Precision phosphonic acid functionalized polyolefin architectures

Article abstract of DOI:10.1021/ma902659y

Polyethylene structures containing precisely placed phosphonic acids were synthesized varying both the frequency of acid appearance along the backbone and the architecture associated with each position. Single, geminal and benzyl attachment schemes are described with symmetry of placement being an important feature. Altering these precision primary structures has a direct effect on secondary structure where changes in thermal behavior become obvious, particularly in terms of crystallization behavior. It is evident, that strong interactions between polymer chains exist, effecting polymer crystallization and solubility depending upon both the length of methylene run-lengths between symmetrically placed acids and whether or not the acid group is protected as the ester or free to participate in hydrogen bonding, which directly influences interchain interaction.

Full text of DOI:10.1021/ma902659y

3690 Macromolecules 2010, 43, 3690–3698
DOI: 10.1021/ma902659y
Precision Phosphonic Acid Functionalized Polyolefin Architectures
†
‡
‡
‡
€
Kathleen L. Opper, Dilyana Markova, Markus Klapper, Klaus Mullen, and
Kenneth B. Wagener*,†
†The George and Josephine Butler Polymer Research Laboratory, Department of Chemistry, University of
Florida, Gainesville, Florida 32611-7200, and ‡Max Planck Institute for Polymer Research, Ackermannweg 10,
55128 Mainz, Germany
Received December 1, 2009; Revised Manuscript Received March 18, 2010
ABSTRACT: Polyethylene structures containing precisely placed phosphonic acids were synthesized
varying both the frequency of acid appearance along the backbone and the architecture associated with
each position. Single, geminal, and benzyl attachment schemes are described with symmetry of placement
being an important feature. Altering these precision primary structures has a direct effect on secondary
structure where changes in thermal behavior become obvious, particularly in terms of crystallization
behavior. It is evident that strong interactions between polymer chains exist, effecting polymer crystallization
and solubility depending upon both the length of methylene run-lengths between symmetrically placed acids
and whether or not the acid group is protected as the ester or free to participate in hydrogen bonding, which
directly influences interchain interaction.
Scheme 1. Efficient Monomer Syntheses
Introduction
The wide range of chemical and physical properties make
polyolefins, specifically polyethylene, the highest volume com-
mercial synthetic polymer produced today.1 The number of
commercial applications can be increased by varying the archi-
tecture and functionality, thereby enhancing the chemical and
physical properties of the otherwise unreactive hydrocarbon
backbone.2-5 Functionalization of polyolefins is typically
achieved using polymerization techniques having common path-
ways of comonomer incorporation or postpolymerization modi-
fications.3,6-8 There are advantages and disadvantages to each
approach. Although polymer composition is easily tunable using
comonomer incorporation, monomer reactivity and catalyst
activity represent possible challenges. Modifying an existing
polymer may result in chain breakage, cross-linking, and unknown
amounts of functionality incorporation.
Polymers containing exact placement of functional groups can
be obtained using a step-growth metathesis polycondensation
technique.9-11 This approach has been utilized to synthesize
strictly linear and otherwise challenging polyethylene (PE) copo-
lymers. After incorporating several traditional ethylene/vinyl
repeat units into a single symmetrical R,ω-diene monomer,
polymerization via metathesis polycondensation followed by
hydrogenation yields a precisely functionalized PE copolymer.
This technique not only allows for the precise and tunable
incorporation of functional groups but also results in unique
polymer structures and morphologies.12,13
To further study PE crystallization in the presence of inter-
active hydrogen bonding groups,14-16 a family of polyethylenes
functionalized with phosphonic acids has been synthesized.
Phosphonic acid-containing polymers already have multiple
applications as membranes for ion transport, exchange, or
barriers,17-21 as well as biomaterials for dental cements, bone
integration or cell adhesion.22-24 Accordingly, creating a well-
defined family of precisely functionalized phosphonic acid-
containing polymer architectures, discussed herein, potentially
increases the range of applications for such polymers,25 as
recently it was shown that order and crystallinity can dramati-
cally improve the proton mobility by generating defined proton
pathways.26 This study comprises a systematic investigation
relating primary and secondary structure of these polymers in
the presence of resilient, highly interactive phosphonic acid
groups.
*Corresponding author. E-mail: wagener@chem.ufl.edu.
pubs.acs.org/Macromolecules
Published on Web 03/25/2010
r 2010 American Chemical Society

Article
Macromolecules, Vol. 43, No. 8, 2010 3691
Figure 1. Phosphonic ester and acid polymer family: (i) 0.25 mol % (Cy3P)2Cl2RudCHPh, 50 °C, 10-3 mmHg; (ii) RhCl(PPh3)3, H2 (40 bar), toluene;
(iii) (1)TMSBr, CH2Cl2, 24 h, (2) MeOH, 24 h.
Figure 2. Phosphonic ester and acid variations in functionality and architecture: (i) 0.25 mol % (Cy3P)2Cl2RudCHPh, 50 °C, 10-3 mmHg;
(ii) RhCl(PPh3)3, H2 (40 bar), toluene; (iii) (1) TMSBr, CH2Cl2, 24 h, (2) MeOH, 24 h.
Table 1. Soluble Phosphonic Ester Molecular Weight and Molecular
Weight Distribution Data
Results and Discussion
Synthesis. Structure control begins with the synthesis of 7
monomers, the attachment of protected phosphonic acid
groups being varied between protected single acids (1-3),
protected geminal acids (4 and 5), and protected benzyl acids
(6 and 7). Methylene spacing between these symmetrically
placed protected phosphonic acid groups is determined using
appropriate alkenyl synthons (Scheme 1). Singly attached
phosphonic acid ester monomers were synthesized by a two-
step, one-pot alkylation reaction.27 Geminal phosphonic
acid ester monomers were prepared using a hydride base
for the alkylation, and benzyl phosphonic acid ester mono-
mers were introduced via an etheral benzene linkage. Speci-
fically, after alkylation chemistry to prepare the diene benzyl
alcohol, bromination using an Appel reaction followed by an
Arbuzov reaction yielded the monomers 6 and 7.
GPC dataa
polymer
Mn
Mw
PDI
15
16
17
18
19
20
21
10.6
23.6
17.9
6.2
19.5
10.6
7.3
17.1
40.4
34.5
11.4
33.3
20.6
16.4
1.61
1.68
1.93
1.82
1.71
1.94
2.23
a In kg/mol obtained in THF relative to PS standards.
are obtained as insoluble polymers. Hydrogenation was also
performed to yield 20 and 21 and these were subsequently
deprotected to generate insoluble precision benzyl phos-
phonic acid polymers 27 and 28.
Figure 1 shows the step-growth metathesis polycondensa-
tion technique using protected singly attached phosphonic acid
monomers 1-3. Polymerization yields unsaturated polymers
8-10, which upon saturation with hydrogen yields precisely
spaced phosphonic acid ester polymers 15-17. Quantitative
deprotection using reaction (iii)27,28 yielded precisely func-
tionalized phosphonic acid polymers 22-24 with the spacing
between acids containing exactly 8, 14, or 20 methylenes. Poly-
mers 22-24 were isolated as insoluble highly interactive poly-
mers after evaporating the methanol and washing with acetone.
The methodology used to alter the architecture of such
precision phosphonic acid polymers is shown in Figure 2,
where geminal acids are introduced as well as benzyl acids.
Polymerization of protected geminal monomers 4 and 5
containing twice the functionality content yielded geminal
phosphonic acid ester polymers 11 and 12, which upon
hydrogenation affords polymers 18 and 19. Upon deprotec-
tion, precision geminal phosphonic acid polymers 25 and 26
As such, solution characterization techniques were utilized on
the soluble phosphonic acid ester polymers in supporting pri-
mary structure, including functionality content. Additional bulk
techniques were utilized in probing acid polymer structure.
Structure. Table 1 shows molecular weight and polydis-
persity data for the soluble, protected phosphonic acid ester
polymers. Throughout, monomodal traces were obtained
with polydispersity indices (PDIs) of about 2 consistent with
the step-growth polymerization technique with the slight
variations due to competing reactions. In general, protected
single phosphonic acid ester polymers have higher molecular
weights with degrees of polymerizations (DPs) of about 50,
while an increase in functionality (either as geminal or etheral
groups) apparently leads to catalyst deactivation. The ex-
ception within single phosphonic acid ester polymers include
16 and 17 with 17 exhibiting a lower DP attributed to
inhibition of ethylene removal. However sufficient molecular
weights for property comparison were obtained after an

3692 Macromolecules, Vol. 43, No. 8, 2010
Opper et al.
Figure 3. Solution 1H NMR spectra in CDCl3 of soluble ester polymers 16, 18, and 20.
iterative addition of 0.25 mol % catalyst halfway through the
polymerization.29 In the extreme case when geminal and
benzyl monomers containing three methylene units under-
went polymerization attempts (not shown), only oligomers
were obtained. High concentration of functional groups
relative to olefin led to the oligomerization under typically
ideal bulk polymerization conditions. Following the path of
lowering the concentration using solvent was not followed as
this would theoretically increase the formation of cyclic
structures specifically preformed into the structure by geminal
substitution and the Thorpe-Ingold effect.
Representative soluble, protected phosphonic acid ester
polymer 1H NMR spectra confirm molecular weight via CH3
end-group integration, hydrogenation shown by the absence
of olefin signal at ∼4.5 ppm and correct phosphonic acid
ester functionality content (Figure 3). The spectrum of single
phosphonic acid ester polymer 16 shows the clean polymer
structure including methine (b), R-methylene (c), β-methy-
lene (d), and unresolved backbone methylene (e) protons
along with the ethyl ester CH2 (a) and CH3 (f). The spectrum of
geminal ester polymer 18 contains R-protons coupled to the
two phosphorus atoms (h), β-methylene (i) and unresolved
backbone methylene (j) protons along with the ethyl ester CH2
(g) and CH3 (k). The spectrum of benzyl ester polymer 20
contains benzene protons (l and m); etheral oxygen backbone
R- (o), β- (q), γ- (r), and unresolved (s) protons; benzyl pro-
Figure 4. IR spectra comparing the 14-methylene spaced polymers
with (a) FT-IR of ester polymers and (b) ATR-IR of acid polymers.
tons (p); and ethyl ester CH2 (n) and CH3 (t). Additionally, all
31P NMR spectra showing a single resonance indicated that
phosphonic acid esters remained intact prior to hydrolysis.
Functional group identity (protected ester compared to
deprotected acid) was further probed using FT-IR and ATR-
IR (Figure 4). The most interesting absorbances result from
the functional group comparing the ester polymers (16, 18,
and 20) to acid polymers (17, 19, and 21) within the repre-
sentative 14-methylene spaced polymers (see Supporting
Information for all polymers). The protected single phos-
phonic acid ester polymer 16 contains absorbances including
PdO stretching vibrations at 1243 cm-1 and P-O-C abor-
bances at 955, 1026, and 1164 cm-1 with the geminal (18)
and benzyl (20) ester polymers displaying similar motions.
Benzyl ester polymer 20 is complicated by 1,3,5-trisubsti-
tuted benzene ring motions: strong benzene in-plane C-H
bending band at 1054 cm-1, weak symmetric C-O-C
stretch at 1040 cm-1, strong etheral C-O-C strong asym-
metric stretch at 1247 cm-1. Other benzene motions include
CdC ring stretches at 1456, and 1603 cm-1, along with
weaker out-of-plane C-H bending bands at 780 and
851 cm-1. Within the representative acid polymers (17, 19,
and 21), the PdO stretch broadens to lower frequency at
about 1143 cm-1, and P-OH stretches are observed at ∼939
and ∼1004 cm-1
.
Thermal Properties. The primary structures of all poly-
mers are exact and precisely defined, stemming from the
features of metathesis polycondensation chemistry. Trends
in secondary structure variation with respect to decomposi-
tion and crystallinity become apparent in the thermal prop-
erties probed by TGA and DSC.
TGA data is particularly valuable relating the profile
shape and decomposition to the acid polymer functionality
amount as titration of insoluble materials was not feasible.
The TGAs of all protected phosphonic acid polymers show a
two-step decomposition profile, attributed to ester and back-
bone decomposition, yet dependent on the exact identity
of either single, geminal or benzyl acid ester polymers

Article
Macromolecules, Vol. 43, No. 8, 2010 3693
Figure 6. Thermogravimetric analysis comparing phosphonic acid
polymers containing 14 and 20 methylenes.
Figure 5. Thermogravimetric analysis comparing phosphonic acid
ester polymers containing 14 and 20 methylenes.
Table 2. Summary of DSC thermal analysis
(Figure 5). Each single, geminal or benzyl acid ester polymer
profile differs drastically from the corresponding depro-
tected acid polymer profiles (Figure 6).
b
c
b
c
Tg
estersa (°C)
Tm
(°C)
ΔHm
(J/g)
Tg
(°C)
Tm
(°C)
ΔHm
(J/g)
acidsa
Shown in Figure 5, the protected single phosphonic acid
ester polymers and geminal ester polymers 16-19 first
decompose at roughly 300 °C from the loss of ethylene from
the ethyl esters.30 The ether linkage effects benzyl ester
polymers 20 and 21 as the first decomposition is much
greater than the ester content. Because of the complexity of
decomposition in all of these functional polymers, this first
mass loss does not exactly correlate as observed in simpler
precision halogen substituted structures.31 However, when
comparing all of the ester polymers 16-21, the residue remain-
ing is highest in polymers containing the most functionality;
i.e., polymers possessing more frequent functional groups
with 14 methylenes have more residue than those with 20
methylenes, polymers having geminal attachment have more
residue than those with single attachment, and polymers
having benzyl attachment have the most residue due to the
ether linked benzyl ester. The mass % loss of the step
decompositions does not quantitatively correlate to any
assumed ethyl, ethoxide, or phosphonate cleavage. The
remaining residue also does not correlate exactly to specific
decomposition products but the general shape of the decom-
position profile correlates to the functionalization.
15
16
17
18
19
20
21
-57
-61
-
22
44
45
23
11, 13
55
30
47
24d
25
48,67
87
23,22
120
42
-42
32
43
-48 47
26d
27
-25
2
28d
46
a Second heat shown at 10 °C/min, except where noted otherwise. b Cp
(J/g°C) were between 0.07 and 0.12. c Peak melting temperature. d First
heat at 10 °C/min after annealing at room temperature for72 h attaining
reproducible endotherms.
undefined loss of functionality coupled to loss of water
(presumably through anhydride formation), followed by a
sharper one-step decomposition resulting from polymer
backbone decomposition. In all cases, there are no simila-
rities in acid decomposition profile shape to ester profile
shape. Quantitatively, the functionality content by mass %
loss again did not match exactly particular expected acid
fragments. However, the trend relating the highest residues
remaining to the most functional polymers is upheld.
While the TGA profiles appear similar between specific
simple, geminal, and benzyl esters and acids, DSC reveals dif-
ferences in the crystallization behavior throughout the com-
plete protected ester and deprotected acid families (Table 2).
Within the deprotected acid polymers shown in Figure 6,
the decomposition profile shape corresponds to a broad

3694 Macromolecules, Vol. 43, No. 8, 2010
Opper et al.
Figure 7. DSC thermograms with arbitrary offsets of (a) semicrystalline ester polymers, second heat shown (b) semicrystalline acid polymers, first heat
after 72 h annealing at room temperature shown.
Amorphous ester polymers are obtained for those spaced with
8 and 14 methylenes (polymers 15, 16, 18, and 20) with glass
transitions ranging from -62 to -24 °C. Semicrystalline ester
polymers are obtained once the functionality is spaced by 20
methylenes (polymers 17, 19, and 21) with crystallization being
attributed to the 20-methylene run-length. Upon hydrolysis to
the acid family, amorphous and semicrystalline trends are
upheld yet with transitions at higher temperatures. The glass
transition temperatures of the amorphous polymers increase by
more than 50 °C, ranging from 32 to 45 °C.
The thermal behavior of semicrystalline polymers is com-
plicated by the strongly interacting phosphonic acid func-
tional groups, which causes the melting temperature to
increase (Table 2) and also affects the crystallization time
scale. In a previous random phosphonic acid-modified poly-
ethylene polymer study containing lower incorporation le-
vels (2.8, 1.8, and 0.8 acids per 100 carbon atoms) than the
precision 20-methylene spaced polymers (5 acids per 100
carbons), crystallization kinetics were significantly affected
and found to be strongly influenced by annealing and the
thermal history.14 It was also observed that when phospho-
nic acid frequency was increased to 7.4 acids per 100 carbons,
similar to 14-methylene spaced polymers, no crystallization
was observed. In the precision single, geminal, and benzyl
phosphonic acid polymer family presented here, a similar
behavior is observed when the run-length is reduced below 20
methylenes. As noted by MacKnight, incorporating acid
groups more frequently, increasing the overall acid content,
results in amorphous polymers from this inability to cocrys-
tallize with short polyethylene segments due to increased
hydrogen bonding and decreased diffusional motion. In-
deed, an amorphous polymer is obtained when the acid
content is effectively doubled with more frequent singly
attached groups along the backbone (see Figure 1, polymers
22 and 24). But when the architecture is altered from singly
attached polymer 24 with twice the acid content via geminal
attachment (26) or with benzyl attachment (28), the 20-
methylene run-length still ensures crystallization.
For the acid polymers containing a run-length of 20
methylenes (Figure 7b), a typical experiment after erasing
thermal history results in no recrystallization in the subse-
quent cooling cycle and thus no melting until 72 h have
passed. After 72 h or longer, a reproducible endotherm is
observed on the first heating cycle, indicating that an equi-
librium structure has been achieved (see Supporting In-
formation). The acid endotherms shown in Figure 7b were
acquired after erasing thermal history, slow cooling, anneal-
ing at room temperature for 72 h and heating at 10 °C/min.
Comparing parts a and b of Figure 7, the acid polymer 24
melts at higher temperature with well-resolved endotherms
compared to the ester polymer 17. Although the precise
geminal ester polymer 19 shows more complex behavior
Figure 8. ATR-IR spectra expansion of 20-methylene spaced semicrys-
talline acid polymers.
upon heating, with a glass transition leading to cold crystal-
lization prior to melting, a broad single endotherm is ex-
hibited by the geminal acid polymer 26. Geminal ester
polymer 19 and geminal acid polymer 26 both have en-
dotherms higher than the single and benzyl polymers. Per-
haps this is due to an organized structure lending from
geminal enhancement of chain folding. Also noteworthy,
even though the acid content is doubled, crystallinity is
retained yet less perfect as indicated by the broadened
melting endotherm. In addition, acid polymer 28 again melts
at a higher temperature compared to the ester polymer 21.
Backbone variations associated with crystallinity between
single, geminal and benzyl acid polymers with the same
thermal history as the DSC samples (prior to heating)
were further investigated by ATR-IR (Figure 8). Singlets at
∼718 cm-1 are apparent in all 20-methylene spaced acid
polymers in contrast to the typical orthorhombic PE doublet
that arises from long trans CH2 sequences rocking at
719 cm-1 and sequences of 5 or more CH2 rocking at
730 cm-1 32,33 Singlets at 1468 cm-1 are also apparent in
.
all 20 methylene spaced acid polymers in contrast to the
typical orthorhombic PE doublet associated with methylene
bending at ∼1460 cm-1. The singlet peaks present in all
spectra suggests similar structural features, yet disorganized
compared to orthorhombic PE.34 With the exact identity of
the unit cell remaining unknown from these data, we have
shown a dependency on run-length in these highly interactive
polymers.
Conclusions
Precision protected phosphonic acid ester and deprotected
phosphonic acid polymer families were synthesized with varying
frequency and architecture. The highly interactive acid primary
structures have implications on secondary structure probed by
thermal behavior. Commonalities in thermal behavior between
esters and acids are found in polymers possessing 14 and
20 methylenes between attachment points. The precision acid

Article
Macromolecules, Vol. 43, No. 8, 2010 3695
polymers containing 20 methylenes display PE endotherms
strongly dependent on annealing. Additionally, this run-length
of 20 methylenes ensures reproducible endotherms attributed to
melting, even in polymer structures containing geminal acid
groups or a benzyl acid group. Further analysis by diffraction,
scattering, and microscopic techniques will delineate these crys-
tallinity differences and give a more accurate quantification of
crystallinity than simple comparison to the heat of fusion of
purely orthorhombic PE. Compared to the layered morphology
observed previously with dimerized carboxylic acid groups,12 the
resilient, highly interactive phosphonic acid hydrogen bonds
appear to display higher ordered structures concomitant with
PE crystallization, lending toward model studies and materials
design in particular applications.
11-bromoundecene were stirred in15 mL of dry THF under
argon. After bringing the solution to -78 °C, 0.9 equiv of LDA
was added dropwise over 30 min and stirred for 30 min addi-
tional. The solution was then warmed to 0 °C and stirred for 1 to
2 h until monoalkylation was observed and alkenyl bromide
disappeared by TLC. After bringing the solution back to
-78 °C, 0.9 equiv of 11-bromoundecene was added slowly and
allowed to dissolve. With the solution at -78 °C, 0.9 equiv of
LDA was added dropwise over 30 min and stirred for
30 additional minutes. The solution was then warmed to 0 °C
and stirred for 2 to 3 h until the conversion from monoalkylation
to diene product was no longer observed. The reaction was
quenched by adding ice cold water. This mixture was then
extracted (3 ꢀ 50 mL) with diethyl ether, dried over magnesium
sulfate and concentrated to a colorless oil. Column chromato-
graphy, using 2:1 ethyl acetate:hexane as the eluent, afforded
dialkylation product 1 in 43% recovered yield.
Experimental Section
Materials and Methods. All 1H (300 MHz) and 13C (75 MHz)
solution NMR spectra were recorded on a Varian Associates
Mercury 300 spectrometer. Chemical shifts for 1H and 13C
NMR were referenced to residual signals from CDCl3 (1H =
7.27 ppm and 13C=77.23 ppm). Thin layer chromatography
(TLC) was performed on EMD silica gel-coated (250 μm
thickness) glass plates. Developed TLC plates were stained with
iodine adsorbed on silica to produce a visible signature. Reac-
tion progress and relative purity of crude products were moni-
tored by TLC and 1H NMR.
Molecular weights and molecular weight distributions were
determined by gel permeation chromatography (GPC) using a
Waters Associates GPCV2000 liquid chromatography system
equipped with a differential refractive index detector (DRI) and
an autosampler. These analyses were performed at 40 °C using
two Waters Styragel HR-5E columns (10 μm PD, 7.8 mm ID,
300 mm length) with HPLC grade THF as the mobile phase at a
flow rate of 1.0 mL/minute. Injections were made at
0.05-0.07% w/v sample concentration using a 220.5 μL injec-
tion volume. Retention times were calibrated versus narrow
molecular weight polystyrene standards (Polymer Laboratories;
Amherst, MA).
Infrared spectra were obtained on a Perkin-Elmer Spectrum
One FTIR equipped with a LiTaO3 detector. Samples were
dissolved in chloroform and cast on a KBr disk by slow solvent
evaporation. Because of rather poor solubility, the spectrum of
the deprotected polymer was obtained by means of an ATR
accessory.
Thermogravimetric analysis (TGA) was performed using a
TA Instruments Q5000 using high resolution dynamic resolu-
tion under nitrogen atmosphere. Differential scanning calori-
metry (DSC) was performed using a TA Instruments Q1000 at a
heating rate of 10 °C/min under nitrogen purge. Temperature
calibrations were achieved using indium and freshly distilled
n-octane while the enthalpy calibration was achieved using
indium. All samples were prepared in hermetically sealed pans
(4-7 mg/sample) and were run using an empty pan as a
reference.
Diethyl Undeca-1,10-dien-6-ylphosphonate (1). Column chro-
matography, using 3:1 ethyl acetate:hexane as the eluent,
afforded dialkylation product 1 in 56% recovered yield. 1H
NMR (CDCl3): δ = 1.30 (t, 6H), 1.49 (br, 6H), 1.64-1.75 (br,
4H), 2.03 (q, 4H), 4.07 (p, 4H), 4.92-5.03 (m, 4H), 5.72-5.85
(m, 2H). 13C NMR (CDCl3): δ = 16.74 (3JCP 5.8 Hz), 27.08
(2JCP 9.1 Hz), 27.97, 28.02, 33.98, 36.10 (1JCP 138 Hz), 61.51
(2JCP 6.9 Hz), 114.91, 138.65. 31P NMR (CDCl3, PPh3 re-
ference): δ = 33.99. Anal. Calcd for C15H29O3P: C, 62.48; H
10.14; O, 16.65; P, 10.74. Found: C, 61.98; H, 10.36. HRMS:
calcd for C15H29O3P [(M þ H)þ] = 289.1927; found =
289.1942.
Diethyl Heptadeca-1,16-dien-9-ylphosphonate (2). Column
chromatography, using 5:2 ethyl acetate:hexane as the eluent,
afforded dialkylation product 2 in 50% recovered yield. 1H
NMR (CDCl3): δ = 1.30 (t, 6H), 1.39 (br, 21H), 1.62-1.69 (br,
4H), 2.02 (q, 4H), 4.08 (p, 4H), 4.90-5.00 (m, 4H), 5.73-5.86
(m, 2H). 13C NMR (CDCl3): δ=16.74 (3JCP 5.9 Hz), 27.77 (2JCP
9.3 Hz), 28.43(3JCP 5.9 Hz), 29.08, 29.13, 29.77, 33.98, 36.20
(1JCP 138 Hz), 114.39, 139.31. 31P NMR (CDCl3, PPh3 re-
ference): δ =34.56. Anal. Calcd for C21H41O3P: C, 67.71; H
11.09; O, 12.88; P, 8.31. Found: C, 67.75; H, 11.20. HRMS:
calcd for C21H41O3P [(M þ H)þ]=373.2866; found = 373.2903.
Diethyl Tricosa-1,22-dien-12-ylphosphonate (3). Column
chromatography, using 2:1 ethyl acetate:hexane as the eluent,
afforded dialkylation product 3 in 43% recovered yield. 1H
NMR (CDCl3): δ = 1.26-1.36 (br, 38H), 1.63-1.69 (m, 4H),
1.98-2.06 (q, 4H), 4.07 (p, 4H), 4.89-5.00 (m, 4H), 5.73-5.86
(m, 2H). 13C NMR (CDCl3): δ = 16.72 (3JCP 5.9 Hz), 27.79
(2JCP 9.3 Hz), 28.39(3JCP 3.6 Hz), 29.13, 29.33, 29.63, 29.67,
29.75, 29.91, 34.01, 36.14 (1JCP 138 Hz), 61.46 (2JCP 6.8 Hz),
114.86, 138.59. 31P NMR (CDCl3, PPh3 reference): δ = 34.70;
Anal. Calcd for C27H53O3P: C, 71.01; H 11.70; O, 10.51; P, 6.78.
Found: C, 70.96; H, 11.72. HRMS: calcd for C27H53O3P [(M þ
H)þ] = 457.3805; found = 457.3783.
General Synthesis of Monomer Containing Geminally Substi-
tuted Phosphonic Acid Esters. Again the appropriate alkenyl
halide synthon was used for each monomer. In a flame-dried
3-necked flask equipped with a magnetic stir bar, 75 mL of
DMF was stirred at 0 °C under a constant argon flow. Using a
powder funnel under continued constant argon flow, 2.4 g of
60% NaH powder (100 mmol, 5 equiv) was added to the flask.
Upon resealing the flask, 5 mL (20.2 mmol, 1 equiv), tetraethyl
methylenediphosphonate was added dropwise over 30 min.
After an additional hour of stirring at 0 °C, 9.7 mL (44.4 mmol,
2.2 equiv) of 11-bromoundecene was added dropwise over
30 min. The reaction was allowed to warm to room temperature
over 4 h and then allowed to stir at room temperature overnight.
Reaction progress was monitored by TLC noting the disap-
pearance of starting materials. The reaction was quenched at
0 °C by first diluting the mixture with hexane 75 mL and then
adding 750 mL of deionized water. The reaction mixture was
then extracted (3 ꢀ 75 mL) hexane. After washing the hexane
Synthesis. All materials were purchased from Aldrich and
used as received, unless noted otherwise. Tetrahydrofuran
(THF) was obtained from a MBraun solvent purification
system. Lithium diisopropyl amide (LDA) was prepared prior
to monomer synthesis. Grubbs’ first generation ruthenium
catalyst, bis(tricyclohexylphosphine)benzylidine ruthenium(IV)-
dichloride, was a generous gift from Materia, Inc. Wilkinson’s
rhodium catalyst, RhCl(PPh3)3, was purchased from Strem
Chemical.
General Synthesis of Monomer Containing Single Directly
Attached Phosphonic Acid Ester. The synthesis was previously
reported with the exception of appropriate alkenyl halide syn-
thon choice for each monomer.27 In a flame-dried 3-necked flask
equipped with a magnetic stir bar, 2.2 mL (15 mmol, 1 equiv) of
diethyl methane phosphonate and 3.3 mL (15 mmol, 1 equiv) of

3696 Macromolecules, Vol. 43, No. 8, 2010
Opper et al.
with water, the crude mixture was concentrated to a light
yellow oil.
Tetraethyl Heptadeca-1,16-diene-9,9-diyldiphosphonate (4).
Column chromatography, using 20:1 ethyl acetate:methanol
as the eluent, afforded dialkylation product 4 in 24% recovered
yield.
(d, 2H). 13C NMR (CDCl3): δ = 25.99, 29.14, 33.75, 68.10,
101.36, 107.39, 114.11, 139.20, 139.45, 160.37.
(3,5-Bis(pent-4-enyloxy)phenyl)benzyl Bromide. 1H NMR
(CDCl3): δ = 1.46 (br, 8H), 1.80 (p, 4H), 2.08 (m, 4H),
3.96 (t, 4H), 4.43 (s, 2H), 4.94-5.08 (m, 4H), 5.77-5.93 (m,
2H), 6.40 (m, 1H), 6.54 (d, 2H). 13C NMR (CDCl3): δ = 28.27,
30.11, 33.70, 67.16, 101.42, 107.38, 115.20, 137.67, 139.54,
160.27.
1H NMR (CDCl3): δ = 1.32 (br, 24H), 1.50 (br, 4H), 1.88 (m,
4H), 2.04 (q, 4H), 4.17 (p, 8H), 4.92-5.02 (m, 4H), 5.75-5.88
(m, 2H). 13C NMR (CDCl3): δ = 16.73 (t), 24.42 (t), 29.07,
29.12, 30.29 (t), 34.00 45.99 (t, 1JCP 123 Hz), 62.55 (t), 114.41,
139.39. 31P NMR (CDCl3, PPh3 reference): δ = 26.72. Anal.
Calcd for C25H50O6P2: C, 59.04; H 9.91; O, 18.87; P, 12.18.
Found: C, 59.03; H, 9.92. HRMS: calcd for C25H50O6P2
[(MþH)þ] = 509.3102; found = 509.3116.
Diethyl 3,5-bis(10-undecenyloxy)phenyl) benzyl Phosphonate
(7). In a 50 mL round-bottom flask equipped with a magnetic
stir bar, benzyl bromide was added with 1.3 equiv of triethyl
phosphite. After refluxing the solution for 72 h, the residual
triethyl phosphite was removed under vacuum and the phos-
phonate was obtained in quantitative yield with no further
1
Tetraethyl Tricosa-1,22-diene-12,12-diyldiphosphonate (5).
Column chromatography, using 50:1 ethyl acetate:methanol
as the eluent, afforded dialkylation product 5 in 28% recovered
yield. 1H NMR (CDCl3): δ = 1.27(br, 40H), 1.88 (m, 4H), 2.05
purification necessary. H NMR (CDCl3): δ = 1.26 (br, 30H),
1.67 (p, 4H), 1.98 (m, 4H), 2.92 (d, 2H), 3.82 (t, 4H), 3.95 (m, 4H),
4.94-5.06 (m, 4H), 5.76-5.92 (m, 2H), 6.38 (q, 1H), 6.45-6.47 (t,
2H). 13C NMR (CDCl3): δ = 16.79, 26.42, 29.73, 33.87, 33.99
(1JCP = 137 Hz), 34.15, 62.53, 68.47, 100.51, 108.80, 114.46,
133.79, 139.59, 160.72. 31P NMR (CDCl3, PPh3 reference): δ =
25.49. Anal. Calcd for C33H57O3P: C, 70.18; H 10.17; O, 14.16; P,
5.48. Found: C, 68.06; H, 9.93. HRMS: calcd for C33H57O3P
[(M þ H)þ] = 565.4022; found = 565.4022.
(q, 4H), 4.16 (p, 8H), 4.91-5.02 (m, 4H), 5.74-5.88 (m, 2H). 13
C
NMR (CDCl3): δ = 16.68 (t), 24.40 (t), 29.14, 29.34, 29.53,
1
29.65, 29.75, 30.23 (t), 30.57, 45.96 (t, JCP 123 Hz), 62.46 (t),
114.28, 139.41. 31P NMR (CDCl3, PPh3 reference): δ = 26.74.;
Anal. Calcd for C31H62O6P2: C, 62.81; H 10.54; O, 16.19; P,
10.45. Found: C, 62.21; H, 10.67. HRMS: Calcd for C31H62O6P2
[(M þ H)þ] = 593.4094; found = 593.4049.
Diethyl 3,5-bis(oct-7-enyloxy)benzylphosphonate (6). 1H
NMR (CDCl3): δ = 1.26-1.31 (t, 6H), 1.42 (br, 12H), 1.78
(m, 4H), 2.06 (m, 4H), 3.05-3.14 (d, 2H), 3.91-3.97 (t, 4H),
3.99-4.11 (m, 4H), 4.94-5.06 (m, 4H), 5.76-5.92 (m, 2H),
6.35-6.37 (q, 1H), 6.45-6.47 (t, 2H). 13C NMR (CDCl3): δ =
16.55, 26.03, 28.97, 29.34, 33.84, 34.16 (1JCP = 137 Hz), 62.53,
68.07, 100.23, 108.41, 114.43, 133.59, 139.11, 160.38. 31P NMR
(CDCl3, PPh3 reference): δ = 25.78. Anal. Calcd for C27H45O3P:
C, 67.47; H 9.44; O, 16.64; P, 6.44. Found: C, 66.26; H,
9.51. HRMS: calcd for C27H45O3P [(M þ H)þ] = 481.3077;
found =481.3097.
General Synthesis of Monomer Containing Benzyl-Substituted
Phosphonic Acid Ester. The phosphonic acid ester was prepared
in three steps detailed from alkylation of alcohol with the
appropriate alkenyl halide synthon, to bromide, to phosphonic
acid ester.
3,5-Bis(10-undecenyloxy)phenyl)benzyl Alcohol. In a 200 mL
round-bottom flask equipped with a magnetic stir bar, 2.8 g
(20 mmol, 1 equiv) of 3,5-dihydroxybenzyl alcohol was dis-
solved in 80 mL acetonitrile. To this mixture, 6.91 g (50 mmol,
2.5 equiv) of K2CO3 and 0.83 g (5 mmol, 0.25 mmol) of KI were
added. After partial dissolution due to insolubility at room
temperature, 7.72 mL (46 mmol, 2.3 equiv) of 11-bromounde-
cene was then added and a reflux condenser attached. After
refluxing at 100 °C for 24 h under argon, the reaction was
allowed to cool to room temperature. After filtering residual
K2CO3 and KI and adding deionized water, the mixture was
extracted with (3 ꢀ 50 mL) ethyl acetate. Upon concentrating
the crude mixture to an oil, the crude product was passed
through a plug of silica. Using 1:1 hexane:dichloromethane,
excess alkenyl bromide was removed. Switching to 1:1 hexane:
ethyl acetate led to isolation of product concentrated as a
General Homopolymerization Conditions. In a flame-dried 50
mL round-bottom flask, an exact amount of monomer was
weighed. Using a 400:1 monomer:catalyst ratio (0.25 mol %),
Grubbs’ first generation catalyst was added and mixed into the
monomer while under a blanket of argon. A magnetic stir bar
was placed into the mixture while a Schlenk adapter was fitted to
the round-bottom. After sealing the flask under argon it was
moved to a high vacuum line. The mixture was stirred and slowly
exposed to vacuum over an hour at room temperature. After
stirring for an hour at room temperature under eventual high
vacuum (10-3 Torr), the flask was lowered into a prewarmed
50 °C oil bath for an appropriate number of days allowing
removal of ethylene bubbling through viscous polymer. Poly-
mers were quenched by dissolution of polymer in an 1:10 ethyl
vinyl ether:toluene solution under argon. Upon precipitation
into an appropriate solvent, the polymers were isolated.
Polymerization of Diethyl Undeca-1,10-dien-6-ylphosphonate
(8). After 5 days of polymerization of 0.548 g of monomer 1 with
400:1 Grubbs first generation catalyst, unsaturated polymer 8
was obtained. 1H NMR (CDCl3): δ = 1.30 (t, 6H), 1.44 (br, 4H),
1
yellowish oil in 82% yield. H NMR (CDCl3): δ = 1.27 (br,
24H), 1.68 (m, 4H), 1.95 (m, 4H), 3.83 (m, 4H), 4.51 (d, 2H),
5.02-5.15 (m, 4H), 5.82-5.97 (m, 2H), 6.46 (m, 1H), 6.53 (d,
2H). 13C NMR (CDCl3): δ = 25.97, 29.27, 33.77, 65.31, 68.02,
100.54, 104.94, 114.14, 139.17, 143.16, 160.50.
(3,5-Bis(pent-4-enyloxy)phenyl)benzyl Alcohol. 1H NMR
(CDCl3): δ = 1.75-1.95 (m, 8H), 2.27 (q, 4H), 3.98 (m, 4H),
4.64 (d, 2H), 5.01-5.13 (m, 4H), 5.80-5.96 (m, 2H), 6.46 (m,
1H), 6.53 (d, 2H). 13C NMR (CDCl3): δ = 28.44, 30.11, 65.4,
67.27, 100.65, 105.15, 115.21, 137.80, 143.27, 160.46.
1.64-1.69 (br, 4H), 1.96 (br, 4H), 4.07 (p, 4H), 5.38 (m, 2H). 13
C
NMR (CDCl3): δ = 16.75 (3JCP 5.7 Hz), 27.08 (2JCP 9.1 Hz),
27.88, 28.37, 29.95, 32.90, 36.10 (1JCP 137 Hz), 61.51 (2JCP 6.8
Hz), 129.89, 130.37. 31P NMR (CDCl3, PPh3 reference): δ =
34.42. GPC data (THF vs polystyrene standards): Mw=14100
g/mol; PDI (Mw/Mn) = 1.75.
(3,5-Bis(10-undecenyloxy)phenyl)benzyl Bromide. In a 200 mL
round-bottom flask equipped with a magnetic stir bar, the benzyl
alcohol derivative obtained was dissolved in 40 mL of THF.
Under a blanket of argon, 1.5 equiv of CBr4 was added. Upon
cooling to 0 °C, 1.5equiv of triphenylphosphine was added. After
warming the mixture to room temperature, progress was mon-
itored by TLC. After being stirred overnight, the reaction was
quenched by precipitating the triphenyl phosphine oxides in
pentane, filtering off the solids, and concentrating the remaining
solution. Purification via column chromatography using a 1:1
hexane:dichloromethane solvent system allowed for product
Polymerization of Diethyl Heptadeca-1,16-dien-9-ylphospho-
nate (9). After 6 days of polymerization of 0.973 g pf monomer 2
with 400:1 Grubbs first generation catalyst, unsaturated poly-
mer 9 was obtained. 1H NMR (CDCl3): δ =1.27-1.39 (br,
23H), 1.65 (br, 4H), 1.95 (br, 4H), 4.06 (p, 4H), 5.37 (m, 2H). 13
C
NMR (CDCl3): δ =16.74 (3JCP 5.7 Hz), 27.84 (2JCP 9.1 Hz),
27.88, 28.46, 29.25, 29.87, 32.81, 36.10 (1JCP 137 Hz), 61.49 (2JCP
6.8 Hz), 130.50, 130.05. 31P NMR (CDCl3, PPh3 reference): δ =
34.52. GPC data (THF vs polystyrene standards): Mw = 33800
g/mol; PDI (Mw/Mn) = 1.68.
1
isolation in 67% yield as a yellowish oil. H NMR (CDCl3):
δ = 1.35 (br, 24H), 1.74 (m, 4H), 2.03 (m, 4H), 3.90 (br, 4H), 4.38
(s, 2H), 5.01-5.13 (m, 4H), 5.80-5.96 (m, 2H), 6.36 (m, 1H), 6.51

Article
Polymerization of Diethyl Tricosa-1,22-dien-12-ylphospho-
Macromolecules, Vol. 43, No. 8, 2010 3697
(br, 4H), 4.07 (m, 4H). 13C NMR (CDCl3): δ = 16.70 (3JCP 5.7 Hz),
27.84 (2JCP 9.1 Hz), 28.54, 29.72, 30.00, 36.10 (1JCP 137 Hz),
61.55 (2JCP 6.8 Hz). 31P NMR (CDCl3, PPh3 reference): δ=34.76.
GPC data (THF vs polystyrene standards): Mw=17100 g/mol; PDI
(Mw/Mn) = 1.61.
Hydrogenation of Polymerized Diethyl Heptadeca-1,16-dien-
9-ylphosphonate (16). After 6 days, saturated polymer 16 was
obtained.1H NMR (CDCl3): δ =1.27-1.39 (br, 31H), 1.65 (br,
4H), 4.06 (m, 4H). 13C NMR (CDCl3): δ =16.74 (3JCP 5.7 Hz),
27.84 (2JCP 9.1 Hz), 27.88, 28.46, 29.25, 29.87, 32.81, 36.10 (1JCP
137 Hz), 61.49 (2JCP 6.8 Hz), 130.50, 130.05. 31P NMR (CDCl3,
PPh3 reference): δ = 34.52. GPC data (THF vs polystyrene
standards): Mw=40400 g/mol; PDI (Mw/Mn) = 1.71.
Hydrogenation of Polymerized Diethyl Tricosa-1,22-dien-12-
ylphosphonate (17). After 6 days, saturated polymer 17 was
nate (10). After 6 days of polymerization of 0.860 g pf monomer
3 with 400:1 Grubbs first generation catalyst, unsaturated
1
polymer 10 was obtained. H NMR (CDCl3): δ = 1.27-1.40
(br, 35H), 1.67-1.72 (m, 4H), 1.97 (br, 4H), 4.09 (m, 4H), 5.38
(m, 2H). 13C NMR (CDCl3): δ = 16.73 (3JCP 5.8 Hz), 27.80
(2JCP 9.3 Hz), 28.44(3JCP 3.6 Hz), 29.43, 29.56, 29.68, 29.82,
29.95, 32.84, 36.20 (1JCP 136 Hz), 61.46 (2JCP 6.9 Hz), 130.07,
130.53. 31P NMR (CDCl3, PPh3 reference): δ = 34.85. GPC
data (THF vs polystyrene standards): Mw = 28700 g/mol; PDI
(Mw/Mn) = 1.82.
Polymerization of Tetraethyl Heptadeca-1,16-diene-9,9-diyl-
diphosphonate (11). After 6 days of polymerization of 0.880 g of
monomer 4 with 400:1 Grubbs first generation catalyst, an
additional portion of catalyst was added. After the polymeriza-
tion was quenched after an additional 6 days, unsaturated
1
obtained. H NMR (CDCl3): δ=1.27-1.44 (br, 43H), 1.62-
1.84 (m, 4H), 4.10 (m, 4H). 13C NMR (CDCl3): δ=16.73 (3JCP
5.8 Hz), 27.82 (2JCP 9.3 Hz), 28.44(3JCP 3.6 Hz), 29.69, 29.89,
29.95, 36.20 (1JCP 136 Hz), 61.46 (2JCP 6.9 Hz). 31P NMR
(CDCl3, PPh3 reference): δ=34.71. GPC data (THF vs poly-
styrene standards): Mw=34500 g/mol; PDI (Mw/Mn)=1.93.
Hydrogenation of Polymerized Tetraethyl Heptadeca-1,16-
diene-9,9-diyldiphosphonate (18). After 6 days, saturated poly-
1
polymer 11 was obtained. H NMR (CDCl3): δ = 1.32 (br,
24H), 1.48 (br, 4H), 1.84-1.95 (br, 8H), 4.17 (p, 8H), 5.38 (m,
2H). 13C NMR (CDCl3): δ =16.72 (t), 24.43 (t), 27.46, 29.22,
1
29.32, 29.95, 30.53, 32.85, 46.00 (t, JCP 123 Hz), 62.52 (t),
130.05, 130.52. 31P NMR (CDCl3, PPh3 reference): δ =26.67.
GPC data (THF vs polystyrene standards): Mw = 10500 g/mol;
PDI (Mw/Mn) = 1.78.
1
mer 18 was obtained. H NMR (CDCl3): δ = 1.32 (br, 24H),
Polymerization of Tetraethyl Tricosa-1,22-diene-12,12-diyldi-
phosphonate (12). After 5 days of polymerization of 1.00 g of
monomer 5 with 400:1 Grubbs first generation catalyst, unsa-
turated polymer 12 was obtained. 1H NMR (CDCl3): δ =
1.27-1.34(br, 36H), 1.48 (br, 4H), 1.94 (br, 8H), 4.16 (p, 8H),
5.38 (m, 2H). 13C NMR (CDCl3): δ = 16.68 (t), 24.43 (t), 27.46,
29.48, 29.59, 29.65, 29.75, 30.28 (t), 30.61, 32.86, 45.97 (t, 1JCP
123 Hz), 62.46 (t), 130.06, 130.51. 31P NMR (CDCl3, PPh3 refe-
rence): δ = 30.75. GPC data (THF vs polystyrene standards):
1.48 (br, 4H), 1.84-1.95 (br, 8H), 4.17 (p, 8H), 5.38 (m, 2H). 13
C
NMR (CDCl3): δ =16.72 (t), 24.43 (t), 27.46, 29.22, 29.32,
1
29.95, 30.53, 32.85, 46.00 (t, JCP 123 Hz), 62.52 (t), 130.05,
130.52. 31P NMR (CDCl3, PPh3 reference): δ =26.67. GPC
data (THF vs polystyrene standards): Mw = 11400 g/mol; PDI
(Mw/Mn) = 1.82.
Hydrogenation of Polymerized Tetraethyl tricosa-1,22-diene-
12,12-diyldiphosphonate (19). After 5 days, saturated polymer 19
was obtained. 1H NMR (CDCl3): δ = 1.25-1.34 (br, 44H), 1.48
(br, 4H), 1.85 (br, 4H), 4.16 (p, 8H). 13C NMR (CDCl3): δ =
16.67 (t), 24.41 (t), 29.58, 29.88, 29.95, 30.18 (t), 30.60, 32.12,
M
w = 28900 g/mol; PDI (Mw/Mn) = 1.68.
Polymerization of Diethyl 3,5-Bis(oct-7-enyloxy)benzylphos-
phonate (13). After 5 days of polymerization of 1.02 g monomer
6 with 400:1 Grubbs first generation catalyst, unsaturated
45.97 (t, JCP 123 Hz), 62.47 (t). 31P NMR (CDCl3, PPh3
1
1
reference): δ=30.74. GPC data (THF vs polystyrene standards):
Mw=33400 g/mol; PDI (Mw/Mn) = 1.71.
polymer 13 was obtained. H NMR (CDCl3): δ = 1.26-1.31
(t, 6H), 1.28 (br, 12H), 1.78 (m, 4H), 2.03 (br, 4H), 3.08 (d, 2H),
3.93 (t, 4H), 3.99-4.11 (m, 4H), 5.42 (m, 2H), 6.35-6.37 (m,
1H), 6.45-6.47 (t, 2H). 13C NMR (CDCl3): δ = 16.40, 25.95,
27.18, 28.94, 29.09, 29.25, 29.57, 29.70, 32.53, 34.03 (1JCP = 138
Hz), 62.10, 67.99, 100.10, 108.30, 129.84, 130.31, 133.42, 160.25.
31P NMR (CDCl3, PPh3 reference): δ = 25.79. GPC data (THF
vs polystyrene standards): Mw = 14700 g/mol; PDI (Mw/Mn) =
2.30.
Hydrogenation of Polymerized Diethyl 3,5-Bis(oct-7-enyloxy)-
benzylphosphonate (20). After 5 days, saturated polymer 20 was
obtained. 1H NMR (CDCl3): δ = 1.26-1.31 (br, 26H), 1.78 (m,
4H), 3.08 (d, 2H), 3.93 (t, 4H), 3.99-4.11 (m, 4H), 6.35-6.37 (m,
1H), 6.45-6.47 (t, 2H). 13C NMR (CDCl3): δ = 16.40, 26.30,
29.51, 29.93, 34.03 (1JCP = 138 Hz), 62.35, 68.28, 100.35, 108.52,
133.42, 160.25. 31P NMR (CDCl3, PPh3 reference): δ = 26.09.
GPC data (THF vs polystyrene standards): Mw = 20600 g/mol;
PDI (Mw/Mn) = 1.94.
Polymerization of Diethyl 3,5-Bis(10-undecenyloxy)phenyl)-
benzylphosphonate (14). After 5 days of polymerization of
0.550 g of monomer 7 with 400:1 Grubbs first generation
catalyst, unsaturated polymer 14 was obtained. 1H NMR
(CDCl3): δ = 1.24-1.43 (br, 30H), 1.75 (m, 4H), 1.98 (m,
4H), 2.92 (d, 2H), 3.91 (br, 4H), 4.03 (m, 4H), 5.39 (m, 2H),
6.34 (br, 1H), 6.44 (br, 2H). 13C NMR (CDCl3): δ = 16.79,
26.42, 29.73, 32.27, 34.15 (1JCP = 137 Hz), 62.53, 68.47, 100.51,
108.80, 114.46, 133.79, 139.59, 160.72. 31P NMR (CDCl3, PPh3
reference): δ = 25.93. GPC data (THF vs polystyrene stan-
dards): Mw=15000 g/mol; PDI (Mw/Mn) = 2.07.
Hydrogenation of Polymerized Diethyl 3,5-Bis(10-undecenyl-
oxy)phenyl) benzyl phosphonate (21). After 5 days, saturated
1
polymer 21 was obtained. H NMR (CDCl3): δ = 1.25-1.44
(br, 34H), 1.77 (m, 4H), 2.92 (d, 2H), 3.91 (br, 4H), 4.03 (m, 4H),
6.34 (br, 1H), 6.44 (br, 2H). 13C NMR (CDCl3): δ = 16.65,
22.93, 26.30, 29.51, 29.67, 29.83, 29.98, 32.15, 34.26 (1JCP = 138
Hz), 62.37, 68.27, 100.34, 108.53, 133.62, 160.49. 31P NMR
(CDCl3, PPh3 reference): δ=25.77. GPC data (THF vs poly-
styrene standards): Mw = 16400 g/mol; PDI (Mw/Mn) = 2.23.
General Hydrolysis Procedure. Into a 2-necked Schlenk
round-bottom flask was transferred polymer ester dissolved in
dry dichloromethane. Then the flask was equipped with a stir
bar and septa. After the flask was flushed with argon, 10 equiv of
bromotrimethylsilane was added dropwise by syringe under a
continuous flow of argon. After the reaction was stirred with a
constant flow of argon for 24 h, the residual reactants were
removed under vacuum prior to adding 20 mL of methanol (not
anhydrous). The reaction was allowed to stir with a constant
flow of argon for another 24 h. Upon removal of residual
methanol and trimethylsilyl species, acid polymer was obtained
in quantitative yield (99%) without any purification necessary.
Following methanolysis, the polymer was precipitated from the
sides of the flask with acetone. The precipitated polymer was
General Hydrogenation Conditions. A solution of unsaturated
polymer was dissolved in toluene and degassed by bubbling
a nitrogen purge through the stirred solution for an hour.
Wilkinson’s catalyst [RhCl(PPh3)3] was added to the solution
along with a magnetic stir bar, and the glass sleeve was sealed in
a Parr reactor equipped with a pressure gauge. The reactor was
filled to 700 psi hydrogen gas and purged three times while
stirring, filled to 700 psi hydrogen, and stirred for an appro-
priate number of days. After degassing of the solution, the crude
solution was isolated, and precipitated into an appropriate
solvent.
Hydrogenation of Polymerized Diethyl undeca-1,10-dien-6-
ylphosphonate (15). After 5 days, saturated polymer 15 was
obtained. 1H NMR (CDCl3): δ = 1.26-1.39 (br, 19H), 1.64-1.69

3698 Macromolecules, Vol. 43, No. 8, 2010
Opper et al.
rinsed through an osmotic filter with acetone and dried at 50 °C
for 24 h. See characterization herein and in the Supporting
Information.
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Acknowledgment. We thank the Army Research Office for
funding. Additional funding provided by Alexander von
Humboldt Foundation, the International Max Planck Research
School for Polymer Materials Science, and NSF is appreciated.
Supporting Information Available: Figures showing pro-
tected polymer and deprotected polymer spectra and depro-
tected polymer annealing thermograms. This material is
available free of charge via the Internet at http://pubs.acs.org.
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