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Published in: Journal of Polymer Research 4/2019

01-04-2019 | ORIGINAL PAPER

Investigation of mercaptan/ε-caprolactam initiated bulk copolymerization of methyl methacrylate with vinyl monomers

Authors: Chien-Pang Wu, Cheng-Chien Wang, Chuh-Yung Chen

Published in: Journal of Polymer Research | Issue 4/2019

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Abstract

The bulk copolymerization of methyl methacrylate (MMA) with vinyl monomers initiated by ε-caprolactam (CL) and n-dodecyl mercaptan (RSH) was investigated. Acrylonitrile (AN) and vinyl acetate (VAc) were used to copolymerize with MMA at 90 °C in the presence of CL and RSH, respectively. As evidenced by first-order kinetics of polymerization, linear increase of molecular weights with monomer conversions, and relatively low PDI values within a range of 1.3 to 1.6, both the copolymerization reactions exhibited living characteristics. Dependences of the copolymerization on the monomer feed ratio was also studied. An increase in the feed ratio of MMA induced an increased rate of copolymerization. In contrast, an increase in the initial loading of vinyl monomer leaded to the decrease in rate of copolymerization. The reactivity ratios of each pair of comonomers were also assessed using Fineman-Ross (FR) method. The results showed that the CL has an important influence on the kinetics of copolymerization, which caused the copolymerization parameters different from the most previously reported values.

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Literature
1.
go back to reference Lin Y, Zheng J, Yao K, Tan H, Zhang G, Gong J, Tang T, Xu D (2015) Synthesis and linear rheological property of comb-like styrene-based polymers with a high degree of branch chain. Polymer 59(0):252–259CrossRef Lin Y, Zheng J, Yao K, Tan H, Zhang G, Gong J, Tang T, Xu D (2015) Synthesis and linear rheological property of comb-like styrene-based polymers with a high degree of branch chain. Polymer 59(0):252–259CrossRef
2.
go back to reference Zhang H, Alkayal N, Gnanou Y, Hadjichristidis NP (2014). Macromol Rapid Commun 35(4):378–390CrossRef Zhang H, Alkayal N, Gnanou Y, Hadjichristidis NP (2014). Macromol Rapid Commun 35(4):378–390CrossRef
3.
go back to reference Yilgör E, Yilgör I (2014) Silicone containing copolymers: Synthesis, properties and applications. Prog Polym Sci 39(6):1165–1195CrossRef Yilgör E, Yilgör I (2014) Silicone containing copolymers: Synthesis, properties and applications. Prog Polym Sci 39(6):1165–1195CrossRef
4.
go back to reference Ito S, Goseki R, Ishizone T, Hirao A (2014) Synthesis of well-controlled graft polymers by living anionic polymerization towards exact graft polymers. Polym Chem 5(19):5523–5534CrossRef Ito S, Goseki R, Ishizone T, Hirao A (2014) Synthesis of well-controlled graft polymers by living anionic polymerization towards exact graft polymers. Polym Chem 5(19):5523–5534CrossRef
5.
go back to reference Hardy CG, Zhang J, Yan Y, Ren L, Tang C (2014) Metallopolymers with transition metals in the side-chain by living and controlled polymerization techniques. Prog Polym Sci 39(10):1742–1796CrossRef Hardy CG, Zhang J, Yan Y, Ren L, Tang C (2014) Metallopolymers with transition metals in the side-chain by living and controlled polymerization techniques. Prog Polym Sci 39(10):1742–1796CrossRef
7.
go back to reference Moad G, Keddie D, Guerrero-Sanchez C, Rizzardo E, Thang SH (2015) Advances in Switchable RAFT Polymerization. Macromol Symp 350(1):34–42CrossRef Moad G, Keddie D, Guerrero-Sanchez C, Rizzardo E, Thang SH (2015) Advances in Switchable RAFT Polymerization. Macromol Symp 350(1):34–42CrossRef
8.
go back to reference Ma J, Zhang H (2015) Kinetic investigations of RAFT polymerization: Difunctional RAFT agent mediated polymerization of methyl methacrylate and styrene. Macromol Res 23(1):67–73CrossRef Ma J, Zhang H (2015) Kinetic investigations of RAFT polymerization: Difunctional RAFT agent mediated polymerization of methyl methacrylate and styrene. Macromol Res 23(1):67–73CrossRef
9.
go back to reference Cheng H, Zhao G, Yan D (1992). J Polym Sci A: Polym Chem 30(10):2181–2185CrossRef Cheng H, Zhao G, Yan D (1992). J Polym Sci A: Polym Chem 30(10):2181–2185CrossRef
10.
11.
go back to reference Hu YH, Chen CY (2003) The effect of end groups on the thermal degradation of poly(methyl methacrylate). Polym Degrad Stab 82(1):81–88CrossRef Hu YH, Chen CY (2003) The effect of end groups on the thermal degradation of poly(methyl methacrylate). Polym Degrad Stab 82(1):81–88CrossRef
12.
go back to reference Hu YH, Chen CY (2003) Study of the thermal behaviour of poly(methyl methacrylate) initiated by lactams and thiols. Polym Degrad Stab 80(1):1–10CrossRef Hu YH, Chen CY (2003) Study of the thermal behaviour of poly(methyl methacrylate) initiated by lactams and thiols. Polym Degrad Stab 80(1):1–10CrossRef
13.
go back to reference Hu YH, Chen CY, Wang CC (2004) Thermal degradation kinetics of poly(n-butyl acrylate) initiated by lactams and thiols. Polym Degrad Stab 84(3):505–514CrossRef Hu YH, Chen CY, Wang CC (2004) Thermal degradation kinetics of poly(n-butyl acrylate) initiated by lactams and thiols. Polym Degrad Stab 84(3):505–514CrossRef
14.
go back to reference Hu YH, Chen CY, Wang CC, Huang YH, Wang SP (2004). J Polym Sci A: Polym Chem 42(19):4976–4993CrossRef Hu YH, Chen CY, Wang CC, Huang YH, Wang SP (2004). J Polym Sci A: Polym Chem 42(19):4976–4993CrossRef
15.
go back to reference Bach LG, Islam MR, Gal YS, Lim KT (2012) Synthesis and Characterization of TiO2/Poly(methyl methacrylate) Nanocomposites via Surface Thiol-Lactam Initiated Radical Polymerization. J Nanosci Nanotechnol 12(7):5976–5980CrossRef Bach LG, Islam MR, Gal YS, Lim KT (2012) Synthesis and Characterization of TiO2/Poly(methyl methacrylate) Nanocomposites via Surface Thiol-Lactam Initiated Radical Polymerization. J Nanosci Nanotechnol 12(7):5976–5980CrossRef
16.
go back to reference Bach LG, Islam MR, Kim JT, Seo S, Lim KT (2012) Encapsulation of Fe3O4 magnetic nanoparticles with poly(methyl methacrylate) via surface functionalized thiol-lactam initiated radical polymerization. Appl Surf Sci 258(7):2959–2966CrossRef Bach LG, Islam MR, Kim JT, Seo S, Lim KT (2012) Encapsulation of Fe3O4 magnetic nanoparticles with poly(methyl methacrylate) via surface functionalized thiol-lactam initiated radical polymerization. Appl Surf Sci 258(7):2959–2966CrossRef
17.
go back to reference Hwang HS, Bae JH, Kim HG, Lim KT (2010) Synthesis of silica–polystyrene core–shell nanoparticles via surface thiol-lactam initiated radical polymerization. Eur Polym J 46(8):1654–1659CrossRef Hwang HS, Bae JH, Kim HG, Lim KT (2010) Synthesis of silica–polystyrene core–shell nanoparticles via surface thiol-lactam initiated radical polymerization. Eur Polym J 46(8):1654–1659CrossRef
18.
go back to reference Hung CY, Wang CC, Chen CY (2013) Enhanced the thermal stability and crystallinity of polylactic acid (PLA) by incorporated reactive PS-b-PMMA-b-PGMA and PS-b-PGMA block copolymers as chain extenders. Polymer 54(7):1860–1866CrossRef Hung CY, Wang CC, Chen CY (2013) Enhanced the thermal stability and crystallinity of polylactic acid (PLA) by incorporated reactive PS-b-PMMA-b-PGMA and PS-b-PGMA block copolymers as chain extenders. Polymer 54(7):1860–1866CrossRef
19.
20.
go back to reference Wu CP, Wang CC, Chen CY (2015) Influence of asymmetric ratio of polystyrene-block-poly(methyl methacrylate) block copolymer on the crystallization rate of PLA. Eur Polym J 66(0):160–169CrossRef Wu CP, Wang CC, Chen CY (2015) Influence of asymmetric ratio of polystyrene-block-poly(methyl methacrylate) block copolymer on the crystallization rate of PLA. Eur Polym J 66(0):160–169CrossRef
21.
go back to reference Mishra A, Daswal S (2006) 1-(Bromoacetyl)pyrene, a novel photoinitiator for the copolymerization of styrene and methylmethacrylate. Radiat Phys Chem 75(9):1093–1100CrossRef Mishra A, Daswal S (2006) 1-(Bromoacetyl)pyrene, a novel photoinitiator for the copolymerization of styrene and methylmethacrylate. Radiat Phys Chem 75(9):1093–1100CrossRef
22.
go back to reference Bhanvase BA, Sonawane SH, Pinjari DV, Gogate PR, Pandit AB (2014) Kinetic studies of semibatch emulsion copolymerization of methyl methacrylate and styrene in the presence of high intensity ultrasound and initiator. Chem Eng Process Process Intensif 85(0):168–177CrossRef Bhanvase BA, Sonawane SH, Pinjari DV, Gogate PR, Pandit AB (2014) Kinetic studies of semibatch emulsion copolymerization of methyl methacrylate and styrene in the presence of high intensity ultrasound and initiator. Chem Eng Process Process Intensif 85(0):168–177CrossRef
23.
go back to reference Chen S, Binder WH (2015) Controlled copolymerization of n-butyl acrylate with semifluorinated acrylates by RAFT polymerization. Polym Chem 6(3):448–458CrossRef Chen S, Binder WH (2015) Controlled copolymerization of n-butyl acrylate with semifluorinated acrylates by RAFT polymerization. Polym Chem 6(3):448–458CrossRef
24.
go back to reference Wang H, Kolodka E, Tande BM (2013) Thermomechanical and Rheological Studies of Copolymers of Methyl Methacrylate with a Series of Linear Vinyl Esters. Ind Eng Chem Res 52(14):5111–5119CrossRef Wang H, Kolodka E, Tande BM (2013) Thermomechanical and Rheological Studies of Copolymers of Methyl Methacrylate with a Series of Linear Vinyl Esters. Ind Eng Chem Res 52(14):5111–5119CrossRef
25.
go back to reference Buchmeiser MR, Marino MG (2012) Co(acac)2-Mediated Radical Polymerization of Acrylonitrile: Control Over Molecular Weights and Copolymerization With Methyl Methacrylate. Macromol Mater Eng 297(9):894–901CrossRef Buchmeiser MR, Marino MG (2012) Co(acac)2-Mediated Radical Polymerization of Acrylonitrile: Control Over Molecular Weights and Copolymerization With Methyl Methacrylate. Macromol Mater Eng 297(9):894–901CrossRef
26.
go back to reference Dossi M, Liang K, Hutchinson RA, Moscatelli D (2010). J Phys Chem B 14(12):4213–4222CrossRef Dossi M, Liang K, Hutchinson RA, Moscatelli D (2010). J Phys Chem B 14(12):4213–4222CrossRef
27.
28.
go back to reference Nicolas J, Brusseau S, Charleux B (2010). J Polym Sci A: Polym Chem 48(1):34–47CrossRef Nicolas J, Brusseau S, Charleux B (2010). J Polym Sci A: Polym Chem 48(1):34–47CrossRef
29.
go back to reference Achilias DS (2007) A Review of Modeling of Diffusion Controlled Polymerization Reactions. Macromol Theory Simul 16(4):319–347CrossRef Achilias DS (2007) A Review of Modeling of Diffusion Controlled Polymerization Reactions. Macromol Theory Simul 16(4):319–347CrossRef
30.
go back to reference Semsarzadeh MA, Abdollahi M (2008) Kinetic study of atom transfer radical homo- and copolymerization of styrene and methyl methacrylate initiated with trichloromethyl-terminated poly(vinyl acetate) macroinitiator. Polymer 49(13–14):3060–3069CrossRef Semsarzadeh MA, Abdollahi M (2008) Kinetic study of atom transfer radical homo- and copolymerization of styrene and methyl methacrylate initiated with trichloromethyl-terminated poly(vinyl acetate) macroinitiator. Polymer 49(13–14):3060–3069CrossRef
31.
go back to reference Gao J, Li D, Wang D, Yang L (2000) Rheological behavior and mechanical properties of blends of chlorinated polyethylene with poly(acrylonitrile–styrene–methyl methacrylate). Eur Polym J 36(11):2517–2522CrossRef Gao J, Li D, Wang D, Yang L (2000) Rheological behavior and mechanical properties of blends of chlorinated polyethylene with poly(acrylonitrile–styrene–methyl methacrylate). Eur Polym J 36(11):2517–2522CrossRef
32.
33.
go back to reference Fineman M, Ross SD (1950) Linear method for determining monomer reactivity ratios in copolymerization. J Polym Sci 5(2):259–262CrossRef Fineman M, Ross SD (1950) Linear method for determining monomer reactivity ratios in copolymerization. J Polym Sci 5(2):259–262CrossRef
34.
go back to reference Yu X, Levine SE, Broadbelt LJ (2008) Kinetic Study of the Copolymerization of Methyl Methacrylate and Methyl Acrylate Using Quantum Chemistry. Macromolecules 41(21):8242–8251CrossRef Yu X, Levine SE, Broadbelt LJ (2008) Kinetic Study of the Copolymerization of Methyl Methacrylate and Methyl Acrylate Using Quantum Chemistry. Macromolecules 41(21):8242–8251CrossRef
35.
go back to reference Khesareh R, McManus NT, Penlidis A (2006) High temperature bulk copolymerization of methyl methacrylate and acrylonitrile. I. Reactivity ratio estimation. J Appl Polym Sci 100(1):843–851CrossRef Khesareh R, McManus NT, Penlidis A (2006) High temperature bulk copolymerization of methyl methacrylate and acrylonitrile. I. Reactivity ratio estimation. J Appl Polym Sci 100(1):843–851CrossRef
36.
go back to reference Ramana Reddy GV, Prasad Babu YP, Rami Reddy NS (2002) Microemulsion and conventional emulsion copolymerizations of methyl methacrylate with acrylonitrile. J Appl Polym Sci 85(7):1503–1510CrossRef Ramana Reddy GV, Prasad Babu YP, Rami Reddy NS (2002) Microemulsion and conventional emulsion copolymerizations of methyl methacrylate with acrylonitrile. J Appl Polym Sci 85(7):1503–1510CrossRef
37.
go back to reference Zhou X, Zhu J, Xing M, Zhang Z, Cheng Z, Zhou N, Zhu X (2011) Synthesis and characters of hyperbranched poly(vinyl acetate) by RAFT polymeraztion. Eur Polym J 47(10):1912–1922CrossRef Zhou X, Zhu J, Xing M, Zhang Z, Cheng Z, Zhou N, Zhu X (2011) Synthesis and characters of hyperbranched poly(vinyl acetate) by RAFT polymeraztion. Eur Polym J 47(10):1912–1922CrossRef
38.
go back to reference Abdollahi M, Sharifpour M (2007) A new simple procedure to calculate monomer reactivity ratios by using on-line 1H NMR kinetic experiments: Copolymerization system with greater difference between the monomer reactivity ratios. Polymer 48(1):25–30CrossRef Abdollahi M, Sharifpour M (2007) A new simple procedure to calculate monomer reactivity ratios by using on-line 1H NMR kinetic experiments: Copolymerization system with greater difference between the monomer reactivity ratios. Polymer 48(1):25–30CrossRef
39.
go back to reference Abdollahi M, Massoumi B, Yousefi MR, Ziaee F (2012) Free-radical homo- and copolymerization of vinyl acetate and n-butyl acrylate: Kinetic studies by online 1H NMR kinetic experiments. J Appl Polym Sci 123(1):543–553CrossRef Abdollahi M, Massoumi B, Yousefi MR, Ziaee F (2012) Free-radical homo- and copolymerization of vinyl acetate and n-butyl acrylate: Kinetic studies by online 1H NMR kinetic experiments. J Appl Polym Sci 123(1):543–553CrossRef
40.
go back to reference Quirk RP, Lynch T (1993) Anionic synthesis of primary amine-functionalized polystyrenes using 1-[4-[N,N-bis(trimethylsilyl)amino]phenyl]-1-phenylethylene. Macromolecules 26(6):1206–1212CrossRef Quirk RP, Lynch T (1993) Anionic synthesis of primary amine-functionalized polystyrenes using 1-[4-[N,N-bis(trimethylsilyl)amino]phenyl]-1-phenylethylene. Macromolecules 26(6):1206–1212CrossRef
41.
go back to reference Quirk RP, Lee B (1992) Experimental Criteria for Living Polymerizations. Polym Int 27(4):359–367CrossRef Quirk RP, Lee B (1992) Experimental Criteria for Living Polymerizations. Polym Int 27(4):359–367CrossRef
42.
go back to reference Dubé MA, Penlidis A (1995) A systematic approach to the study of multicomponent polymerization kinetics?the butyl acrylate/methyl methacrylate/vinyl acetate example: 1. Bulk copolymerization. Polymer 36(3):587–598CrossRef Dubé MA, Penlidis A (1995) A systematic approach to the study of multicomponent polymerization kinetics?the butyl acrylate/methyl methacrylate/vinyl acetate example: 1. Bulk copolymerization. Polymer 36(3):587–598CrossRef
43.
go back to reference Ma YD, Won YC, Kubo K, Fukuda T (1993) Propagation and termination processes in the free-radical copolymerization of methyl methacrylate and vinyl acetate. Macromolecules 26(25):6766–6770CrossRef Ma YD, Won YC, Kubo K, Fukuda T (1993) Propagation and termination processes in the free-radical copolymerization of methyl methacrylate and vinyl acetate. Macromolecules 26(25):6766–6770CrossRef
44.
go back to reference Brar AS, Charan S (1993) Reactivity ratios and microstructure determination of (vinyl acetate)-(methyl methacrylate) copolymers. Eur Polym J 29(5):755–759CrossRef Brar AS, Charan S (1993) Reactivity ratios and microstructure determination of (vinyl acetate)-(methyl methacrylate) copolymers. Eur Polym J 29(5):755–759CrossRef
45.
go back to reference Scorah MJ, Hua H, Dubé MA (2001) Bulk and solution copolymerization of methyl methacrylate and vinyl acetate. J Appl Polym Sci 82(5):1238–1255CrossRef Scorah MJ, Hua H, Dubé MA (2001) Bulk and solution copolymerization of methyl methacrylate and vinyl acetate. J Appl Polym Sci 82(5):1238–1255CrossRef
Metadata
Title
Investigation of mercaptan/ε-caprolactam initiated bulk copolymerization of methyl methacrylate with vinyl monomers
Authors
Chien-Pang Wu
Cheng-Chien Wang
Chuh-Yung Chen
Publication date
01-04-2019
Publisher
Springer Netherlands
Published in
Journal of Polymer Research / Issue 4/2019
Print ISSN: 1022-9760
Electronic ISSN: 1572-8935
DOI
https://doi.org/10.1007/s10965-019-1756-y

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