 16.
    Temnikov MN, Zhiltsov AS, Muzafarov AM et al (2014) Comparison of effectiveness of various approaches to direct synthesis of alkoxysilanes. Silicon 7(2):69CrossRefGoogle Scholar
  17. 17.
    Ohta Yoshiro, Yoshizako Mamoru Process for the production of trialkoxysilanes. US4,931,578Google Scholar
  18. 18.
    Rochow EG (1948) Methyl silicate from silicon and methanol. J Am Chem Soc v 70:2170CrossRefGoogle Scholar
  19. 19.
    Yamada Yoshinori, Harada Masayoshi (1991) Production of trialkoxysilane. JPH05,178,864Google Scholar
  20. 20.
    Schattenmann FJ (2002) Method of making organyltriorganooxysilanes. US 6,455,721Google Scholar
  21. 21.
    Rochow EG (1972) Method for preparing alkoxy derivatives of silicon germanium tin thallium and arsenic. US 3,641,077Google Scholar
  22. 22.
    Hyde JF (1953) Silanol derivatives of the dimethyl substituted organosilicon compounds. J Am Chem Soc 75:2166CrossRefGoogle Scholar
  23. 23.
    Kantor SW (1953) The hydrolysis of methoxysilanes dimethylsilanediol. J Am Chem Soc 75:2712CrossRefGoogle Scholar
  24. 24.
    Kalinina A, Strizhiver N et al (2015) Polycondensation of diethoxydimethylsilane in active medium. Silicon 7(2):95CrossRefGoogle Scholar
  25. 25.
    Gruzd AS, Trofimchuk ES et al (2013) Novel polyolefin/silicon dioxide/H3PO4 composite membranes with spatially heterogeneous structure for phosphoric acid fuel cell. Int J Hydrog Energy 38:4132CrossRefGoogle Scholar
  26. 26.
    Popova EN, Yudin VE et al (2013) Carbon-reinforced plastics based on hybrid polyimide-organosilicon binders. Russ J Appl Chem 86(12):8739CrossRefGoogle Scholar
  27. 27.
    Vernigorov KB, Muzafarov AM et al (2012) Investigation of the structure of a polyimide modified by hyperbranched polyorganosiloxanes. Inorg Mater Appl Res 3(2):81CrossRefGoogle Scholar

Copyright information

© Springer International Publishing Switzerland 2016

Authors and Affiliations

  1. 1.A.N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussia
  2. 2.N.S. Enikolopov Institute of Synthetic Polymeric MaterialsRussian Academy of SciencesMoscowRussia

Personalised recommendations