INVESTIGATION OF THE EFFECT OF THE DIFFERENT FACTORS ON THE STAR-POLYACRYLATE PREPARATION BY ATRP METHOD SUPERVISOR : Assoc.Prof.Dr. NGUYEN CUU KHOA STUDENT : PHAM THI MINH DIEU Contents Literature review What is ATRP?  Free radical polymerization:  Controlled/living radical polymerization  Atom transfer radical polymerization (ATRP) based on a transition metal halide/ nitrogen based ligand catalyst. • A synthesis route for a wide variety of different polymers and material composites. • Poorly controlled, high molecular weights, high PDI and poorly defined products. A wide variety of monomers have been used to synthesize polymers by ATRP with predetermined molecular weight and functional end group. I. Literature review Atom transfer radical polymerization (ATRP) Components of ATRP • Monomer: styrene, acrylate , methacrylate • Initiator: alkyl halide such as aryl, carbonyl,… • Catalyst : - Transition metal : Cu, Fe, Ni, Ru, - Nitrogen based ligand : bpy, TEPA, PMDETA, … • Additives I. Literature review Processes in normal ATRP R-X + M t n Y/L m R + XM t n+1 Y/L m R + M R-M Initiation R + R M M ( ) n M nM Propagation: Reversible termination: R M M ( ) n + XM t n+1 Y/L m R M M ( ) n X + M t n Y/L m I. Literature review ATRP’s features • Long-lived polymer chains gradient, block and graft copolymers • Predetermined molecular weight • Halogen end group transformation • Narrow polydispersity • First-order kinetics behavior I. Literature review Polymeric materials made by ATRP I. Literature review State of art ATRP research I. Literature review  Suresh K. Jewrajka and Broja M. Mandal (2003) studied the ATRP of acrylamide in water or in glycerol-water 2-Cl-PA or 2- Br-PA and CuX bipyridine complex as catalyst. The ln Mo/M vs t plots are curved to start with but become linear The chain extension experiment confirms the living nature of the polymers  Huiqi Zhang, Bert Klumperman (2006) investigated the kinetics of CuBr-mediated homogeneous ATRP of MMA using as NHBMI ligand and HEBIB as initiator. When ≤10% Cu(II) relative to Cu(I) was added, the ln([M]0/[M] ~ (t2/3) . When [Cu(II)]0 >10%, ln([M]0/[M] ~ t; Rp ~ [initiator], [Cu(I)] and [Cu(II)]-1 . Keq and kt were determined to be 7.2 × 10-8 and 8.9 × 107 M-1 s-1 State of art ATRP research I. Literature review  K. A. Davis, H. Paik, and K. Matyjaszewski (1999) investigated the dependence of Rp on the concentrations of initiator, catalyst, Cu(II), and temperature of MA using dNbpy as the catalyst and MBrP as the initiator. Keq=1.2 × 10-9 at 90°C, ΔHapp = 27.5 kcal/mol. With CuPF6/dNbpy catalyst, kapp was approximately 40 times that of the corresponding CuBr/dNbpy catalyzed reaction and ΔHapp = 10.3 kcal/mol.  K. Matyjaszewski and Jianhui Xia (1997) investigated the ATRP of styrene employing a CuX/dNbpy catalyst and RX initiators, was first order with respect to monomer, initiator, and Cu(I) concentrations. The relationship between kapp and Cu(II) shows a decay behavior. The fastest polymerization rate was observed with a ratio of ligand to metal of 2:1. State of art ATRP research I. Literature review  In Vietnam, Tran Huu Nghi and Nguyen Thi Hanh, et.al (2010) synthesized star-poly(methyl acrylate) by ATRP with triglyceride 2-bromopropionate as initiator and the complex CuBr/TEPA as catalyst. Poly(Methyl acrylate) are attached to the APTES modified silica particles to make hybrid material. [...]... increase in the alkyl group of monomer and [M]o/[I]o ratio  The polymerization of MA using CuBr/PMDETA catalyst showed first-order kinetic behavior Rp decreased with the addition of CuBr2 and increase with the addition of Cu(0) Keq = 9.37×10-7 Recommendations  Investigate the effect of the others factors on ATRP such as initiator,temperature, reaction time,…  The effect of factors on ATRP of n-butyl... Discussion Kinetic studies of ATRP  The polymerization rate show first order respect to monomer  The polymerization rate decreased with the addition of CuBr2 and increased with the addition of Cu(0)  The effect of CuBr2 on polymerization rate wasn’t clear when the monomer concentration increased  The polymerization rate was slow when the [M]o/[I]o ratio increased III Results & Discussion Determination... Results & Discussion The effect of monomers on reaction time Monomers Reaction time (h) Methyl acrylate 2 2615.6 3077 3.74 n-Butyl acrylate 5 5639.6 4342 4.49 n-Octyl acrylate 15 Mna Mnthe o PDI  The reaction time increased with the length of the alkyl group of monomers  The polymerization rate followed the order MA > n-BA > n-OA III Results & Discussion The effect of ligand on reaction time Set I (mol)... Synthesizing star- polyacrylates Investigation The effect of ligands, chain length of monomers and additives Kinetic studies of ATRP The living nature of the polymers II Experimental section Methyl acrylate Monomers Initiator n-Butyl acrylate n-Octyl acrylate Triglyceride 2bromopropionate INVESTIGATION POLYMERIZATION Additives Cu Catalyst CuBr 2 TEPA Ligands PMDETA CuBr The effect of ligands, monomer...Objective  Synthesize the star- polyacrylate of n-butyl acrylate, n-octyl acrylate using triglyceride 2-bromopropionate as a initiator and CuBr/TEPA as a catalyst  Investigate the effect of different factors such as ligands, monomers, additives… on the star- poly( methyl acrylate) synthesis by ATRP I Experimental section Polymerization Preparation of CuBr, CuBr2, Triglyceride 2-bromopropionate and n-octyl... with the addition of monomer The polymers were “living” Conclusion  Star- polyacrylates of three monomers (MA, n-BA, n-OA) were synthesized using triglyceride 2-bromopropionate as an initiator and CuBr/TEPA as a catalyst Structures of polymers were determined by NMR; Mn and PDI by GPC  When TEPA was used as a ligand, the polymerization was faster compared to PMDETA  The reaction time increase with the. .. II Experimental section Preparation  CuBr, CuBr2  The initiator (triglyceride 2-bromopropionate) was synthesized by esterification of 2-bromopropionic acid and glycerol in microwave oven  n-Octyl alcohol and acrylic acid were esterified in microwave oven in presence of H2SO4 as catalyst and hydroquinone as inhibitor II Experimental section Initiator Triglyceride  2-Bromopropionic acid (9ml)  Glycerol... NaHCO3  Column chromatography  Chloroform : n-hexan  = 4:1  Esterification  Wash  Purify  Initiator  In microwave  180W, 10min II Experimental section Polymerization CuBr +TEPA or PMDETA Monomer Complex formation NP9 Triglyceride Polymerization Remove catalyst Polymers N2 atmosphere 30min T=80oC HCl 5% II Experimental section The effect on reaction time Monomers: Molecule Substances Quantity... reaction, 0.2g of the solution was withdrawn to analyze by GPC III Results & Conclusion CuBr Initiator:Triglyceride CuBr2 Polyacrylate III Results & Conclusion 1H-NMR spectra of poly(n-butyl acrylate) Sol COOCH2CH2CH2CH3 Br CH2 n CH HCOCOH2C CH3 CH3 Br CH2 CH HCOCOH2C CH3 (2b) (3b) 7b CHOCOCH CH CH2 Br n COOCH2CH2CH2CH3 n (1b) 5b (4b) (5b) (6b) (7b) COOCH2CH2CH2CH3 6b 4b 2b III Results & Conclusion 13C-NMR... 600 (13) 300 (8) 300 (11) 300 (14) 200 (9) 200 (12) 200 (15) MA MA MA Mole Mole Mole At regular time intervals , the samples were withdrawn to determine the monomer conversion II Experimental section The “living” nature of the polymers The polymers produced in a three-stage monomer addition experiment (Cu or CuBr2 as additives) Substances Substances Substances Initiator Initiator Initiator CuBr CuBr . INVESTIGATION OF THE EFFECT OF THE DIFFERENT FACTORS ON THE STAR-POLYACRYLATE PREPARATION BY ATRP METHOD SUPERVISOR : Assoc.Prof.Dr. NGUYEN CUU KHOA STUDENT : PHAM THI MINH DIEU Contents Literature. section Polymerization  Preparation of CuBr, CuBr2, Triglyceride 2-bromopropionate and n-octyl acrylate  Synthesizing star-polyacrylates Investigation  The effect of ligands, chain length of. 2-bromopropionate as a initiator and CuBr/TEPA as a catalyst.  Investigate the effect of different factors such as ligands, monomers, additives… on the star-poly( methyl acrylate) synthesis by ATRP. I.