Preparation of Ultralow Molecular Weight Poly(vinyl chloride) with Sub-micrometer Particles <italic style="font-style: italic">via</italic> Precipitation Polymerization

Peng Cui; Chang-Tong Song; Xian-Hong Zhang; Dong Chen; Yu-Hong Ma; Wan-Tai Yang

doi:10.1007/s10118-019-2252-x

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Preparation of Ultralow Molecular Weight Poly(vinyl chloride) with Sub-micrometer Particles via Precipitation Polymerization

ARTICLE | Updated：2021-02-18

- Preparation of Ultralow Molecular Weight Poly(vinyl chloride) with Sub-micrometer Particles via Precipitation Polymerization
- Chinese Journal of Polymer Science Vol. 37, Issue 7, Pages: 646-653(2019)
- Affiliations：
  
  a.State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
  b.College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China
- Author bio：
  
  xhzhang@mail.buct.edu.cn (X.H.Z.)
  yangwt@mail.buct.edu.cn (W.T.Y.)
- Funds：
- DOI：10.1007/s10118-019-2252-x
  CLC：
- Received：16 January 2019，
  
  Revised：2019-3-5，
  
  Accepted：08 March 2019，
  
  Online First：04 April 2019，
  
  Published：2019-07
- Accepted：
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Citation: Cui, P.; Song, C. T.; Zhang, X. H.; Chen, D.; Ma, Y. H.; Yang, W. T. Preparation of ultralow molecular weight poly(vinyl chloride) with sub-micrometer particles via precipitation polymerization. Chinese J. Polym. Sci. 2019, 37, 646–653

Peng Cui, Chang-Tong Song, Xian-Hong Zhang, et al. Preparation of Ultralow Molecular Weight Poly(vinyl chloride) with Sub-micrometer Particles via Precipitation Polymerization[J]. Chinese Journal of Polymer Science, 2019, 37(7): 646-653. DOI: 10.1007/s10118-019-2252-x.
Citation: Cui, P.; Song, C. T.; Zhang, X. H.; Chen, D.; Ma, Y. H.; Yang, W. T. Preparation of ultralow molecular weight poly(vinyl chloride) with sub-micrometer particles via precipitation polymerization. Chinese J. Polym. Sci. 2019, 37, 646–653 DOI： 10.1007/s10118-019-2252-x.

Peng Cui, Chang-Tong Song, Xian-Hong Zhang, et al. Preparation of Ultralow Molecular Weight Poly(vinyl chloride) with Sub-micrometer Particles via Precipitation Polymerization[J]. Chinese Journal of Polymer Science, 2019, 37(7): 646-653. DOI: 10.1007/s10118-019-2252-x. DOI：

摘要

Abstract

Poly(vinyl chloride)

with ultralow molecular weight

produced by free radical polymerization either at high temperature or in the presence of chain transfer agents

is widely used as special resins and polymer process additives. This paper reports a new process

called self-stabilized precipitation polymerization

in which the polymerization of vinyl chloride monomer (VCM) is conducted in hydrocarbon diluents without addition of any suspending agent or emulsifier. The merits of this novel strategy include: (1) PVC resins with ultra-low number-average molecular weight (

) from 4000 to 15000

which is much lower than

of those prepared by conventional suspension and emulsion polymerizations

(2) sub-micrometer PVC particles with near spherical morphology

and (3) the very simple post-polymerization separation process. Under mild stirring

polymerization proceeds stably and smoothly. The influences of main process factors

such as solvents

initiator and monomer concentrations

polymerization time

and temperature on both particle morphology and

of the polymer products are investigated systematically. The molar ratio of ―CH

―CHCl―/―CH＝CH―CH

CHCl

a good indicator of structural defects

is about 1000/0.1 which means the low molecular weights do not result from chain transfer to the monomers. Then the mechanism of this polymerization is proposed. In summary

this novel polymerization technology provides a straightforward method for preparing PVC particulate products with low

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references

Saeki, Y.; Emura, T . Technical progresses for PVC production . Prog. Polym. Sci. , 2002 . 27 2055 - 2131 . DOI: 10.1016/S0079-6700(02)00039-4 http://doi.org/10.1016/S0079-6700(02)00039-4 .

Brandrup, J.; Immergut, E. H. Polymer handbook . Wiley, New York, 1989 .

Xu, X.; Guo, S . A study on morphological structure of low molecular weight PVC prepared by vibromilling degradation . Polym. Plast. Technol. Eng. , 1995 . 34 621 - 632 . DOI: 10.1080/03602559508012208 http://doi.org/10.1080/03602559508012208 .

Huang, Z.; Pan, P.; Bao, Y. Z . Solution and aqueous miniemulsion polymerization of vinyl chloride mediated by a fluorinated xanthate . J. Polym. Sci., Part A: Polym. Chem. , 2016 . 54 2092 - 2101 . .

Abreu, C. M.; Mendonça, P. V.; Serra, A. N. C.; Coelho, J. F.; Popov, A. V.; Gryn’ova, G.; Coote, M. L.; Guliashvili, T . Reversible addition-fragmentation chain transfer polymerization of vinyl chloride . Macromolecules , 2012 . 45 2200 - 2208 . DOI: 10.1021/ma300064j http://doi.org/10.1021/ma300064j .

Percec, V.; Popov, A. V.; Ramirez-castillo, E.; Weichold, O . Living radical polymerization of vinyl chloride initiated with iodoform and catalyzed by nascent Cu 0 /tris(2-aminoethyl)amine or polyethyleneimine in water at 25 °C proceeds by a new competing pathways mechanism . J. Polym. Sci., Part A: Polym. Chem. , 2003 . 41 3283 - 3299 . DOI: 10.1002/pola.10937 http://doi.org/10.1002/pola.10937 .

Smallwood, P . The formation of grains of suspension poly(vinyl chloride) . Polymer , 1986 . 27 1609 - 1618 . DOI: 10.1016/0032-3861(86)90112-6 http://doi.org/10.1016/0032-3861(86)90112-6 .

Georgiadou, S.; Thomas, N.; Gilbert, M.; Brooks, B . Nonaqueous polymerization of vinyl chloride: An environmentally friendly process . J. Appl. Polym. Sci. , 2009 . 112 2472 - 2481 . DOI: 10.1002/app.v112:4 http://doi.org/10.1002/app.v112:4 .

Balakrishnan, T.; Ford, W. T . Particle size control in suspension copolymerization of styrene, chloromethylstyrene, and divinylbenzene . J. Appl. Polym. Sci . , 1982 . 27 133 - 138 . DOI: 10.1002/app.1982.070270115 http://doi.org/10.1002/app.1982.070270115 .

Negre, M.; Bartholin, M.; Guyot, A . Functionalized resins, 1. Gel and macroporous chloromethylated styrenic resins prepared in the presence of toluene as a pore forming agent . Die Angew. Makromol. Chem. , 1982 . 106 67 - 77 . DOI: 10.1002/apmc.1982.051060106 http://doi.org/10.1002/apmc.1982.051060106 .

Chonde, Y.; Liu, L. J.; Krieger, I. M . Preparation and surface modification of poly(vinylbenzyl chloride) latices . J. Appl. Polym. Sci. , 1980 . 25 2407 - 2416 . DOI: 10.1002/app.1980.070251025 http://doi.org/10.1002/app.1980.070251025 .

Prince, K . Water dilutable secondary stabilisers in suspension polymerisation of vinyl chloride monomer . Plast Rubber Compos. , 1999 . 28 105 - 108 . DOI: 10.1179/146580199101540187 http://doi.org/10.1179/146580199101540187 .

Sperling, L. H. Introduction to physical polymer science . John Wiley & amp; Sons, 2005 .

Machleidt, R., The meson theory of nuclear forces and nuclear structure. in Advances in nuclear physics , Vol 19, ed. by Negele, J. W.; Vogt, E. Springer, Boston, MA, 1989 , p. 189−376.

Bao, Y.; Brooks, B . Particle features of poly(vinyl chloride) resins prepared by a new heterogeneous polymerization process . J. Appl. Polym. Sci. , 2003 . 90 954 - 958 . DOI: 10.1002/app.12685 http://doi.org/10.1002/app.12685 .

Butters, G. Particulate nature of PVC: Formation, structure and processing . Applied Science Publishers, 1982 .

Xie, T.; Hamielec, A.; Wood, P.; Woods, D . Suspension, bulk, and emulsion polymerization of vinyl chloride-mechanism, kinetics, and reactor modelling . J. Vinyl Technol. , 1991 . 13 2 - 25 . DOI: 10.1002/(ISSN)1548-0585 http://doi.org/10.1002/(ISSN)1548-0585 .

Yuan, H.; Kalfas, G.; Ray, W . Suspension polymerization . J. Macromol. Sci., Part C: Polym. Rev. , 1991 . 31 215 - 299 . DOI: 10.1080/15321799108021924 http://doi.org/10.1080/15321799108021924 .

Cebollada, A.; Schmidt, M.; Farber, J.; Capiati, N.; Valles, E . Suspension polymerization of vinyl chloride. I. Influence of viscosity of suspension medium on resin properties . J. Appl. Polym. Sci. , 1989 . 37 145 - 166 . DOI: 10.1002/app.1989.070370111 http://doi.org/10.1002/app.1989.070370111 .

Freidlina, R. K.; Velichko, F.; Zlotskii, S.; Rakhmankulov, D.; Terent’ev, A. B. Radical telomerization . Khimiya, Moscow, 1988 .

Mickley, H. S.; Michaels, A. S.; Moore, A. L . Kinetics of precipitation polymerization of vinyl chloride . J. Polym. Sci. , 1962 . 60 121 - 140 . DOI: 10.1002/pol.1962.1206017006 http://doi.org/10.1002/pol.1962.1206017006 .

Kronman, A.; Groshev, G.; Leshina, L.; Sitnikova, E.; Sulina, T . Polymerization of vinyl chloride in the presence of alcohols . Russian J. Appl. Chem. , 2001 . 74 1007 - 1009 . DOI: 10.1023/A:1013007810113 http://doi.org/10.1023/A:1013007810113 .

Xing, C. M.; Yang, W. T . A novel, facile method for the preparation of uniform, reactive maleic anhydride/vinyl acetate copolymer micro- and nanospheres . Macromol. Rapid Commun. , 2004 . 25 1568 - 1574 . DOI: 10.1002/(ISSN)1521-3927 http://doi.org/10.1002/(ISSN)1521-3927 .

Xing, C. M.; Yang, W. T . Stabilizer-free dispersion copolymerization of maleic anhydride and vinyl acetate. I. Effects of principal factors on microspheres . J. Polym. Sci., Part A: Polym. Chem. , 2005 . 43 3760 - 3770 . DOI: 10.1002/pola.20871 http://doi.org/10.1002/pola.20871 .

Xing, C. M.; Yu, Y.; Yang, W. T . Stabilizer-free dispersion copolymerization of maleic anhydride and vinyl acetate. II. Polymerization features . Macromol. Chem. Phys. , 2006 . 207 621 - 626 . DOI: 10.1002/macp.200500527 http://doi.org/10.1002/macp.200500527 .

Liu, Z. J.; Chen, D.; Zhang, J. F.; Liao, H. D.; Chen, Y. Z.; Sun, Y. F.; Deng, J. Y.; Yang, W. T . Self-stabilized precipitation polymerization and its application . Research , 2018 . 2018 9370490 .

Luo, W.; Liu, J. X.; Ma, Y. H.; Zhang, B.; Yang, W. T . Preparation of polymer nanoparticles from renewable biobased furfuryl alcohol and maleic anhydride by stabilizer-free dispersion polymerization . J. Polym. Sci., Part A: Polym. Chem. , 2012 . 50 3606 - 3617 . DOI: 10.1002/pola.v50.17 http://doi.org/10.1002/pola.v50.17 .

Ramram, M. B.; Chen, D.; Ma, Y.; Wang, L.; Yang, W . Stabilizer-free precipitation copolymerization of renewable bio-based α -methylene- γ -butyrolactone and styrene . J. Macromol. Sci., Part A , 2016 . 53 484 - 491 . DOI: 10.1080/10601325.2016.1189281 http://doi.org/10.1080/10601325.2016.1189281 .

Barclay, L . Formation and structure of PVC particles . Angew. Makromol. Chem.: Appl. Macromol. Chem. Phys. , 1976 . 52 1 - 20 . .

Tseng, C. M.; Lu, Y. Y.; El-Aasser, M. S.; Vanderhoff, J. W . Uniform polymer particles by dispersion polymerization in alcohol . J. Polym. Sci., Part A: Polym. Chem. , 1986 . 24 2995 - 3007 . DOI: 10.1002/pola.1986.080241126 http://doi.org/10.1002/pola.1986.080241126 .

Thomson, B.; Rudin, A.; Lajoie, G . Dispersion copolymerization of styrene and divinylbenzene: Synthesis of monodisperse, uniformly crosslinked particles . J. Polym. Sci., Part A: Polym. Chem. , 1995 . 33 345 - 357 . DOI: 10.1002/pola.1995.080330301 http://doi.org/10.1002/pola.1995.080330301 .

Zhang, F.; Bai, Y. W.; Ma, Y. H.; Yang, W. T . Preparing of monodisperse and cation-charged polystyrene particles stabilized with polymerizable quarternary ammonium by dispersion polymerization in a methanol-water medium . J. Colloid Interf. Sci. , 2009 . 334 13 - 21 . DOI: 10.1016/j.jcis.2009.02.040 http://doi.org/10.1016/j.jcis.2009.02.040 .

Yan, Q.; Bai, Y. W.; Meng, Z.; Yang, W. T . Precipitation polymerization in acetic acid: Synthesis of monodisperse cross-linked poly(divinyl benzene) microspheres . J. Phys. Chem. B , 2008 . 112 6914 - 6922 . DOI: 10.1021/jp711324a http://doi.org/10.1021/jp711324a .

Chatelain, J . Two stage bulk polymerisation process of vinyl chloride . British Polym. J. , 1973 . 5 457 - 465 . DOI: 10.1002/(ISSN)1934-256X http://doi.org/10.1002/(ISSN)1934-256X .

Bao, Y. Z.; Brooks, B. W . Phase‐equilibrium behavior of vinyl chloride/n‐butane and its application in determination of vinyl chloride heterogeneous polymerization kinetics . J. Polym. Sci., Part A: Polym. Chem. , 2001 . 39 2179 - 2188 . DOI: 10.1002/pola.1194.abs http://doi.org/10.1002/pola.1194.abs .

Bao, Y. Z.; Brooks, B. W . Influences of some polymerization conditions on particle properties of suspension poly(vinyl chloride) resin . J. Appl. Polym. Sci. , 2002 . 85 1544 - 1552 . DOI: 10.1002/app.10786 http://doi.org/10.1002/app.10786 .

Abreu, C. M. R.; Mendonça, P. V.; Serra, A. C.; Noble, B. B.; Guliashvili, T.; Nicolas, J.; Coote, M. L.; Coelho, J. F. J . Nitroxide-mediated polymerization of vinyl chloride at low temperature: Kinetic and computational studies . Macromolecules , 2016 . 49 490 - 498 . DOI: 10.1021/acs.macromol.5b02017 http://doi.org/10.1021/acs.macromol.5b02017 .

Hansen, F. K.; Ugelstad, J . Particle nucleation in emulsion polymerization. II. Nucleation in emulsifier-free systems investigated by seed polymerization . J. Polym. Sci., Part A: Polym. Chem. , 1979 . 17 3033 - 3045 . DOI: 10.1002/pol.1979.170171001 http://doi.org/10.1002/pol.1979.170171001 .

Goodall, A. R.; Wilkinson, M. C.; Hearn, J . Mechanism of emulsion polymerization of styrene in soap-free systems . J. Polym. Sci., Part A: Polym. Chem. , 1977 . 15 2193 - 2218 . DOI: 10.1002/pol.1977.170150912 http://doi.org/10.1002/pol.1977.170150912 .

Hansen, F. K.; Ugelstad, J . Particle nucleation in emulsion polymerization. I. A theory for homogeneous nucleation . J. Polym. Sci., Part A: Polym. Chem. , 1978 . 16 1953 - 1979 . DOI: 10.1002/pol.1978.170160814 http://doi.org/10.1002/pol.1978.170160814 .

Shen, S.; Sudol, E. D.; El-Aasser, M. S . Dispersion polymerization of methyl methacrylate: Mechanism of particle formation . J. Polym. Sci., Part A: Polym. Chem. , 1994 . 32 1087 - 1100 . DOI: 10.1002/pola.1994.080320611 http://doi.org/10.1002/pola.1994.080320611 .

Xu, J.; Jung, K.; Boyer, C . Oxygen tolerance study of photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization mediated by Ru(bpy) 3 Cl 2 . Macromolecules , 2014 . 47 4217 - 4229 . DOI: 10.1021/ma500883y http://doi.org/10.1021/ma500883y .

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⁰

Preparation of Ultralow Molecular Weight Poly(vinyl chloride) with Sub-micrometer Particles via Precipitation Polymerization

DOI：10.1007/s10118-019-2252-x

摘要

Abstract

关键词

Keywords

references