Cu (0) wire Mediated Synthesis and Chain Extension of Poly(methyl

acrylate) Macroinitiator

Abstract

Cu(0) pre activated wire catalyzed SET-LRP of Methyl Acrylate with various chain
lengths (DPn= 20,40 and 60) initiated with EBiB in DMSO and in the presence of N
based ligand (Me6TREN) at 25 ˚C for three hours were studied. Analyzing by using GPC
and NMR showed well-controlled polymerization with narrow molecular weight
distributions (Ð~ 1.033, 1.004, 1.001) respectively. The chain extension of PMA (DPn=
20 and 60) was conducted successfully without further addition of Cu(0) or ligand.

Introduction
Atom transfer radical polymerization (ATRP) is a reversible deactivation radical

polymerization (RDRP) technique that using a complex of a transition metal and ligand

as the mediating species. Using a mediating species to help the activation and

deactivation of propagating species revolutionized the field of radical polymerization

since the 1990s in order to mimic a living ionic polymerization. ATRP was first reported

by Matyjaszewski and Wang in 19951, Sawamoto and coworkers2, at the same time

Percec and Barboiu were working on similar research3. In 2006, single- electron transfer

living radical polymerization (SET-LRP) was developed by Percec et al4. Percec and

coworkers reported that the Cu(0) mediated Living Radical Polymerization in polar

media in the presence of N-based ligands and alkyl halide initiators at 25˚C yielding high

molar mass polymers in an ultrafast synthesis5.

SET-LRP is a great alternative to ATRP. ATRP mechanism is basically based on the

equilibrium between the propagating radicals and the dormant species mostly in the form

1
of initiating alkyl halides/ macromolecular species (PnX). The dormant species react

regularly with the rate constant of activation (Kact) and transition metal complex in their

lower oxidation state Mtm/ L acting as activator (where Mtm corresponds to transition

metal species in oxidation state m and L is a ligand) resulting in the formation of the

growing radical (Pn*) and the deactivators transition metal complexes in their higher

oxidation state attached to halide ligands X-Mm+1 / L. In the reverse reaction (Kdeact), the

deactivator reacts with the propagating radical to re-form the dormant species and the

activator, (scheme 1) shows the activation and deactivation steps that push the

equilibrium to the left side forming a low concentration radical which reduce termination

reaction and ensure chain growth6.

Scheme 1: ATRP equilibrium6

Similar to ATRP, SET-LRP is based on the equilibrium between the dormant species

and active species and the end capping deactivating species is Cu(II) halide. However,

rather than Cu(I)X in ATRP, Cu(0) is the active catalyst in SET-LRP7. (Scheme 2) shows

the mechanism of SET-LRP.

2
 Scheme 2: general mechanism for SET-LRP7

ATRP is the most widely used Controlled radical polymerization technique due to the

commercial availability of the required reagents including alkyl halide initiators, ligands

and transition metal compounds beside the large range of polymerizable monomers that

can be used with this technique under various conditions8.

The field of SET-LRP is developing rapidly for its various and easy methods and

versatile applications for industrial or pharmaceutical uses. Since this current research

presents Cu (0) mediated SET-LRP, many papers about this area were reported regarding

the reaction conditions9-15, methods16-25, media26-30 and instrumental analysis31-34 of SET-

LRP.

3
Experimental Section

General Procedure for Cu (0) mediated SET-LRP of Methyl Acrylate (DPn= 60)

MA (2 ml, 60 equiv.), DMSO (2 ml), EBiB (0.054 ml, 1 equiv.) Me6TREN (0.011 ml,

0.12 equiv.) and pre-activated Copper wire (5 cm) were added to a septum sealed tube in

an oil bath. The copper wire was wrapped around a stirring bar and the mixture was

deoxygenated by bubbling with nitrogen for 15 min. Then the polymerization was

allowed to commence for 22 h at 25 ˚C. Samples were taken after 3 h and 22 h under a

nitrogen blanket and passed through a short column of alumina to remove dissolved

copper salts prior to analysis by 1H NMR and SEC.

General Procedure for Cu (0) mediated SET-LRP of Methyl Acrylate (DPn= 40)

MA (1.32 ml, 40 equiv.), DMSO (1.32 ml), EBiB (0.054 ml, 1 equiv.) Me6TREN (0.011

ml, 0.12 equiv.) and pre-activated Copper wire (5 cm) were added to a septum sealed

tube in an oil bath. The copper wire was wrapped around a stirring bar and the mixture

was deoxygenated by bubbling with nitrogen for 15 min. Then the polymerization was

allowed to commence for 22 h at 25 ˚C. Samples were taken after 3 h and 22 h under a

nitrogen blanket and passed through a short column of alumina to remove dissolved

copper salts prior to analysis by 1H NMR and SEC.

General Procedure for Cu (0) mediated SET-LRP of Methyl Acrylate (DPn= 20)

MA (0.6 ml, 60 equiv.), DMSO (0.6 ml), EBiB (0.054 ml, 1 equiv.) Me6TREN (0.011 ml,

0.12 equiv.) and pre-activated Copper wire (5 cm) were added to a septum sealed tube in

an oil bath. The copper wire was wrapped around a stirring bar and the mixture was

deoxygenated by bubbling with nitrogen for 15 min. Then the polymerization was

allowed to commence for 22 h at 25 ˚C. Samples were taken after 3 h and 22 h under a

4
nitrogen blanket and passed through a short column of alumina to remove dissolved

copper salts prior to analysis by 1H NMR and SEC.

General Procedure for Chain Extension of PMA (DPn= 60)

General Procedure for Cu (0) mediated SET-LRP of Methyl Acrylate (DPn= 60) followed

by chain extension with MA. After 18 h of the ATRP of methyl acrylate, 2ml of methyl

acrylate and DMSO were added respectively under a nitrogen blanket to the mixture and

left for more 24 h. Samples of before and after the chain extension were taken to be

analyzed using NMR and SEC.

General Procedure for Chain Extension of PMA (DPn= 20)

General Procedure for Cu (0) mediated SET-LRP of Methyl Acrylate (DPn= 20) followed

by chain extension with MA. After 18 h of the ATRP of methyl acrylate, 0.6ml of methyl

acrylate and DMSO were added respectively under a nitrogen blanket to the mixture and

left for more 24 h. Samples of before and after the chain extension were taken to be

analyzed using NMR and SEC.

Materials

Methyl Acrylate (MA), Ethyl 2-bromoisobutyrate (EtBriB), Dimethyl sulfoxide (DMSO),

Tris (2-aminoethyl) amine (Me6TREN) all materials were used as purchased with no

further purification or distillation.

Scheme 3: Cu (0)/ Me6TREN catalyzed LRP of MA

5
Results and Discussion

In this work, the Cu (0) mediated LRP of MA for different (DPn = 20, 40, 60) showed

well controlled polymerization in high dispersities (Ð~ 1.033, 1.004, 1.001) respectively.

This work found that deoxygenating plays a great role in this polymerization. All

reactions were carried out under an inert atmosphere of oxygen-free nitrogen from the

beginning of the polymerization instead of degassing for only 15 min which affected the

polymerization positively. The samples were taken after 3 and 22 hours showed that the

polymerization was stopped after 3 hours; therefore, all samples analyzed in this research

were taken after 3 hours. In all the three polymerizations, color changed in the first 30

min into green, (Figure 1). However, the chain extension of PMA (DPn= 20 and 60) were

carried out successfully (Ð~ 1.001, 1.159) without further addition of Cu(0) or ligand.

The chain extensions was conducted by adding MA and DMSO respectively under

nitrogen blanket after 18 h of the ATRP of MA and allows the reaction to commence for

24 h. Samples of before and after the chain extension were taken and proved the success

of the chain extension of PMA.

6
 Figure 1: Cu (0) mediated living radical polymerization of MA after 3 hours

NMR analysis

The conversion of the monomer was confirmed using 1H NMR by monitoring the

signals (A,B,C and D ) that corresponded to the monomer (MA) and calculating the

remained amount of the monomer by integrating the three peaks (A,B, and C) to find out

the amount that was consumed during the polymerization. Figure 2 shown below the

spectrum of Poly methyl acrylate (DPn= 40) as an example. 1H NMR shows a decreased

in intensity of protons corresponding to the monomer ( 6.34,  5.71,   ppm) and

increased in intensity of protons corresponding to the methyl group that attached to the

polymer ( 3.50 ppm). That confirmed along with the results from the GPC that the

conversion of MA ~99%. The 1H NMR spectrum of the chain extension of PMA

(DPn=20) (figure 3) showed a complete conversion of the monomer. (Figure 4) showed

the 1H NMR of the chain extension of PMA (DPn= 60) and confirmed it was conducted

successfully.

7
Figure 2: 1H NMR chemical shifts (400MHz, ppm) of Protons for the poly methyl

acrylate DPn = 40

Figure 3: 1H NMR spectrum of the chain extension of PMA (PD=20)

Figure 4: 1H NMR spectrum of the chain extension of PMA (PD=60)

8
GPC analysis

ATRP of MA samples were run in GPC showed well-controlled poly methyl acrylate

with narrow molecular weight distribution (Ð> 1.20). In addition, there were great

correlation between the experimental molecular weight and theoretical values which is

another confirmation on the controlled polymerization (figures 5, 6, and 7). However,

(figures 8 and 9) showed below the GPC results for the chain extension of PMA and

proved they were done successfully.

Figure 5: SEC of PMA (DPn = 60)

Figure 6: SEC of PMA (DPn = 40)

9
 Figure 7: SEC of PMA (DPn = 20)

Figure 8: SEC of the chain extension of PMA (DPn = 20)

Figure 9: SEC of the chain extension of PMA (DPn = 60)

10
Conclusion

Cu (0) pre-activated wire catalyzed SET-LRP of Methyl Acrylate with various chain

lengths (DPn= 20, 40 and 60) initiated with EBiB in DMSO in the presence of N based

ligand (Me6TREN) at 25 ˚C for three hours was presented. Analyzing by using GPC and

NMR, the results showed well-controlled polymerization with narrow molecular weight

distributions (Ð~ 1.033, 1.004, 1.001) respectively. The chain extension of PMA was also

successfully conducted without addition of Cu(0) or ligand and the results were presented

in this paper. Further work can be done using higher DPn and/ or different initiator,

ligands, and solvents with MA.

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