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AngewandteInternational Edition
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Accepted Article
Title: Synthesis of structurally controlled poly(N-vinyl amide)sand poly(vinyl amine)s and their block copolymers usingorganotellurium-mediated radical polymerization
Authors: Weijia Fan and Shigeru Yamago
This manuscript has been accepted after peer review and appears as anAccepted Article online prior to editing, proofing, and formal publicationof the final Version of Record (VoR). This work is currently citable byusing the Digital Object Identifier (DOI) given below. The VoR will bepublished online in Early View as soon as possible and may be differentto this Accepted Article as a result of editing. Readers should obtainthe VoR from the journal website shown below when it is publishedto ensure accuracy of information. The authors are responsible for thecontent of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201902940Angew. Chem. 10.1002/ange.201902940
Link to VoR: http://dx.doi.org/10.1002/anie.201902940http://dx.doi.org/10.1002/ange.201902940
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Synthesis of structurally controlled poly(N-vinyl amide)s and
poly(vinyl amine)s and their block copolymers using
organotellurium-mediated radical polymerization
Weijia Fan and Shigeru Yamago*[a]
Abstract: Controlled polymerization of acyclic N-vinyl amides, i.e., N-
methyl-N-vinylacetamide (NMVA), N-vinylacetamide (NVA) and N-
vinylformamide (NVF), by organotellurium-mediated radical
polymerization (TERP) is reported. The corresponding poly(N-vinyl
amide)s with controlled molecular weight and low dispersity (Ð < 1.25)
were obtained with high monomer conversion in all cases. This is the
first report for the controlled polymerization of NVF. Hydrolysis of the
polymers, in particular PNVF, occurred quantitatively under mild
conditions, giving structurally controlled poly(vinyl amine)s. Block
copolymers containing poly(N-vinyl amide) and poly(vinyl amine)
segments were also synthesized in a controlled manner.
Poly(N-vinyl amide)s are one of the most important water-soluble
polymers and have numerous applications in biomedicals,
pharmaceuticals, cosmetics, foods, printing inks, and textiles.[1] In
particular, hydrolysis of poly(N-vinyl amide)s prepared from
acyclic N-vinyl amides, i.e., N-methyl-N-vinylacetamide (NMVA),
N-vinylacetamide (NVA) and N-vinylformamide (NVF), give
poly(vinyl amine)s (PVAs), which are pH-sensitive polymers and
are utilized in modern biological and materials sciences and
technologies, such as in vehicles for drug and gene delivery.[2]
Therefore, controlling the macromolecular structure of poly(N-
vinyl amide)s and synthesizing block copolymers consisting of
these water-soluble polymers as a segment would provide
advanced materials with improved and/or new properties.
Poly(N-vinyl amide)s are prepared by radical polymerization of
N-vinyl amides. Therefore, the use of reversible deactivation
radical polymerization (RDRP), which is also known as living
radical polymerization, is the method of choice for structural
control and block copolymer synthesis because RDRP is now
widely used for the controlled polymerization of a variety of
functionalized monomers.[3] However, N-vinyl amides are
unconjugated monomers, and their controlled polymerization is
more difficult than that of conjugated monomers. Several
controlled polymerizations of cyclic N-vinyl amides, i.e., N-
vinylpyrrolidone and N-vinylcaprolactam, have been reported
using organostibine-mediated radical polymerization,[4]
organotellurium-mediated radical polymerization (TERP),[5] atom
transfer radical polymerization (ATRP),[6] reversible addition-
fragmentation-chain transfer polymerization (RAFT),[7] and cobalt-
mediated radical polymerization (CRP);[8] however, the cyclic
amide cannot be hydrolyzed to PVA.
A single example has been reported for the controlled
polymerization of NMVA under CRP conditions, giving PNMVA
with controlled molecular weight and low dispersity (Ð), [8b] but the
monomer conversion was rather low (<65%). CRP of NVA also
gave PNVA with low Ð but only moderate monomer conversion
(<50%). Furthermore, though the resulting PNVAs were
hydrolyzed to PVAs with up to 95% conversion, the harsh reaction
conditions (6 mol L-1 aqueous HCl at 120 °C for 64 h) were
unattractive considering the synthesis of functional materials.[9]
The hydrolysis of PNVF would proceed under much milder
conditions than that of PVNA. However, while RDRP of NVF was
attempted using CMRP and RAFT, these methods could not
control the polymerization.[10] Because the successful controlled
polymerization of ethylene [11] and 1,1-difluoroethylene,[12] which
are highly challenging unconjugated monomers by RDRP, has
been recently reported, the controlled polymerization of NVF
appears to be the remaining significant challenge in RDRP.
Among the RDRP methods already reported, such as nitroxide-
mediated polymerization,[13] ATRP,[14] RAFT,[15] and CRP,[16] we
focused on TERP considering its high versatility of polymerizable
monomer families and high flexibility in block copolymer
synthesis[17] originated from its unique polymerization
mechanism.[17c,18] Here, we report the controlled polymerization
of NMVA, MVA, and NVF by TERP, which resulted in the
corresponding PNVAs with controlled molecular weight and low Ð
(Scheme 1). This is the first example of the controlled
polymerization of NVF. Hydrolysis of PNVF proceeded under
much mild conditions than that of PVNA and gave structurally
controlled PVA with quantitative conversion. Furthermore, block
copolymers consisting of PVA segments could also be
synthesized for the first time by hydrolysis of block copolymers
consisting of PNVF segments.
Scheme 1. TERP of N-vinyl amides and subsequent transformations
The feasibility of the controlled polymerization of acyclic N-
vinyl amides by TERP was first examined using NMVA (50 equiv.)
as a monomer in the presence of organotellurium chain transfer
agent 1 and dimethyl 2,2'-azobis(2-methylpropionate) (V-601,
[a] W. Fan, Prof. Dr. S. Yamago
Institute for Chemical Research, Kyoto University
Uji, Kyoto 611-0011 (Japan)
E-mail: yamago@scl.kyoto-u.ac.jp
Supporting information and the ORCID identification number for
the author of this article can be found under:
https://doi.org./xxxx
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0.40 equiv.) at 60 °C.[18] Monitoring of the polymerization by 1H
NMR spectroscopy and size exclusion chromatography (SEC)
suggested pseudo-first-order kinetics and linear growth of number
average molecular weight (Mn(SEC)) for the monomer conversion
while maintaining a low Ð (Scheme 2a). Monomer conversion
reached 93% after 5 h, and PNMVA with Mn(SEC) = 7000 and
narrow Ð (= 1.08) was obtained after reduction of the polymer end
group by Bu3SnH (Table 1, run 1). The discrepancy of Mn between
Mn(SEC) and the theoretical value (Mn(theo) = 4700) is due to the lack
of appropriate calibration standards, and the Mn values
determined by 1H NMR spectroscopy (Mn(NMR) = 4600) and MALDI
TOF mass spectrometry (Mn(MS) = 4400, Scheme 2b) were very
close to Mn(theo). These results clearly demonstrate the controlled
polymerization of NMVA.
2500 3000 3500 4000 4500 5000 5500 6000
3297.40 (n = 32)
4982.95 (n = 49)3396.51 (n = 33)
3495.59 (n = 34)3495.59 (n = 34)
3594.70 (n = 35)
3693.71 (n = 36)
3891.93 (n = 38)
4586.60 (n = 45)
4387.40 (n = 43)
4288.30 (n = 42)
4189.17 (n = 41)
m/z
4090.13 (n = 40)
4487.45 (n = 44)
4684.72 (n = 46)
4784.73 (n = 47)
4883.89 (n = 48)
3990.92 (n = 39)
3792.87 (n = 37)
5082.14 (n = 50)
0 20 40 60 80 1000.0
2.0k
4.0k
6.0k
8.0k Mn(SEC)
Mn(MS)
Mn(theo)
Mn
Conversion (%)
1.0
1.2
1.4
1.6
1.8
2.0
Ð
Ð
Scheme 2. TERP of NMVA. a) Kinetic monitoring and b) MALDI TOF mass spectra after reduction of the polymer end-group
High molecular weight PNMVAs were also synthesized by
increasing the amount of NVMA (100-500 equiv., runs 2-4). The
monomer conversion reached high values (80-95%) in all cases,
and PNMVAs with low dispersity (Ð = 1.08-1.25) were formed in
all cases. The Mn(SEC) values were higher than the Mn(theo) values
in all cases, and the difference can be explained by the polymer
standards, as the deviation in runs 2-4 (ca. 40-60%) is essentially
the same as that observed in run 1 (50%). The high end-group
fidelity (95%) was ascertained by a chain extension experiment
for a PNMVA (Mn(SEC) = 16700, Ð = 1.06) sample prepared using
100 equiv. of NMVA with 95% monomer conversion by adding
NMVA (500 equiv.) and further polymerization (see Supporting
Information). These results indicate the successful controlled
polymerization of NVMA.
Table 1. TERP of acyclic N-vinyl amides
Run Monomer Equiv. t
(h) Conv. (%) [a]
Mn(theo) Mn [b] Ð[b]
1 NVMA 50 5 93 4,700 7,000 1.08
(4,400)[c]
(4,600)[a]
2 100 7 95 9,500 15,200 1.08
(9,700) [a]
3 200 10 90 18,000 25,600 1.10
4 500 24 80 43,200 65,600 1.25
5 NVA 50 6 96 4,200 7,000 1.08
(4,300)[c]
(4,500)[a]
6 100 12 88 7,600 12,800 1.08
(7,500)[a]
7 200 25 85 14,600 20,100 1.25
8 500 25 70 29,900 38,500 1.28
9 NVF[d] 50 7 90 3,300 5,200 1.12
(3,400)[a]
10 100 12 81 5,900 6,850 1.08
(5,900)[a]
11 200 20 87 12,500 14,500 1.15
12 500 30 81 28,900 27,700 1.20
[a] Determined by 1H NMR. [b] Determined by SEC calibrated with PMMA
standards. [c] Determined by MALDI TOF mass spectrometry. [d] Mn and Ð were
determined by SEC calibrated with PEO standards.
Next, TERP of NVA was examined under the same conditions
used for that of NMVA (runs 5-8). The polymerization of NVA also
proceeded in a controlled manner, as indicated by the pseudo-
first-order kinetics and linear growth of Mn by monomer
conversion in the experiment using 50 equiv. of NVA (see
Supporting Information). Nearly quantitative conversion (96%)
occurred after 6 h, and PNVA with Mn(SEC) = 7000 and Ð = 1.08
was obtained (run 5). The discrepancy between Mn(SEC) and
Mn(theo) was again due to the polymer standards, as Mn(NMR) and
Mn(MS) are almost identical to Mn(theo). PNVAs with high molecular
weights were also prepared in a controlled manner by increasing
the amount of NVA (runs 6-8). The corresponding high molecular
weight PNVAs (Mn(SEC) = 12800-38500) with low dispersity (Ð =
1.08-1.28) were obtained with high monomer conversion (70-
88%) in all cases. The amount of dead polymer for the PNVA
prepared with 100 equiv. of NVA was 3%, as determined by a
chain extension experiment (see Supporting Information). These
results illustrated the successful control of NVA polymerization by
TERP.
Finally, TERP of NVF was examined under otherwise identical
conditions (runs 9-12). The controlled polymerization also took
place, as indicated by the pseudo-first order kinetics and linear
growth of Mn by monomer conversion in the polymerization of 50
equiv. of NVF. After 90% monomer conversion, PNVF with Mn(SEC)
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= 5200 and Ð = 1.12 was obtained (run 9). The difference
between Mn(SEC) and Mn(theo) was also clarified by determining Mn
by NMR spectroscopy. Additionally, high molecular weight PNVFs
were synthesized in a controlled manner by increasing the
amount of NVF from 100 to 500 equiv. (runs 10-12). The Mn(SEC)
became close to Mn(theo) and the dispersity slightly increased as
the amount of NVF increased, suggesting a slight loss of control.
However, the dispersity of PNVF synthesized using 500 equiv. of
monomer was still low (Ð =1.20), clearly suggesting the
successful control of NVF polymerization for the first time.
During these studies, we recognized that these acyclic N-vinyl
amide monomers are highly sensitive to acid; we experienced the
selective formation of a dimer derived from an acid-catalyzed
reaction instead of the desired polymerization.[19] While we could
not ascertain the origin of the acid, the addition of a catalytic
amount of a weakly nucleophilic base, such as N,N-
diisopropylethylamine or 2,6-lutidine, was effective in such cases.
Poly(N-vinyl amide)s with controlled Mns and low Ðs were
obtained in the presence of the base (see Supporting Information).
Also, when we carefully control the generation of acid in a hood
and a glove box, the desired controlled polymerization proceeded
reproducibly.
All poly(N-vinyl amide)s synthesized in this study were
successfully converted to the corresponding poly(vinyl N-
methylamine)s and PVAs (3) by acid- or base-catalyzed
hydrolysis (Scheme 1). PNMVA and PNVA were hydrolyzed
under acidic conditions as reported previously by Debuigne.[9] For
example, PNMVA (Mn = 12,300, Ð = 1.11) was heated with 6.0
mol L-1 HCl aqueous solution at 120 °C for 64 h in a sealed tube,
and poly(vinyl N-methylamine) with Mn = 11,000 and Ð = 1.26 was
obtained in 90% after neutralization of the product and purification
by dialysis. 1H NMR analysis of the product revealed quantitative
hydrolysis of the acetyl group. PNVA (Mn = 15,300, Ð = 1.08) was
also hydrolyzed to PVA with Mn = 11,800 and Ð = 1.15 under the
same acidic conditions. The hydrolysis of PNVF (Mn = 15900, Ð =
1.22) took place under much milder conditions than that for
PNMVA and PNVA, i.e., 2.0 mol L-1 aqueous HCl solution at 80 °C
for 6 h, giving PVA with Mn = 12,800 and Ð = 1.20. The hydrolysis
under basic conditions took place much faster than that under
acidic conditions; treatment of PNVF (Mn = 15,900, Ð = 1.22) with
aqueous 2.0 mol L-1 NaOH solution at 80 °C for 3 h afforded
quantitative conversion to PVA with Mn = 10800 and Ð = 1.17.[20]
The 1H NMR and FT-IR spectra clearly showed the complete
removal of the formyl group, and the unimodal SEC trace of PVA
with low Ð demonstrated successful hydrolysis while maintaining
a well-controlled polymer structure. Moreover, PVAs with higher
molecular weights (Mn up to 25,700) were readily synthesized by
the hydrolysis of the corresponding high molecular weight PNVFs
(see Supporting Information).
Block copolymers consisting of PVA segments were
synthesized (Scheme 3a). For example, the PNVF macroinitiator
(Mn(SEC) = 18300, Ð = 1.20) prepared from 1 and NVF (300 equiv.)
with 85% monomer conversion was dissolved in water and heated
at 60 °C with N,N-dimethylacrylamide (DMAA, 500 equiv.) in the
presence of 4,4'-azobis(4-cyanovaleric acid) (ACVA, 0.2 equiv.)
for 20 h. The formation of desired block copolymer 4 (R3 =
CONMe2) consisting of two water-soluble block segments was
confirmed by SEC by the disappearance of the PNVF macro
initiator and the formation of a new unimodal peak corresponding
to PNVF-b-PDMAA with Mn(SEC) = 78,400 and Ð = 1.42. Moreover,
the obtained copolymer was dissolved in 2.0 mol L-1 aqueous
NaOH solution and heated for 3 h; PNVF was quantitatively
hydrolyzed to PVA according to the 1H NMR spectra (Figure S7
in Supporting Information), while the acrylamide segments of
PDMAA could not be hydrolyzed to carboxylic acid under such
16 18 20 22 24
PSt
Mn = 19300,
Ð =1.20
6 (PSt-b-PNVA)
Mn = 31900,
Ð =1.08
Elution time (min)
18 20 22 24
Elution time (min)
PNVF
Mn = 18300, Ð = 1.20
4 (PNVF-b-PDMAA)
Mn = 78400, Ð = 1.42
Mn = 70000, Ð = 1.40
5 (PVA-b-PDMAA)
Scheme 3. a) Synthesis of block copolymers 5 and 6. Conditions: i: 1, NVF (300
equiv.), AIBN (0.2 equiv.), 60 °C, 15 h, 85% conversion of NVF, Mn = 18300, Ð
= 1.20. ii: DMAA (500 equiv.), ACVA (0.2 equiv), water, 60 °C, 20 h, 85%
conversion of DMAA, iii: Bu3SnH (1.5 equiv.), h (3 W white LED), 60 °C, 5 h,
Mn(SEC) = 78400, Ð = 1.42. iv: 2 mol L-1 NaOH/H2O, 80 °C, 3 h, >99% conversion,
Mn(SEC) = 70,000 and Ð = 1.40. v: 1, styrene (200 equiv.), 100 °C, 17 h, 96%
styrene conversion, Mn(SEC) = 19,300, Ð = 1.20. vi: NVA (200 equiv.), AIBN (0.2
equiv.), DMF, 60 °C, 20 h, 57% NVA conversion, Mn(SEC) = 31,900, Ð = 1.08. b)
SEC traces for the synthesis of block copolymer 5, and c) those of 6.
mild conditions due to the different reactivity of vinylamide and
acrylamide. Finally, PVA-b-PDMAA 5 was selectively obtained
(Mn(SEC) = 70,000, Ð = 1.40). (Scheme 3a).
An amphiphilic diblock copolymer consisting of polystyrene
(PSt) and PNVA was also synthesized; PSt macroinitiator (Mn(SEC)
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= 19,300, Ð = 1.20) prepared by 1 and styrene (200 equiv.) at
100 °C for 17 h (96% conversion) was dissolved in DMF and
heated with NVA (200 equiv.) at 60 °C for 20 h. Conversion of
NVA reached 57%, and the target diblock copolymer 6 was
obtained (Mn(SEC) = 31,900, Ð = 1.08). The SEC traces before and
after the blocking polymerization clearly demonstrated the
successful synthesis of the desired diblock copolymer. (Scheme
3b)
In summary, TERP of acyclic N-vinyl amides, i.e., NVMA, NVA,
and NVF, proceeded in a controlled manner with high monomer
conversion in all cases. This is the first example of the successful
controlled synthesis of PNVF. Hydrolysis of the acetyl and formyl
groups of the resulting polymers afforded structurally controlled
polyamines. The mild conditions for the hydrolysis of PNVF are
highly attractive for the fabrication of functional polymer materials
consisting of PVA segments. This approach was exemplified by
the synthesis of a block copolymer with a poly(N-vinyl amide)
segment. These results expand the synthetic scope of RDRP as
well as materials design based on poly(N-vinyl amide)s and PVAs.
Acknowledgements
This work was partly supported by the JSPS KAKENHI Grant No.
16H06352. We thank Profs. Keita Sakakibara and Yoshinobu
Tsujii of ICR, Kyoto University, for assistance with the SEC
measurements of the water-soluble polymers and for helpful
suggestions and discussions.
Keywords: vinyl amides • reversible deactivation radical
polymerization • TERP • poly(vinyl amine)
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Structurally controlled poly(vinyl amide)s and poly(vinyl amine)s are synthesized by organotellurium-mediated polymerization of acyclic vinyl amides and subsequent hydrolysis of the amides. A block copolymer having poly(vinyl amine) segment was also synthesized.
Weijia Fan, Shigeru Yamago*
Page No. – Page No.
Synthesis of structurally
controlled poly(N-vinyl
amide)s and poly(vinyl
amine)s and their block
copolymers using
organotellurium-mediated
radical polymerization
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