ARTICLE
WWW.POLYMERCHEMISTRY.ORG
Synthesis of 3,6,9-Trioxaundecanedioic Acid Divinyl
Ester (DEVE)
2.19 (m, 4H, 2 ꢄ CH2AC¼¼O), 1.67–1.55 (m, 4H, 2 ꢄ CH2);
13C NMR (50 MHz, CDCl3, d, ppm): 173.0 (C¼¼O), 132.9
(Carom), 129.2 (Carom), 129.1 (Cipso), 127.3 (Carom), 63.7
(OACH2), 33.7 (CH2AC¼¼O), 25.4 (CH2), 24.2 (CH2).
Pd(OAc)2 (0.75 g, 3.34 mmol), KOH (0.38 g, 6.79 mmol), and
500 ppm of hydroquinone as inhibitor were added to a
stirred solution of 3,6,9-trioxaundecanedioic acid (15.1 g,
68.7 mmol) in a large excess of vinyl acetate (175 g). The
reaction mixture was heated to 60 ꢁC for 48 h under argon
atmosphere. The cooled solution was diluted with ethyl ace-
tate and extracted with water. The organic layer was dried
over sodium sulfate and concentrated. The product was puri-
fied by kugelrohr distillation at 140 ꢁC and 0.3 mbar, yield-
ing 6.2 g of DEVE as a colorless liquid.
Synthesis of Hexanedioic Acid Divinyl Ester (4VE)
To a stirred solution of 2 (0.65 g, 1.27 mmol) in THF (5 mL)
cooled in an ice bath, a 30% aqueous solution of H2O2 (0.45
g, 13.2 mmol) was added dropwise during 5 min keeping
ꢁ
the temperature at 0 C for additional 30 min. Then, the mix-
ture was stirred at room temperature for 12 h. The reaction
mixture was diluted with CHCl3 (20 mL) and washed with
water (15 mL) and brine (15 mL). The organic layer was
dried over sodium sulfate and concentrated. The crude prod-
uct was dissolved in CHCl3 (15 mL), diisopropyl amine (0.50
g, 4.94 mmol) was added to the solution, and the reaction
mixture was refluxed for 12 h. The cooled reaction mixture
was concentrated, and the residue was purified by column
chromatography (silica gel, petroleum ether/ethyl acetate,
5:1) to afford 0.15 g of 4VE as a colorless liquid.
Yield 33%. 1H NMR (200 MHz, CDCl3, d, ppm): 7.26 (dd, 3J
¼ 13.9 Hz, 3J ¼ 6.3 Hz, 2H, 2 ꢄ CH¼¼CH2), 4.89 (dd, 3J ¼
13.9 Hz, 2J ¼ 1.4 Hz, 2H, 2 ꢄ CH¼¼CHH), 4.60 (dd, 3J ¼ 6.3
Hz, 2J ¼ 1.6 Hz, 2H, 2 ꢄ CH¼¼CHH), 4.21 (s, 4H, 2 ꢄ
CH2AC¼¼O), 3.80–3.64 (m, 8H, 2 ꢄ OACH2ACH2AO), 13C
NMR (50 MHz, CDCl3, d, ppm): 167.7 (C¼¼O), 140.5
(CH¼¼CH2), 98.5 (CH¼¼CH2), 71.0 (CH2), 70.7 (CH2), 68.2
(CH2); IR (ATR, cmꢀ1): 2932, 2882, 1768, 1649, 1240, 1181,
1112, 949, 875; GC–MS (m/z): 253, 207, 191, 129, 87.
Yield 60%. 1H NMR (200 MHz, CDCl3, d, ppm): 7.26 (dd, 3J
¼ 13.9 Hz, 3J ¼ 6.3 Hz, 2H, 2 ꢄ ACH¼¼CH2), 4.86 (dd, 3J ¼
2
3
14.1 Hz; J ¼ 1.4 Hz, 2H, 2 ꢄ ACH¼¼CHH), 4.55 (dd, J ¼ 6.3
Synthesis of 2-(Phenylseleno)ethanol (1)
2
Hz, J ¼ 1.6 Hz, 2H, 2 ꢄ ACH¼¼CHH), 2.48–2.33 (m, 4H, 2 ꢄ
To a stirred solution of diphenyl diselenide (8.00 g, 25.6
ACH2AC¼¼O), 1.79–1.62 (m, 4H, 2 ꢄ CH2); 13C NMR (50
MHz, CDCl3, d, ppm): 170.1 (C¼¼O), 141.0 (ACH¼¼CH2), 97.6
(ACH¼¼CH2), 33.3 (ACH2AC¼¼O), 23.8 (CH2).
ꢁ
mmol) in anhydrous ethanol (50 mL) cooled to 0 C, a solu-
tion of NaBH4 (2.92 g, 77.3 mmol) in anhydrous ethanol (50
mL) was added in small portions during 10 min under argon.
After discoloration of the solution, 2-chloroethanol (1.77 g,
Photo-Differential Scanning Calorimetry
ꢁ
51.6 mmol) was added dropwise at 0 C during 15 min. Then
Photo-DSC experiments were conducted on
a modified
the mixture was refluxed for 3 h, cooled to room temperature,
and filtered. The filtrate was concentrated under reduced
pressure. The residue was dissolved in ethyl acetate (100 mL)
and extracted with 1 M HCl solution (50 mL). The organic
layer was dried over sodium sulfate, filtered, and concentrated
under reduced pressure. The residue was purified by column
chromatography (silica gel, petroleum ether/ethyl acetate,
4:1) to afford 8.6 g of compound 1 as a yellowish oil.
Netzsch DSC 204 F1 Phoenix. The measurements were carried
R
out using 5 wt % of IrgacureV 819 as photoinitiator at 25 C
ꢁ
under nitrogen atmosphere. Photoreactivity of the monomers
was tested by weighing about 10 mg of the sample with an
accuracy of 60.1 mg into an aluminum DSC pan, which was
subsequently placed in the DSC chamber. The samples were
purged with nitrogen for 5 min and irradiated with a filtered
R
UV light (280–500 nm) from a double light guide (OmniCureV
2000) attached to the top of the DSC unit with a light inten-
sity of 3 W cmꢀ2 at the exit of the light guide. The samples
were exposed to the light for at least 10 min, and the heat
flow was recorded as a function of time. The double bond
conversion (DBC) was calculated according to eq 1.
1
Yield 83%. H NMR (200 MHz, CDCl3, d, ppm): 7.59–7.46 (m,
3
2H, Harom), 7.32–7.22 (m, 3H, Harom), 3.76 (t, J ¼ 6.3 Hz, 2H,
3
OACH2), 3.08 (t, J ¼ 6.3 Hz, 2H, SeACH2), 2.34 (s, 1H, OH).
Synthesis of Hexanedioic Acid 2-(phenylseleno)Ethyl
Ester (2)
M DHP
EDC.HCl (1.77 g, 9.23 mmol), 4-dimethylaminopyridine (0.19
g, 1.57 mmol), and hexanedioic acid (0.50 g, 3.42 mmol)
were added consecutively to a stirred solution of 1 (1.62 g,
8.03 mmol) in DMF (15 mL). The reaction mixture was
stirred for 16 h at room temperature. Afterward, the solution
was diluted with ethyl acetate (50 mL) and washed with 1
M HCl (2 ꢄ 25 mL). The organic layer was dried over
Na2SO4 and concentrated under reduced pressure. The crude
product was purified by column chromatography (silica gel,
petroleum ether/ethyl acetate, 4:1) to afford 1.1 g of com-
pound 2 as a colorless oil.
DBC ¼
(1)
2 DH0;P
where M is the molecular weight of the monomer in g
molꢀ1, DHP is the heat of polymerization expressed by peak
area in J gꢀ1, and DH0,P is the theoretical heat of polymeriza-
tion set to 87.8 kJ molꢀ1 for vinyl esters,10 80 kJ molꢀ1 for
acrylates,20 and 60 kJ molꢀ1 for methacrylates.20 The factor
of 2 in the denominator is due to two double bonds per
molecule.
The rate of polymerization Rp was determined from eq 2.
1
Yield 63%. H NMR (200 MHz, CDCl3, d, ppm): 7.59–7.41 (m,
h ꢅ q
3
4H, Harom), 7.33–7.18 (m, 6H, Harom), 4.29 (t, J ¼ 7.2 Hz, 4H,
RP ¼
(2)
2 ꢄ OACH2), 3.07 (t, 3J ¼ 7.1 Hz, 4H, 2 ꢄ SeACH2), 2.33–
DH0;P
4932
JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY 2011, 49, 4927–4934