Supporting Information for. Synthesis of amphiphilic copolymers based on acrylic acid,
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1 Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 07 Supporting Information for Synthesis of amphiphilic copolymers based on acrylic acid, fluoroalkyl acrylates and n-butyl acrylate in organic, aqueousorganic and aqueous media via RAT polymerization N. S. Serkhacheva а,. I. Smirnov a, А. V. Tolkachev a,b, N. I. Prokopov a, A. V. Plutalova c, E. V. Chernikova c,*, E.Yu. Kozhunova d, and A. R. Khokhlov d,e a Moscow Technological University, Institute of ine Chemical Technologies, Vernadskogo pr., 8, Moscow, 957, Russian ederation; b Max-Planck Institute of Colloids and Interfaces, Am Mühlenberg, 7 Potsdam, Germany; c aculty of Chemistry, Lomonosov Moscow State University, Leninskie gory /, Moscow, 999, Russian ederation, ax: , Tel: ; d aculty of Physics, Lomonosov Moscow State University, Leninskie gory /, Moscow, 999, Russian ederation e Institute of Advanced Energy Related Nanomaterials, University of Ulm, Albert Einstein Allee,, D-8908, Ulm, Germany chernikova_elena@mail.ru Table of Contents ig. S. The instantaneous values of monomer ( ) and copolymer ( ) composition ; dyad composition A A A A and A A A B (c) calculated according to the terminal unit model using r A = 0.9, r B =0. (), r A =.0, r B =0. (), and r A = 0.0, r B =0. () for monomer mixture containing 5 mol. % of monomer A.... ig. S. The particle size distribution for wt. % solution of Cop- in DM and in the mixture DM/acrylic acid/pa ; DM/monomers = 70/0 v/v, acrylic acid/pa = 90/0 mole %... ig. S. H NMR and 9 NMR spectra of the copolymer obtained at 7 % monomer conversion in copolymerization of acrylic acid and,,,,,-hexafluorobutyl acrylate in DM in the presence of BTC and subjected to methylation; acrylic acid/hba = 90/0 mole %...5
2 ig. S. The SEC curves normalized by the unit area for triblock copolymers synthesized in DM (70 wt.%) in the presence of Pol-A; [Pol-A] = mole/l, [AIBN] = mole/l, 75 o C; molar ratio of butyl acrylate to HBA 90 : 0 and 85 :5... ig. S5. H NMR and 9 NMR spectra of the triblock copolymer obtained at 99 % monomer conversion in copolymerization of butyl acrylate and,,,,,- hexafluorobutyl acrylate in the presence of Pol-A in DM and subjected to methylation; [Pol-A] = mole/l, [AIBN] = mole/l, DM/monomers = 70/0 v/v, [butyl acrylate]/[hba] = 90/0 mole %....7 ig. S. H NMR and 9 NMR spectra of the triblock copolymer obtained at 99 % monomer conversion in emulsion copolymerization of butyl acrylate and,,,,,- hexafluorobutyl acrylate in the presence of Pol-A and subjected to methylation; [Pol-A] = mole/l, [PSK] =. 0 - mole/l, monomers : water = : v/v, [butyl acrylate]/[hba] = 90/0 mole %...8 ig. S7. H NMR and 9 NMR spectra of the triblock copolymer obtained at 9 % monomer conversion in dispersion copolymerization of butyl acrylate and,,,,,- hexafluorobutyl acrylate in the presence of Pol-A in methanol/water (80/0 v/v) mixture and subjected to methylation; media/monomers = 7/ v/v, [butyl acrylate]/[hba] = 90/0 mole %; [Pol-A] =. 0 - mole/l, [AIBN] =. 0 - mole/l....9 Table S. Molecular weight characteristics of the copolymers of acrylic acid and,,,,,- hexafluorobutyl acrylate (95 : 5 mole %), acrylic acid and,,,,,,5,5- octafluoropentyl acrylate (90 : 0 mole %) synthesized in DM in the presence of trithiocarbonates....0 Table S. Molecular weight characteristics of the grown copolymers (mode ) of butyl acrylate and,,,,,-hexafluorobutyl acrylate synthesized in DM in the presence of trithiocarbonates.... Table S. Molecular weight characteristics of the grown copolymers of butyl acrylate and,,,,,-hexafluorobutyl acrylate, butyl acrylate and,,,,,,5,5-octafluoropentyl acrylate (mode ) synthesized by emulsifier-free emulsion polymerization in the presence of trithiocarbonates....
3 ig. S. The instantaneous values of monomer ( ) and copolymer ( ) composition ; dyad composition A A A A and A A A B (c) calculated according to the terminal unit model using r A = 0.9, r B =0. (), r A =.0, r B =0. (), and r A = 0.0, r B =0. () for monomer mixture containing 5 mol. % of monomer A. 0, 0, 0, A ', ' ' f A 0,0 0,08 0,0 0,0 0, Conversion, % 0, A A A B 0, 0, 0, Conversion, % A A A A (c) Conversion, % 0
4 ig. S. The particle size distribution for wt. % solution of Cop- in DM and in the mixture DM/acrylic acid/pa ; DM/monomers = 70/0 v/v, acrylic acid/pa = 90/0 mole %.
5 ig. S. H NMR and 9 NMR spectra of the copolymer obtained at 7 % monomer conversion in copolymerization of acrylic acid and,,,,,-hexafluorobutyl acrylate in DM in the presence of BTC and subjected to methylation; acrylic acid/hba = 90/0 mole % S S n p k z S H C 5 CH Intensity f (ppm) S S n p k z S H C CH Intensity f (ppm)
6 ig. S. The SEC curves normalized by the unit area for triblock copolymers synthesized in DM (70 wt.%) in the presence of Pol-A; [Pol-A] = mole/l, [AIBN] = mole/l, 75 o C; molar ratio of butyl acrylate to HBA 90 : 0 and 85 :5. Conversion P M Conversion P M
7 ig. S5. H NMR and 9 NMR spectra of the triblock copolymer obtained at 99 % monomer conversion in copolymerization of butyl acrylate and,,,,,-hexafluorobutyl acrylate in the presence of Pol- A in DM and subjected to methylation; [Pol-A] = mole/l, [AIBN] = mole/l, DM/monomers = 70/0 v/v, [butyl acrylate]/[hba] = 90/0 mole % S S 50 S 00 H C 5 7 CH CH H C f (ppm) S S 0 H C S CH CH H C f (ppm)
8 ig. S. H NMR and 9 NMR spectra of the triblock copolymer obtained at 99 % monomer conversion in emulsion copolymerization of butyl acrylate and,,,,,-hexafluorobutyl acrylate in the presence of Pol-A and subjected to methylation; [Pol-A] = mole/l, [PSK] =. 0 - mole/l, monomers : water = : v/v, [butyl acrylate]/[hba] = 90/0 mole %. 8
9 ig. S7. H NMR and 9 NMR spectra of the triblock copolymer obtained at 9 % monomer conversion in dispersion copolymerization of butyl acrylate and,,,,,-hexafluorobutyl acrylate in the presence of Pol-A in methanol/water (80/0 v/v) mixture and subjected to methylation; media/monomers = 7/ v/v, [butyl acrylate]/[hba] = 90/0 mole %; [Pol-A] =. 0 - mole/l, [AIBN] =. 0 - mole/l S S n m p k l z S H 5 7 C 8 H C CH CH f (ppm) S S n m p k l z S H C CH H C CH f (ppm)
10 Table S. Molecular weight characteristics of the copolymers of acrylic acid and,,,,,-hexafluorobutyl acrylate (95 : 5 mole %), acrylic acid and,,,,,,5,5-octafluoropentyl acrylate (90 : 0 mole %) synthesized in DM in the presence of trithiocarbonates. RAT agent Monomer Conversion, % M n, kda M theor n, kda M w /M n BTC mole/l HBA Cop-H5 0 - mole/l HBA BTC 0 - mole/l PA Cop- 0 - mole/l PA Note: In the case of Cop-H5 and Cop-, the molecular weight characteristics of the grown copolymers (mode ) are given. 0
11 Table S. Molecular weight characteristics of the grown copolymers (mode ) of butyl acrylate and,,,,,-hexafluorobutyl acrylate synthesized in DM in the presence of trithiocarbonates. RAT agent HBA, mole % Conversion, % M n, kda M w /M n BTC Pol-A Cop-H
12 Table S. Molecular weight characteristics of the grown copolymers of butyl acrylate and,,,,,-hexafluorobutyl acrylate, butyl acrylate and,,,,,,5,5-octafluoropentyl acrylate (mode ) synthesized by emulsifier-free emulsion polymerization in the presence of trithiocarbonates. RAT agent Monomer, mole % Conversion, % M n, kda M w /M n Pol-A HBA, Cop-H5 HBA, Cop- PA, Cop-0 PA,
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