Poly(Alkyl Glycidate Carbonate)s as Degradable Pressure-Sensitive Adhesives

Article abstract of DOI:10.1002/anie.201811894

Insertion of CO₂ into the polyacrylate backbone, forming poly(carbonate) analogues, provides an environmentally friendly and biocompatible alternative. The synthesis of five poly(carbonate) analogues of poly(methyl acrylate), poly(ethyl acrylate), and poly(butyl acrylate) is described. The polymers are prepared using the salen cobalt(III) complex catalyzed copolymerization of CO₂ and a derivatized oxirane. All the carbonate analogues possess higher glass-transition temperatures (T_g=32 to ?5 °C) than alkyl acrylates (T_g=10 to ?50 °C), however, the carbonate analogues (T_d≈230 °C) undergo thermal decomposition at lower temperatures than their acrylate counterparts (T_d≈380 °C). The poly(alkyl carbonates) exhibit compositional-dependent adhesivity. The poly(carbonate) analogues degrade into glycerol, alcohol, and CO₂ in a time- and pH-dependent manner with the rate of degradation accelerated at higher pH conditions, in contrast to poly(acrylate)s.

Full text of DOI:10.1002/anie.201811894

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Accepted Article
Title: Poly(Alkyl Glycidate Carbonate)s as Degradable Pressure
Sensitive Adhesives
Authors: Anjeza Beharaj, Iriny Ekladious, and Mark W Grinstaff
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201811894
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10.1002/anie.201811894
Angewandte Chemie International Edition
COMMUNICATION
Poly(Alkyl Glycidate Carbonate)s as Degradable Pressure
Sensitive Adhesives
Anjeza Beharaj, Iriny Ekladious, and Mark W.
Grinstaff*
Abstract: Polyacrylates are widely used in industry; however,
their all aliphatic backbone leads to minimal degradability with
challenges in recovery and recyclability. Insertion of CO2 into the
backbone, forming poly(carbonate) analogues of poly(acrylate)s
provides an environmentally friendly and biocompatible
alternative polymer. The synthesis of five poly(carbonate)
analogues of poly(methyl acrylate), poly(ethyl acrylate), and
poly(butyl acrylate) is described. The polymers are prepared via
the salen cobalt(III) complex catalyzed copolymerization of CO2
and a derivatized oxirane. All the carbonate analogues possess
higher glass transition temperatures (Tg = 32 to -5 OC) than alkyl
acrylates (Tg = 10 to -50 OC), however, the carbonate analogues
(Td=~230 OC) undergo thermal decomposition at lower
temperatures than their acrylate counterparts (Td=~380 OC).
Figure 1. Commercially available poly(acrylate)s (A) poly(methyl acrylate)
Additionally, we synthesized constitutionally isomeric poly(alkyl
carbonates) in which the pendant ester group is in the reverse
orientation to the backbone. Compared to the acrylate derivative,
the reverse analogues possess lower glass transition
temperatures (Tg = 24 to 0 OC). However, the polymerization
reactions are 10X more efficient and with more polymer
produced than the cyclic carbonate byproduct. The poly(alkyl
carbonates) exhibit compositional dependent adhesivity, and two
of the analogues possess comparative peel strength to Duct
Tape® and Scotch Tape®. Finally, the poly(carbonate)
analogues degrade into glycerol, alcohol, and CO2 in a time and
pH dependent manner with the rate of degradation accelerated
at higher pH conditions, in contrast to the poly(acrylate)s.
(PMA), poly(ethyl acrylate) (PEA), and poly(butyl acrylate) (PBA) their
corresponding glycidate carbonates (B) poly(methyl acrylate carbonate)
PMAc, poly(ethyl acrylate carbonate) PEAc, poly(butyl acrylate carbonate)
PBAc, and glycidyl isomers (C) poly(glycidyl ethyl ester carbonate) PGC-E
poly(glycidyl butyl ester carbonate) PGC-B.
adhesivity (Figure 1).
The insertion of a carbonate moiety into the backbone of
these acrylate polymers introduces an inherent glycidate or
glycerol substructure allowing the carbonate analogue polymers
to degrade into safe natural metabolites.(e.g., carbon dioxide,
glycerol, glycidates, alcohols, and benign acids). Furthermore,
given the polymer structure, we propose that these polymers
can be synthesized via a green renewable process using CO2
compared to a free radical polymerization reaction.12,13 Herein
we report the synthesis and characterization of poly(carbonate)
analogues of poly(methyl acrylate) (PMA), poly(ethyl acrylate)
(PEA), and poly(butyl acrylate) (PBA) by the copolymerization of
CO2 and the corresponding alkyl glycidate. Additionally, we
describe the role pendant chain steric interactions and
electronics play in monomer reactivity as well as the properties
of the resultant polymers via the study of two constitutionally
isomeric polymers where the pendant group esters are in
opposite orientation (Figure 1).
Poly(alkyl acrylate)s are commodity polymers used in the
pharmaceutical, cosmetic, automotive, adhesive, electronics,
textiles, plastics, and paint industries.1–5 For example, formula-
tions of these poly(acrylate)s are used as pressure-sensitive
adhesives (PSAs) in consumer-grade tapes, baby diapers,
medical bandages, etc.6,7 The PSA sector is among the fastest
growing in the adhesive market, and new formulations with
increased adhesivity, degradability, or stimuli-responsive
characteristics are of interest.8 However, their wide-spread
industrial use on the multi-ton scale affords a significant non-
degradable waste stream in society due to their all aliphatic
carbon backbone.9 As mounting plastic waste affects all aspects
of life on earth, it is important to take into consideration a
polymer’s complete lifecycle from synthesis, to use, to
degradation.10,11 We hypothesize that introducing a cleavable
carbonate linkage within the poly(acrylate) backbone will give a
degradable polymer while maintaining key properties, such as
Polymers incorporating
a glycerol backbone are of
significant interest due to their degradability, biocompatibility,
and chemical tunability.14–23 Glycerol is listed as Generally
Recognized As Safe (GRAS) by the Food and Drug
Administration, and as such, linear, branched, hyperbranched,
and dendritic polyglycerols are being investigated for a wide-
variety of medical and non-medical use.24–33
To install the carbonate moiety within the polymer back-bone,
we selected
a polymerization methodology pioneered and
brought to fruition by Coates,34 Darensbourg,35 Frey,36
Inoue,37,38 Lu,39,40, and Nozaki.41,42 Specifically, the
poly(carbonate)s were synthesized via the copolymerization of
an oxiranyl monomer and CO2 using a metal salen catalyst with
a quaternary ammonium salt, rac-[SalcyCoIIIDNP]DNP, as
shown in scheme 1 (SI page 5). Polymer selectivity was
determined by 1H NMR spectroscopy as the ratio of the
polymeric methine hydrogen to the cyclic carbonate methine
hydrogen. Turn over frequency (TOF) was calculated as
[*]
A. Beharaj, I. Ekladious, Prof. M.W. Grinstaff
Departments of Chemistry, Biomedical Engineering, and Medicine
Boston University
Boston, MA 02215 (USA)
E-mail: mgrin@bu.edu
Homepage: http://people.bu.edu/mgrin
Supporting information for this article is available on the WWW
under http://dx.doi.org/______________
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COMMUNICATION
([product]/[product
+
monomer])·catalyst loading·h−1 as
above. These epoxide monomers are less sterically crowded
and the electron withdrawing effect of the carbonyl is removed,
while still preserving the ester functionality in the resulting
polymer (Figure 1). The ethyl glycidyl ester and butyl glycidyl
ester monomers efficiently polymerize in the presence of the
cobalt salen catalyst (1000:1 monomer: catalyst loading) at 25
oC under 1.54 MPa of CO2 with significantly greater TOF values
(up to 10 fold) to give the corresponding polymeric constitutional
isomers with moderate molar mass (Mn = 5.9 kg/mol to 9.9
kg/mol) and low dispersities of <1.2 (Figure 2 and Table 1). A
similar trend in TOF and selectivity, to that of the glycidate
polymerization, is observed with the values decreasing with
increasing carbon number of the pendant ester (ethyl and butyl:
TOF=171 h-1 and 129 h-1 and selectivity 99% and >99%,
respectively). Decreasing the monomer:catalyst loading gives
higher TOF values (with the optimal ratio being 2000:1) while
increasing the temperature affords more cyclic carbonate (SI
tables 4-5).
determined by 1H NMR (SI figure 1). Finally, number average
molecular weight and dispersity were determined via GPC
analysis in THF with polystyrene standards.
Scheme 1. CO2 catalysed via a cobalt salen complex (rac-
[SalcyCoIIIDNP]DNP) to yield polycarbonates. Please note that the
polymerization conditions in scheme 1 enable comparisons between the
various monomers. Optimization tables for all of the monomers can be
found in SI tables 1-5.
The low TOF values and polymer molar mass observed
The carbonate acrylate mimetics polymerize with low TOF
values in the presence of the cobalt salen catalyst (1000:1
monomer: catalyst loading) at 25 oC and 1.54 MPa of CO2 to
give PMAc, PEAc, and PBAc (Mn=7.3 to 10.6 kg/mol with
narrow dispersities <1.2) and significant formation of the cyclic
carbonate (Figure 2 and Table 1). Of the three monomers, the
methyl ester glycidate displays the highest polymer selectivity of
72%, compared to 54% for the ethyl ester and 48% for the butyl
ester monomers. The catalytic TOF of the glycidate epoxides
decreases with increasing carbon number of the pendant ester
(24, 15 and 5.6 h-1 for methyl, ethyl, and butyl respectively).
These low TOF values are similar to the value reported for the
polymerization of poly(benzyl glycidate carbonate) (TOF = 11 h-
Table 1. Thermal Properties of Acrylates and Carbonates.
Polymer
PMA
Mn(Kg/mol) [a]
Ð(Mw/Mn)
1.9
Tg(oC) [b]
Td(oC)[c]
389
26
10
PEA
99
1.8
-27
-50
17
384
PBA
95
1.7
376
PMAc
PEAc
PBAc
PGC-E
PGC-B
7.3
10.6
9.8
9.9
5.9
1.2
236
1.2
32
244
1.3
-5
237
1.2
24
214
1
) under the same temperature and catalyst loading.20 Upon
1.2
0
228
screening the polymerization conditions, similar trends are
observed for all monomers. Raising the reaction temperature
increases turnover rates but diminishes polymer selectivity,
preferring the formation of cyclic carbonate. Increasing catalyst
loading affords a bell curve with an optimal polymer selectivity
centered at 500:1 mono-mer:catalyst loading (SI Tables 1-3).
Next, we investigated the copolymerization of CO2 and the
corresponding oxiranyl glycidyl monomers where the pendant
[a] Molar mass and dispersity are determined by GPC analysis with
polysty-rene standards. [b] The glass transition is measured via DSC. [c]
Thermal decomposition is determined from the TGA curve at 50% weight
loss.
with the ester glycidate polymerizations are likely
a
consequence of the carbonyl group alpha to the methine carbon
of the epoxide affording increased: 1) steric hindrance during the
polymerization reaction; and 2) reactivity of the more substituted
methine carbon of the epoxide via the electron withdrawing
effects from the adjacent carbonyl. In support of this
interpretation, Darensbourg et al. reported a low TOF of 9.3 h-1
for the synthesis of poly(tert-butyl 3,4-dihydroxybutanoate
carbonate) which is an oxirane containing a bulky side chain.43
Additionally, gaussian model (B3LYP, NBO) of the epoxide
LUMO of the methine carbon-oxygen sigma* is lower than the
methylene carbon-oxygen sigma* (SI figure 21). This effect is
also experimentally observed, as 13C NMR of glycidyl polymers
exhibit 100% head-to-tail polymer backbone formation,
indicating nucleophilic attack only on the least substituted side of
the epoxide. However, 13C NMR of the glycidate polymers
display
head-to-tail,
tail-to-tail,
and
head-to-head
regiosequences as well, indicating nucleophilic attack on the
more substituted carbon is also occurring. (SI figures 12-16).
All the polymers exhibit bimodal distributions (SI figure
19A) due to residual water molecules (e.g., in the reactor
chamber) starting new polymer chains through nucleophilic
Figure 2. Polymerization efficiency of epoxide monomers with CO2 and
rac-[salcyCoIIIDNP]DNP. Reactions were performed in neat monomer (10
mmol) in an 8 mL autoclave under 1.52 MPa of CO2 with catalyst loading
of 1000:1 at 25 oC. N=3, Avg ± STD.
group esters are in the opposite orientation to the epoxide used
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o
attack of the epoxide. This is a known phenomenon in these
reactions as previously discussed by Darensbourg.44
Additionally, Maldi-ToF chain-end analysis indicates the main
distribution corresponds to a hydroxyl initiator and hydroxyl
terminal group, while the minor distribution is initiated with
dinitrophenolate (from the catalyst) and a hydroxyl terminal
group. (SI 19B). Although bimodal, these polymers exhibit
narrow dispersities (<1.2) when integrating over both peaks. The
polymers, like the poly(alkyl acrylate)s, are soluble in polar
aprotic solvents such as dimethylformamide, tetrahydrofuran,
dichloromethane, dimethylsulfoxide and acetonitrile, while not
soluble in relatively polar protic solvents such as water and
methanol.
at 50% weight loss (~380 C) compared to all of the carbonate
analogues (~225 oC).
The cytotoxicity of all the acrylate and carbonate polymers
was evaluated against NIH 3T3 fibroblast cells at a high
concentration of 2.5 mg/mL for 24 hours in transwell plates (SI
figure 22). One-way ANOVA testing (p >0.05) revealed no
statistical significance between the control and polymer groups,
indicating that the polymers do not leech cytotoxic compounds.
To determine the effect of introducing a carbonate linkage
into the poly(alkyl acrylate) structure on the adhesive properties,
peel tests were conducted at 180O between glass (SiO2) and A4
paper (Figure 3). Only room temperature viscous polymers were
examined. PBA exhibits the weakest peel strength (0.13 N/cm)
while PEA possess the highest (8.04 N/cm). The poly butyl
carbonate analogues, PBAc and PGC-B, are stronger
adhesives than PBA, but weaker than PEA. The relative
enhancement in adhesivity with the carbonate polymers likely
reflects increased polymer-polymer van der walls forces and
dipole interactions compared to the aliphatic poly(acrylate)s.
PBAc (4.3 N/cm) and PGC-B (2.1 N/cm) exhibit comparable
adhesive strength to commercial Duct Tape, (3.9 N/cm, 3M
2929) and scotch tape (1.7 N/cm, 3M 810), respectively. All of
the carbonate and acrylate polymers display cohesive failure in
testing, consistent with failure in the bulk layer of the material.
Aliphatic polymers are immune to most degradation
methods and are only degraded by specific microbes. The
process itself is long and, thus, polyacrylates exhibit main chain
degradation in soil at a rate of 0.12% per 6 month, if at all.45 In
contrast, polycarbonates are known to degrade via UV radiation,
oxidative cleavage, water erosion, as well as microbial, thus,
polycarbonate life expectancy peaks at 3 years.46 To evaluate
the effect of introducing a carbonate linkage into the polymer
backbone on degradation, studies with PEAc, PGC-E, and PEA
were conducted over a 35 day period (Figure 4). The polymers
were dissolved in a THF/water solution of 3:1 v/v %, and the
number average molecular weight (Mn) was monitored via GPC
analysis as a function of time. The pH of the buffer solution was
varied from 5 to 9 so as to cover a range of environmental and
biomedical relevance.
We hypothesize that the proximity of the carbonyl
functionality to the polymer backbone in PMAc, PEAc, and
PBAc will restrict polymer motion leading to enhanced
crystallinity, greater decomposition temperatures (Td), and
higher glass transition temperatures (Tg) compared to PGC-E,
and PGC-B, as well as PMA, PEA and PBA. At room
temperature, PMA is a pliable solid with a Tg of 10 oC, while
PEA and PBA are viscous liquids and possess lower Tg values
of -27 oC and -50 oC respectively. No melting and/or
crystallization temperatures are observed for PMA, PEA and
PBA. In contrast, PMAc, PGC-E, and PEAc are brittle solids at
o
room temperature with Tg = 17, 24, and 32 C, respectively. All
of the carbonate analogues possess higher Tg than their
corresponding poly(acrylate) derivatives (Table 1). This finding is
attributed to the sp2 hybridization of the carbonate in the
backbone limiting bond rotation, and, thus, leading to greater
polymer rigidity.
Additionally, PGC-E possesses a lower Tg (24 oC) com-
o
pared to PEAc (32 C). The higher Tg value for PEAc is likely
attributed to the side-chain carbonyl group, which imparts
backbone rigidity and facilitates interchain packing through
dipole interactions to form a more thermally stable bulk material.
o
Unexpectedly, PGC-B exhibits a higher Tg (0 C) than PBAc (-5
oC), suggesting that the pendant chain carbon length dominates
The molar mass of PEA remained relatively constant over
the one month period at all three pH ranges (although some
pendant ester hydrolysis is occurring) as the initial and final Mn
were not statistically different from each other (One way ANOVA,
p >0.05). Indeed, there was significant error in the acrylate data
due to high dispersity of the commercial acrylate polymer. Both
PEAc and PGC-E showed appreciable degradation in all three
conditions. Degradation occurred fastest at pH 9 and slowest at
pH 5 for both polymers. PGC-E exhibited the fastest degradation
rates with t1/2= 2, 18, and >35 days for pH 9, 7, and 5,
respectively. PEAc exhibited degradation with t1/2= 33, >35, >35
days for pH 9, 7, and 5, respectively. PGC-E degraded faster
than PEAc in all three buffers. Additionally, none of the polymers
degraded in neat organic solvent (THF) for a span of 30 days
(data not shown). As the degradation products are CO2 and
benign alcohols and acids, these ecologically friendly products
are part of a renewable cycle (Figure 4.). As more than 260
million metric tons of plastic products are made per annum47,
tailoring polymers for faster or controlled degradation is critical to
meet the ever-increasing demand for plastic goods in a growing
world economy.
Figure 3. Peel strength of poly(acrylate)s, poly(carbonate) analogues, and
commercial adhesives at 22 OC. (180O on glass following ASTM D903;
N=3, Avg ± STD)
polymer packing when longer than two units. Furthermore, as
mentioned above, PBAc contains varied regiosequences in its
backbone chain, while PGC-B is perfectly alternating. This
irregularity in PBAc likely leads to a larger packing volume. The
polyacrylate materials exhibit higher thermal decomposition (Td)
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COMMUNICATION
In conclusion, five novel carbonate polymers that struc-
turally mimic widely utilized commercial poly(acrylate)s are
amenable to preparing polymers possessing varied alkyl ester
chain lengths with narrow dispersities. The thermal and
degradation properties of these two constitutional isomer
polymers are significantly different. The PMAc, PEAc, and
PBAc polymers possess higher Tgs than their PGC-E/B
counterparts as well as higher Tgs than the commercial
poly(acrylate)s. Additionally, the carbonates retain the adhesive
properties of their acrylate analogues. Introduction of the
carbonate linkage within the polymer backbone provides a
means for polymer degradation of both polymers unlike the
poly(acrylate)s. Due to the degradable nature and the relatively
benign degradation products, these polymers add to the
repertoire of known biodegradable and biocompatible
carbonates, and will be of interest for applications in the
biomedical/pharmaceutical and consumer product space.
Acknowledgements
Acknowledgements Text. This work was supported in part by the
NSF (DMR-1410450 and DMR-1507081). NMR facilities at
Boston University are supported by the NSF (CHE-0619339).
Keywords: polycarbonates • pressure sensitive adhesive •
carbon dioxide • polyacrylates • degradable • glycerol
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Anjeza Beharaj
Iriny Ekladious
Mark W. Grinstaff
0000-0003-4686-8123
0000-0003-1192-1414
0000-0002-5453-3668
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10.1002/anie.201811894
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Degradable poly(alkyl glycidate carbonate)s, synthesized via the salen cobalt(III) complex catalyzed co-polymerization of CO2
and glycidate, are novel pressure sensitive adhesives.
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