INVESTIGATION OF THE EFFECT OF THE DIFFERENT FACTORS ON THE STAR POLYACRYLATE PREPARATION BY ATRP METHOD

INVESTIGATION OF THE EFFECT OF THE DIFFERENT FACTORS ON THE STAR-POLYACRYLATE PREPARATION BY ATRP METHOD SUPERVISOR : Assoc.Prof.Dr..  Free radical polymerization:  Controlled/livin

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

Literature review

Experimental section

Results &

Discussion Recommendation

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, …

species with any suitable ligand)

Sometimes an additive such as oxygen, zerovalent or phenol is used For a successful ATRP, other factors, such as solvent and temperature, must also be taken into

consideration

I Literature review

Processes in normal ATRP

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

ATRP of acrylamide in water or in glycerol-water Cl-PA or Br-PA and CuX bipyridine complex as catalyst The ln Mo/M vs t

2-plots are curved to start with but become linear The chain extension experiment confirms the living nature of the polymers

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

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, ΔHHapp = 27.5 kcal/mol With CuPF6/dNbpy catalyst, kapp was approximately 40 times that of the corresponding CuBr/dNbpy catalyzed reaction and ΔHHapp = 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

 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

and n-octyl acrylate

Investigation

II Experimental section

POLYMERIZATION

Monomer

sInitiator

CatalystAdditives

r2

Methyl acrylate n-Butyl acrylate n-Octyl

CuB r

INVESTIGATION

TEPA PMDETA

The effect of ligands, monomer additives

Kinetic studies

“Living” nature

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

II Experimental section

Column chromatography

Chloroform : n-hexan

 = 4 : 1

H2O, NaHCO3

Initiator Triglyceride

The effect on reaction time

Substances Quantity Molecule (mmol) Molar ratioInitiator 0.26ml 0.75 1

The effect on reaction time

(2) 0.019 0.009 0 0.009 10.64 0 0.073 (3) 0.018 0.018 0 0 10.08 0.072 0

(4) 0.018 0.018 0 0 10.84 0 0.072 (5) 0.018 0.009 0.009 0 10.27 0.07

(6) 0.018 0.009 0.009 0 10.87 0.072 The molar ratio [I]/[Cu I ] +[Cu II ]/[L]/[MA] = 1:1:4:600

II Experimental section

Kinetic studies of ATRP

The ATRP of MA using CuBr/PMDETA as a catalyst

Substances Quantity Mole Molar ratio

Initiator 0.34ml 1×10 -3 1 CuBr 0.072g 0.5×10 -3 0.5

Cu 0.032g 0.5×10 -3 0.5 PMDETA 0.835ml 4×10 -3 4

MA

54ml 0.6 600 (10) 27ml 0.3 300 (11) 18ml 0.2 200 (12)

Substances Quantity Mole Molar ratio

Substances Quantity Mole Molar ratio

Initiator 0.34ml 1×10 -3 1 CuBr 0.072g 0.5×10 -3 0.5 CuBr2 0.112g 0.5×10 -3 0.5 PMDETA 0.835ml 4×10 -3 4

MA

54ml 0.6 600 (13) 27ml 0.3 300 (14) 18ml 0.2 200 (15)

At regular time intervals , the samples were withdrawn

to determine the monomer conversion

II Experimental section

The “living” nature of the polymers

Substances Quantity Molecule

The polymers produced in a three-stage monomer addition

experiment (Cu or CuBr2 as additives)

Substances Quantity Molecule

III Results & Conclusion

CuBr2

CuBr

PolyacrylateInitiator:Triglyceride

1H-NMR spectra of poly(n-butyl acrylate)

CHOCOCH

CH3CH HCOCOH2C

HCOCOH2C COOCH2CH2CH2CH3

CH2 Br n

CH3CH

CH3CH

III Results & Conclusion

13C-NMR spectra of poly(n-butyl acrylate)

CHOCOCH

CH3CH HCOCOH2C

HCOCOH2C COOCH2CH2CH2CH3

CH2 Br n

CH3CH

CH3CH

COOCH2CH2CH2CH3

CH2

COOCH2CH2CH2CH3

CH2Br

Br

(4b) (5b) (6b) (7b) (1b)

13C-NMR DEPT of poly(n-butyl acrylate)

CH2 Br n

CH3CH

CH3CH COOCH2CH2CH2CH3

CH2

COOCH2CH2CH2CH3

CH2Br

Br

(4b) (5b) (6b) (7b) (1b)

1H-NMR spectra of poly(n-octyl acrylate)

CHOCOCH

CH3

CH HCOCOH2C

HCOCOH2C COOCH2CH2(CH2)5CH3

CH2 Br n

CH3CH

CH3CH

6c-10c

III Results & Discussion

13C-NMR spectra of poly(n-octyl acylate)

III Results & Discussion

CHOCOCH

CH3

CH HCOCOH2C

HCOCOH2C COOCH2CH2(CH2)5CH3

CH2 Br n

CH3CH

CH3CH

COOCH2CH2(CH2)5CH3

CH2

COOCH2CH2(CH2)5CH3

CH2Br

Br

(4c) (5c) (6c)-(10c) (1c)

4c

sol

10c 6c 9c

The effect of monomers on reaction time

The effect of ligand on reaction time

[I]/[Cu I ] +[Cu II ]/[L]/[MA] = 1:1:4:600

The polymerization rate of TEPA is faster than

PMDETA

The catalyst activity increased with the increasing

number of nitrogen coordination sites.

III Results & Discussion

Kinetic studies of ATRP

0 0.2 0.4 0.6 0.8 1 1.2 1.4

The relationship between ln([M]o/[M]) and time

III Results & Discussion

Kinetic studies of ATRP

monomer.

of Cu(0).

clear when the monomer concentration increased.

III Results & Discussion

Determination of equilibrium constant

III Results & Discussion

0 20 40 60 80 100 120 0

0.05 0.1 0.15 0.2 0.25

0.3

f(x) = 0 x − 0.02 R² = 0.98

[I]o=2[CuBr]o=2[CuBr2]o= [PMDETA]o/4=[MA]o/200

“Living” polymerization

The polymers were “living”

The GPC peak shifted from low Mn to high Mn with the addition of monomer

GPC traces of PMA

[I]/[CuBr]/[TEPA]=1:1:2 [I]/[CuBr] + [CuBr 2 ]/[TEPA]=1:1:2 [I]/[CuBr] + [Cu]/[TEPA]=1:1:2

III Results & Discussion

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 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

 Investigate the effect of the others factors on ATRP

such as initiator,temperature, reaction time,…

 The effect of factors on ATRP of n-butyl acrylate

and n-octyl acrylate should be explored

 Find out the more effective way to remove the

catalyst from polymer

 The time of complex reaction should be prolonged

Thank for your attention!

H N N

H

H N

ethoxylate nonylphenol

Kinetics of ATRP

 The rate of monomer consumption in the propagation step is provided by :

 Equation (2) express the steady-state assumption for the concentration of propagating radical

 and therefore,

Substitution of eq (3) in eq (1)

Neutralize 10g of CuO

Remove residual CuO

30min

Filter

Reduce

Vacuum filter, wash

Dry under vacuum

1H-NMR of nOA

13C-NMR of nOA