NOVEL FUNCTIONAL POLYMERS PREPARED BY RING-OPENING METATHESIS
POLYMERIZATION (ROMP) OF NORBORNENE AND OXANORBORNENE
Abstract:
Monomers and Catalysts:
INTRODUCTION
Ring-opening metathesis polymerization (ROMP) of cycloolefins has evolved as a powerful tool
for synthesis of polymers with superior performance properties.1 Well defined and active
cycloolefin ROMP initiators have been developed based on ruthenium that also exhibit a
favorable functional group tolerance. Examples of such initiators include the first generation
Grubb’s ruthenium catalyst [(PCy3)2Cl2Ru(benzylidene)] (C1: PCy3 = tricyclohexylphosphine)2,
the second generation Grubb’s ruthenium catalyst [(H2IMes)(PCy3)Cl2Ru(benzylidene)] (C2:
H2IMes = N,N-bis(mesityl)-4,5-dihydroimidazol-2-yl)3 and the Umicore M1 initiator, dichloro(3-phenyl-1H-inden-1-ylidene)bis(PCy3)ruthenium(II) (C3: PCy3 = tricyclohexylphosphine)4.
Herein we report the synthesis, characterization, and industrial applications of novel
homopolymers, as well as random, block and alternating copolymers of norbornene and
oxanorbornene and its derivatives catalyzed by the ruthenium based initiators C1, C2 and C3.
RESULTS AND DISCUSSION
The monomers were prepared by
1. (a) Grubbs, R. H. Handbook of Metathesis; Wiley-VCH: Weinheim, 2003; (b) Buchmeiser, M.
R. Chem Rev 2000, 100, 1565–1604; (c) Slugovc, C. Macromol Rapid Commun 2004, 25,
1283–1297.
2. (a) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew Chem Int Ed 1995, 34,
2039–2041; (b) Sanford, M. S.; Love, J. A.; Grubbs, R. H. J Am Chem Soc 2001, 123, 6543–
6554.
3. Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R. H. Tetrahedron Lett 1999, 40, 2247–2250.
4. Ana M. Lozano Vila, Stijn Monsaert, Renata Drozdzak, Stanislaw Wolowiec, Francis
Verpoort; Advanced Synthesis & Catalysis 2009, Volume 351 Issue 16, Pages 2689 - 2701
Materials and methods:
Synthesis of monomers:
Monomer M1:
Materials: Furan (Aldrich) and maleic anhydride (Aldrich) were used as purchased. Dry Et2O
was supplied through Department. The reaction was carried out in a nitrogen atmosphere.
Procedure: Maleic anhydride (98g, 1mol) was weighed in a three-necked 1L round-bottom
flask, equipped with a magnetic stirrer, a dropping funnel and a reflux condenser. The system
was kept under a N2 atmosphere. Et2O (~350 ml) was added through the septum by a syringe.
The mixture was heated to 35°C to dissolve maleic anhydride. When maleic anhydride was
completely dissolved in Et2O, 10% excess of furan (80ml, 1.1mol) was added. The reaction
mixture was stirred at 35°C for 48h until white solid appeared in the flask. The solid was filtered
and washed with copious amounts of Et2O. The product was dried under reduced pressure for
12h at room temperature and then 12h at 33oC (yield 80%). The product was found to be pure
and was used for future reactions without any purification. However, the product can be
recrystallized from Et2O or THF.
Product specification: white solid powder, - soluble in THF, acetone, DMSO and water melting point is 110.4 C - decomposition temperature (retro Diels-Alder reaction) is 150 C
Monomer M2:
Materials: Dicyclopentadiene (Aldrich), dimethyl fumarate (Aldrich) and THF (Fisher) were
used as purchased. The synthesis was carried out in a nitrogen atmosphere.
Procedure: Cracking of dicyclopentadiene (DCPD). Two necked round bottom flask (250ml)
fitted with stirrer bar, an air condenser and a distillation head was filled with DCPD and heated
to 185oC. DCPD cracked at 160oC to produce cyclopentadiene (CPD, b.p.= 40oC). CPD was
collected in a pre-weighed Shlenk immersed in dry ice to prevent fast dimerisation of CPD.
Diels-Alder reaction between CPD and dimethyl fumarate (DMFum). [0061] Dimethyl
fumarate (200.43g, 1.4 mol) was dissolved in THF (1.2L) at 60oC in a round-bottomed flask (2L)
fitted with a dry ice/acetone dropping funnel, condenser, thermometer, and stirrer bar. Freshly
cracked CPD (92.4g, 1.4 mol) was added dropwise with intensive stirring. During the addition of
CPD temperature rose from 60oC up to 70oC. The reaction proceeded for 24hrs at 60oC. The
reaction was stopped and half of the solvent was removed on a rotary evaporator. Then the
reaction mixture was placed in the freezer. White solid product was recovered and dried under
reduced pressure for 24h at 28oC (yield 90%). Note: CPD should be weighed accurately. Excess
of CPD in reaction mixture is dimerised during the reaction to DCPD, which cannot be separated
from product.
Product specification: - white solid powder, - soluble in THF, acetone, CHCl3, hexane and
toluene - melting point is 34.6-35.8 oC - decomposition temperature (retro Diels-Alder reaction)
is 151oC
Monomer M3:
Materials: p-toluenesulphonic acid (Aldrich) and diethyl ether (Fisher) were used as received.
Dry methanol was supplied through Department. Monomer 1 (synthesized as described above).
The reaction was carried out in a nitrogen atmosphere.
Procedure: Monomer 1 (50.46g, 0.3 mol) was placed in two-necked round bottom flask (500ml)
equipped with a condenser and a stirrer bar and dissolved in dry methanol (300 ml) at 90oC for
1h. Then a solution of p-toluenesulphonic acid (0.72g, 3.8·10-3 mol) in dry methanol (5ml) was
added. The reaction mixture was heated at 90oC for 12h. The bulk of solvent was removed on a
rotary evaporator and Et2O was added to precipitate the product. The product was recovered and
dried under reduced pressure for 24h at 40oC (yield 25%).
Product specification: - white solid powder, - soluble in THF, acetone, CHCl3 and water
Monomer M4:
Materials: Fumaryl chloride (Aldrich) and diethyl ether (Fisher) were used as received. Furan
was shaken with NaOH, dried (MgSO4) and distilled under N2. Dry methanol was supplied
through Department. Triethylamine (Fluka) was dried with CaH2, then distilled and collected
over 4 Å molecular sieves. The reaction was carried out in a nitrogen atmosphere.
Procedure: (1.5 ml, 13 mmol) was added dropwise to pre-cooled (0 °C, ice bath) furan (1 ml, 13
mmol). After stirring at 0 °C for 30 min, the solution entirely solidified to give a pale yellow
solid. Anhydrous methanol (5 ml, 0.1 mol) and distilled triethylamine (4.2 ml, 30 mmol) were
dissolved in ether (50 ml) at 10 °C. To this solution, the solid obtained as described above was
added cautiously in small portions and the resulting suspension was stirred for 30 min. Then cold
water (40 ml) was added to give a solution that was extracted with ether (2 x 20 ml). The organic
extracts were combined, washed with water (40 ml) and brine solution (20 ml), dried (MgSO4)
and concentrated in vacuo to give a fluffy solid (pale yellow). It was recrystallized as white
needles from ether in 72% yield.
Product specification: - white solid crystals, - soluble in THF, acetone, CHCl3 and ether
Ring-opening metathesis polymerization (ROMP) \ and copolymerization (ROMCP) in the
presence of Umicore ruthenium initiator (UM)
Materials: Dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine) ruthenium(II)
(Umicore catalyst (UM), Strem), hydroquinone (Aldrich) and hexane (Fisher) were used as
received. THF (Fisher) was deoxygenated before use. Monomer 1, Monomer 2 and Monomer 3
were obtained as described above. The reactions were carried out under a nitrogen atmosphere.
ROMP of Monomer 1 (M1)
Procedure: M1 (1g, 0.006mol) was dissolved in deoxygenated THF (~10ml) and then the
solution of UM (0.056g, 6.02·10-5mol) in THF (2 ml) was added to the solution of M1 (mole
ratio [M]/[Ru] = 100) with constant stirring. The gel was formed during the reaction. The
reaction was stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min.
More THF was added and then the polymer was precipitated into hexane (10-fold excess)
containing hydroquinone (around 0.1g as an inhibitor). The product Polymer 1 was dried under
reduced pressure for 40h at 35°C (yield 98%).
Product specification: [0068] Brown colored gel is not soluble in THF, DMF, hexane, and
water.
ROMP of Monomer 2 (M2)
Procedure: M2 (0.57g, 0.0027 mol) was dissolved in deoxygenated THF (~5ml) and then the
solution of UM (0.0126g, 1.36·10-5mol) in THF (1 ml) was added to the solution of M2 (mole
ratio [M]/[Ru] = 200) with constant stirring. The reaction was stopped after 12h by adding of
vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated into hexane (10fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product Polymer 2 was
dried under reduced pressure for 40h at 35°C (yield 90%).
Product specification: Polymer is quit rubbery and has pale pink color. Soluble in THF,
acetone, CHCl3.
Example 7 ROMP of Monomer 3 (M3)
Procedure: M3 (0.48g, 0.0022 mol) was dissolved in deoxygenated THF (~5ml) and then the
solution of UM (0.0104g, 1.12·10-5mol) in THF (1 ml) was added to the solution of M3 (mole
ratio [M]/[Ru] = 200) with constant stirring. The reaction was stopped after 12h by adding of
vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated into hexane (10fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product Polymer 3 was
dried under reduced pressure for 40h at 35°C (yield 98%).
Product specification: Polymer is quit rubbery and has pale pink color. Soluble in THF,
acetone, CHCl3.
ROMP of Monomer 4 (M4)
Procedure: M3 (0.28g, 0.00123 mol) was dissolved in deoxygenated THF (~5ml) and then the
solution of UM (0.0057g, 6.17·10-6mol) in THF (1 ml) was added to the solution of M4 (mole
ratio [M]/[Ru] = 200) with constant stirring. The reaction was stopped after 12h by adding of
vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated into hexane (10fold excess) containing hydroquinone (around 0.05g as an inhibitor). The product Polymer 4 was
dried under reduced pressure for 40h at 35°C (yield 85%).
Ring-opening metathesis random copolymerization of M2 and M1 [M2]/[M1]/[UM] =
150/50/1.
Procedure: Mixture of M1 (0.039g, 2.38·10-4 mol) and M2 (0.15g, 7.14·10-4 mol) was dissolved
in deoxygenated THF (~5ml) and then the solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7
ml) was added to the solution of monomers mixture with constant stirring. The reaction was
stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer
was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an
inhibitor). The product Copolymer 1 was dried under reduced pressure for 40h at 35°C (yield
89% after second precipitation). 1H NMR shows the content of M1 and M2 in the Copolymer 1
23% and 77%, respectively.
Product specification: Copolymer 1 has pale yellow color. Soluble in THF, acetone, DMF,
DCM and chloroform, soluble in ethanol or methanol if left for a long time.
Ring-opening metathesis random copolymerization of M2 and M1, [M2]/[M1]/[UM] =
100/100/1
Procedure: Mixture of M1 (0.079g, 4.76·10-4 mol) and M2 (0.1g, 4.76·10-4 mol) was dissolved
in deoxygenated THF (~6ml) and then the solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7
ml) was added to the solution of monomers mixture with constant stirring. The reaction was
stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer
was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an
inhibitor). The product Copolymer 2 was dried under reduced pressure for 40h at 35°C (yield
85% after second precipitation). 1H NMR shows the content of M1 and M2 in the Copolymer 2
43% and 57%, respectively.
32
Product specification: Copolymer 2 has pale yellow color. Soluble in THF, acetone and DMF,
soluble in ethanol or methanol if left for a long time.
Ring-opening metathesis random copolymerization of M2 and M1, [M2]/[M1]/[UM] =
50/150/1.
Procedure: Mixture of M1 (0.12g, 7.14·10-4 mol) and M2 (0.05g, 2.38·10-4 mol) was dissolved
in deoxygenated THF (~10ml) and then the solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7
ml) was added to the solution of monomers mixture with constant stirring. The reaction was
stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer
was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an
inhibitor). Received Copolymer 3 is not soluble completely in THF after reprecipitation in to
hexane. The product Copolymer 3 was dried under reduced pressure for 40h at 35°C (yield 86%
after second precipitation). 1H NMR shows the content of M1 and M2 in the Copolymer 3 66%
and 34%, respectively.
Product specification: Copolymer 3 has pale yellow color.
Ring-opening metathesis random copolymerization of M3 and M1, [M3]/[M1]/[UM] =
150/50/1.
Procedure: Mixture of M1 (0.039g, 2.38·10-4 mol) and M3 (0.15g, 7.14·10-4 mol) was dissolved
in deoxygenated THF (~5ml) and then the solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7
ml) was added to the solution of monomers mixture with constant stirring. The reaction was
stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer
was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an
inhibitor). The product Copolymer 4 was dried under reduced pressure for 40h at 35°C (yield
90% after second precipitation). The chemical shifts of two monomer units are overlapping and
hence difficult to define the composition by 1H NMR.
Product specification: Copolymer 4 has pale yellow color. Soluble in THF, DMF, DCM and
chloroform, soluble in ethanol or methanol if left for a long time.
Ring-opening metathesis random copolymerization of M3 and M1, [M3]/[M1]/[UM] =
100/100/1
Procedure: Mixture of M1 (0.079g, 4.76·10-4 mol) and M3 (0.1g, 4.76·10-4 mol) was dissolved
in deoxygenated THF (~6ml) and then the solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7
ml) was added to the solution of monomers mixture with constant stirring. The reaction was
stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer
was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an
inhibitor). The product Copolymer 5 was dried under reduced pressure for 40h at 35°C (yield
93% after second precipitation). The chemical shifts of two monomer units are overlapping and
hence difficult to define the composition by 1H NMR.
Product specification: Copolymer 5 has pale yellow color. Soluble in THF, acetone and DMF,
soluble in ethanol or methanol if left for a long time.
Ring-opening metathesis random copolymerization of M3 and M1, [M3]/[M1]/[UM]=
50/150/1
Procedure: Mixture of M1 (0.12g, 7.14·10-4 mol) and M3 (0.05g, 2.38·10-4 mol) was dissolved
in deoxygenated THF (~10ml) and then the solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7
ml) was added to the solution of monomers mixture with constant stirring. The reaction was
stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer
was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an
inhibitor). Received Copolymer 6 is not soluble completely in THF after reprecipitation in to
hexane. The product Copolymer 6 was dried under reduced pressure for 40h at 35°C (yield 86%
after second precipitation). The chemical shifts of two monomer units are overlapping and hence
difficult to define the composition by 1H NMR.
Product specification: Copolymer 6 has pale yellow color.
Ring-opening metathesis random copolymerization of M4 and M1, [M4]/[M1]/[UM] =
150/50/1
Procedure: Mixture of M1 (0.076g, 3.09·10-4 mol) and M4 (0.196g, 9.26·10-4 mol) was
dissolved in deoxygenated THF (~5ml) and then the solution of UM (0.0057g, 6.17·10-6 mol) in
THF (0.7 ml) was added to the solution of monomers mixture with constant stirring. The reaction
was stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The
polymer was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.05g as
an inhibitor). The product Copolymer 7 was dried under reduced pressure for 40h at 35°C (yield
90% after second precipitation). The chemical shifts of two monomer units are overlapping and
hence difficult to define the composition by 1H NMR.
Product specification: Copolymer 7 has pale yellow color. Soluble in THF, DMF, DCM and
chloroform.
Ring-opening metathesis random copolymerization of M4 and M1, [M4]/[M1]/[UM] =
100/100/1
Procedure: Mixture of M1 (0.138g, 8.34·10-4 mol) and M4 (0.18g, 8.34·10-4 mol) was dissolved
in deoxygenated THF (~6ml) and then the solution of UM (0.0077g, 8.34·10-6 mol) in THF (0.7
ml) was added to the solution of monomers mixture with constant stirring. The reaction was
stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer
was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.05g as an
inhibitor). The product Copolymer 8 was dried under reduced pressure for 40h at 35°C (yield
93% after second precipitation). The chemical shifts of two monomer units are overlapping and
hence difficult to define the composition by 1H NMR. Product specification: Copolymer 8 has
pale yellow color. Soluble in THF, acetone and DMF.
38
Ring-opening metathesis random copolymerization of M4 and M1, [M4]/[M1]/[UM]=
50/150/1
Procedure: Mixture of M1 (0.264g, 0.0016 mol) and M4 (0.112g, 5.3·10-4 mol) was dissolved in
deoxygenated THF (~10ml) and then the solution of UM (0.0098g, 1.06·10-5 mol) in THF (0.7
ml) was added to the solution of monomers mixture with constant stirring. The reaction was
stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer
was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an
inhibitor). Received Copolymer 9 is not soluble completely in THF after reprecipitation in to
hexane. The product Copolymer 9 was dried under reduced pressure for 40h at 35°C (yield 86%
after second precipitation). The chemical shifts of two monomer units are overlapping and hence
difficult to define the composition by 1H NMR.
Product specification: Copolymer 9 has pale yellow color. Soluble in THF, acetone and DMF.
Example 18 Ring-opening metathesis block copolymerization of M2 and M1,
[M2]/[M1]/[UM] = 75/25/1.
Procedure: M2 (0.075g, 3.57·10-4 mol) was dissolved in deoxygenated THF (~5ml) and then the
solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7 ml) was added to the solution of M2 with
constant stirring. The reaction mixture was stirred for 4h and then solution of M1 (0.02g,
1.19·10-4 mol) in THF was added dropwise. The reaction mixture was stirred during for 10h and
then stopped by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was
precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor).
The product Copolymer 10 was dried under reduced pressure for 40h at 35°C (yield 98% after
the second precipitation). 1H NMR shows the content of M1 and M2 in the Copolymer 10 18%
and 82%, respectively.
Product specification Copolymer 10 has pale yellow color. Soluble in THF, DMF, DCM and
chloroform, soluble in ethanol or methanol if left for a long time.
Example 19 Ring-opening metathesis block copolymerization of M2 and M1,
[M2]/[M1]/[UM] = 50/50/1
Procedure: M2 (0.05g, 4.76·10-4 mol) was dissolved in deoxygenated THF (~5ml) and then the
solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7 ml) was added to the solution of M2 with
constant stirring. The reaction mixture was stirred for 4h and then solution of M1 (0.04g,
4.76·10-4 mol) in THF was added dropwise. The reaction mixture was stirred during for 10h and
then stopped by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was
precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor).
The product Copolymer 11 was dried under reduced pressure for 40h at 35°C (yield 92% after
the second precipitation). 1H NMR shows the content of M1 and M2 in the Copolymer 11 18%
and 82%, respectively.
Product specification Copolymer 11 has pale yellow color. Soluble in THF, DMF and acetone.
Soluble in ethanol or methanol if left for a long time.
Ring-opening metathesis block copolymerization of M2 and M1, [M2]/[M1]/[UM]= 25/75/1.
Procedure: M2 (0.025g, 1.19·10-4 mol) was dissolved in deoxygenated THF (~10ml) and then
the solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7 ml) was added to the solution of M2
with constant stirring. The reaction mixture was stirred for 4h and then solution of M1 (0.06g,
3.57·10-4 mol) in THF was added dropwise. The reaction mixture was stirred during for 10h. The
gel was formed during the reaction. The reaction was stopped by adding of vinylethyl ether (0.1
ml) and stirring for 30 min. The polymer was precipitated into hexane (10-fold excess)
containing hydroquinone (around 0.1g as an inhibitor). The product Copolymer 12 was dried
under reduced pressure for 40h at 35°C (yield 89%). 1H NMR shows the content of M1 and M2
in the Copolymer 12 75% and 23%, respectively.
Product specification Copolymer 12 has pale yellow color. Insoluble in THF, DMF, DCM and
chloroform
Ring-opening metathesis block copolymerization of M3 and M1, [M3]/[M1]/[UM] =
75/25/1.
Procedure: M3 (0.075g, 3.57·10-4 mol) was dissolved in deoxygenated THF (~5ml) and then the
solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7 ml) was added to the solution of M3 with
constant stirring. The reaction mixture was stirred for 4h and then solution of M1 (0.02g,
1.19·10-4 mol) in THF was added dropwise. The reaction mixture was stirred during for 10h and
then stopped by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was
precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor).
The product Copolymer 13 was dried under reduced pressure for 40h at 35°C (yield 92% after
the second precipitation). The chemical shifts of two monomer units are overlapping and hence
difficult to define the composition by 1H NMR.
Product specification Copolymer 13 has pale yellow color. Soluble in THF, DMF, DCM and
chloroform, soluble in ethanol or methanol if left for a long time.
Ring-opening metathesis block copolymerization of M3 and M1, [M3]/[M1]/[UM] =
50/50/1.
Procedure: M3 (0.05g, 4.76·10-4 mol) was dissolved in deoxygenated THF (~5ml) and then the
solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7 ml) was added to the solution of M3 with
constant stirring. The reaction mixture was stirred for 4h and then solution of M1 (0.04g,
4.76·10-4 mol) in THF was added dropwise. The reaction mixture was stirred during for 10h and
then stopped by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was
precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor).
The product Copolymer 14 was dried under reduced pressure for 40h at 35°C (yield 96% after
the second precipitation). The chemical shifts of two monomer units are overlapping and hence
difficult to define the composition by 1H NMR. Product specification Copolymer 14 has pale
yellow color. Soluble in THF, DMF, DCM and chloroform, soluble in ethanol or methanol if left
for a long time.
Ring-opening metathesis block copolymerization of M3 and M1, [M3]/[M1]/[UM]= 25/75/1.
Procedure: M3 (0.025g, 1.19·10-4 mol) was dissolved in deoxygenated THF (~10ml) and then
the solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7 ml) was added to the solution of M3
with constant stirring. The reaction mixture was stirred for 4h and then solution of M1 (0.06g,
3.57·10-4 mol) in THF was added dropwise. The reaction mixture was stirred during for 10h. The
gel was formed during the reaction. The reaction was stopped by adding of vinylethyl ether (0.1
ml) and stirring for 30 min. The polymer was precipitated into hexane (10-fold excess)
containing hydroquinone (around 0.1g as an inhibitor). The product Copolymer 15 was dried
under reduced pressure for 40h at 35°C (yield 89%). The chemical shifts of two monomer units
are overlapping and hence difficult to define the composition by 1H NMR. Product
specification Copolymer 15 has pale yellow color. Insoluble in THF, DMF, DCM and
chloroform.
Ring-opening metathesis block copolymerization of M2 and M3, [M2]/[M3]/[UM] =
50/50/1.
Procedure: M2 (0.05g, 4.76·10-4 mol) was dissolved in deoxygenated THF (~5ml) and then the
solution of UM (0.0044g, 4.76·10-6 mol) in THF (0.7 ml) was added to the solution of M2 with
constant stirring. The reaction mixture was stirred for 4h and then solution of M3 (0.05g,
4.76·10-4 mol) in THF was added dropwise. The reaction mixture was stirred during for 10h and
then stopped by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was
precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor).
The product Copolymer 16 was dried under reduced pressure for 40h at 35°C (yield 88% after
the second precipitation). 1H NMR shows the content of M2 and M3 in the Copolymer 13 58%
and 42%, respectively.
Product specification Copolymer 16 has pale yellow color. Soluble in THF, DMF, DCM and
chloroform.
Ring-opening metathesis block copolymerization of M4 and M1, [M3]/[M1]/[UM] =
100/100/1.
Procedure: M4 (0.220g, 1.04·10-3 mol) was dissolved in deoxygenated THF (~5ml) and then the
solution of UM (0.0096g, 1.04·10-5 mol) in THF (0.7 ml) was added to the solution of M4 with
constant stirring. The reaction mixture was stirred for 4h and then solution of M1 (0.172g,
1.04·10-3 mol) in THF was added dropwise. The reaction mixture was stirred during for 10h and
then stopped by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was
precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor).
The product Copolymer 17 was dried under reduced pressure for 40h at 35°C (yield 92% after
the second precipitation). The chemical shifts of two monomer units are overlapping and hence
difficult to define the composition by 1H NMR.
Product specification Copolymer 17 has pale yellow color. Soluble in THF, DMF, DCM and
chloroform.
Ring-opening metathesis block copolymerization of M4 and M1, [M4]/[M1]/[UM] =
50/150/1.
Procedure: M4 (0.083g, 3.95·10-4 mol) was dissolved in deoxygenated THF (~5ml) and then the
solution of UM (0.0073g, 7.9·10-6 mol) in THF (0.7 ml) was added to the solution of M4 with
constant stirring. The reaction mixture was stirred for 4h and then solution of M1 (0.197g,
0.0012 mol) in THF was added dropwise. The reaction mixture was stirred during for 10h and
then stopped by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was
precipitated into hexane (10-fold excess) containing hydroquinone (around 0.05g as an
inhibitor). The product Copolymer 18 was dried under reduced pressure for 40h at 35°C (yield
91% after the second precipitation). The chemical shifts of two monomer units are overlapping
and hence difficult to define the composition by 1H NMR. Product specification Copolymer 18
has pale yellow color. Soluble in THF, DMF, DCM and chloroform, soluble in ethanol or
methanol if left for a long time.
Ring-opening metathesis polymerization (ROMP) and copolymerization (ROMCP) in the
presence of Grubbs ruthenium initiator 1st generation (G1)
Materials for all ROMP and ROMCP reactions in the presence of G1 initiator: Grubbs
ruthenium initiator 1st generation (G1, Aldrich), hydroquinone (Aldrich) and hexane (Fisher)
were used as received. THF (Fisher) was deoxygenated before use. Monomer 1, Monomer 2 and
Monomer 3 were obtained as described above. The reactions were carried out under a nitrogen
atmosphere.
ROMP of Monomer 1 (M1). OOOOOOOOG1, G2 or G2m
THF, RT
m
G1, THF, RT Polymer 5 Monomer 1 Scheme 27 Procedure:
[0091] M1 (2g, 0.012mol) was dissolved
in deoxygenated THF (~20ml) and then the solution of G1 (0.05g, 6.07·10-5mol) in THF (1 ml)
was added to the solution of M1 (mole ratio [M]/[Ru] = 200) with constant stirring. The gel was
formed during the reaction. The reaction was stopped after 12h by adding of vinylethyl ether (0.1
ml) and stirring for 30 min. More THF was added and then the polymer was precipitated into
hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product
Polymer 5 was dried under reduced pressure for 40h at 35°C (yield 95%). Product
specification: Brown colored gel is not soluble in THF, DMF, hexane, and water.
49
Example 28 ROMP of Monomer 2 (M2).
COOMe
CO OM e
G1, THF , RT
MeO OC COOMe
G1, THF, RT
Scheme 28 Polymer 6 Monomer 2 Procedure:
[0092] M2 (0.64g, 0.0031 mol) was dissolved in
deoxygenated THF (~5ml) and then the solution of G1 (0.0126g, 1.53·10-5mol) in THF (1 ml)
was added to the solution of M2 (mole ratio [M]/[Ru] = 200) with constant stirring. The reaction
was stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The
polymer was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g as
an inhibitor). The product Polymer 6 was dried under reduced pressure for 40h at 35°C (yield
95%). Product specification: Polymer is quit rubbery and has pale pink color. Soluble in THF,
acetone, CHCl3. Example 29 ROMP of Monomer 3 (M3).
COOMe
COOMe UM, THF, RT
O
COOMe COOMe
G1, THF, RT
Scheme 29 OMonomer 3 Polymer 7 Procedure:
[0093] M3 (0.53g, 0.0025 mol) was dissolved in
deoxygenated THF (~5ml) and then the solution of G1 (0.0104g, 1.26·10-5mol) in THF (1 ml)
was added to the solution of M3 (mole ratio [M]/[Ru] = 200) with constant stirring. The reaction
was stopped after 12h by adding of vinylethyl ether (0.1 ml) and
50
stirring for 30 min. The polymer was precipitated into hexane (10-fold excess) containing
hydroquinone (around 0.1g as an inhibitor). The product Polymer 7 was dried under reduced
pressure for 40h at 35°C (yield 94%). Product specification: Polymer is quit rubbery and has
pale pink color. Soluble in THF, acetone, CHCl3. Example 30 Ring-opening metathesis
random copolymerization of M2 and M1 [M2]/[M1]/[G1] = 150/50/1.
COOMeCOOMeCOOMeMeOOCOOOOOOOOG2Monomer 1 Monomer 2 Copolymer 19 ,THF, RT, 15h
nm+
G1, THF, RT Scheme 30 Procedure:
[0094] Mixture of M1 (0.044g, 2.67·10-4 mol) and M2 (0.17g,
8.02·10-4 mol) was dissolved in deoxygenated THF (~5ml) and then the solution of G1 (0.0044g,
5.34·10-6 mol) in THF (0.7 ml) was added to the solution of monomers mixture with constant
stirring. The reaction was stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for
30 min. The polymer was precipitated into hexane (10-fold excess) containing hydroquinone
(around 0.1g as an inhibitor). The product Copolymer 19 was dried under reduced pressure for
40h at 35°C (yield 92% after second precipitation). 1H NMR shows the content of M1 and M2 in
the Copolymer 19 21% and 79%, respectively. Product specification: Copolymer 19 has pale
yellow color. Soluble in THF, DMF, DCM and chloroform, soluble in ethanol or methanol if left
for a long time.
51
Example 31 Ring-opening metathesis random copolymerization of M2 and M1,
[M2]/[M1]/[G1] = 100/100/1. COOMeCOOMeCOOMeMeOOCOOOOOOOOG2,THF, RT, 15h
nm+
Procedure: [0095] Mixture of M1
(0.088g, 5.34·10-4 mol) and M2 (0.11g, 5.34·10-4 mol) was dissolved in deoxygenated THF
(~3ml) and then the solution of G1 (0.0044g, 5.34·10-6 mol) in THF (0.7 ml) was added to the
solution of monomers mixture with constant stirring. The reaction was stopped after 12h by
adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated into
hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product
Copolymer 20 was dried under reduced pressure for 40h at 35°C (yield 95% after second
precipitation). 1H NMR shows the content of M1 and M2 in the Copolymer 20 26% and 74%,
respectively. Product specification: Copolymer 20 has pale yellow color. Soluble in THF,
acetone and DMF, soluble in ethanol or methanol if left for a long time.
52
Example 32 Ring-opening metathesis random copolymerization of M2 and M1,
[M2]/[M1]/[G1] = 50/150/1. COOMeCOOMeCOOMeMeOOCOOOOOOOOG2Monomer 1 Monomer 2
G1, THF, RT Monomer 1 Monomer 2 Copolymer 20 Scheme 31
Copolymer 21 ,THF, RT, 15h
nm+
G1, THF, RT Scheme 32 Procedure:
[0096] Mixture of M1 (0.13g, 8.00·10-4 mol) and M2 (0.056g,
2.67·10-4 mol) was dissolved in deoxygenated THF (~3ml) and then the solution of G1 (0.0044g,
5.34·10-6 mol) in THF (0.7 ml) was added to the solution of monomers mixture with constant
stirring. The reaction was stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for
30 min. The polymer was precipitated into hexane (10-fold excess) containing hydroquinone
(around 0.1g as an inhibitor). Received Copolymer 21 is not soluble completely in THF after
reprecipitation in to hexane. The product Copolymer 21 was dried under reduced pressure for
40h at 35°C (yield 94% after second precipitation). 1H NMR shows the content of M1 and M2 in
the Copolymer 21 51% and 49%, respectively. Product specification: Copolymer 21 has pale
yellow color. Soluble in THF, acetone and DMF, soluble in ethanol or methanol if left for a long
time.
53
Example 33 Ring-opening metathesis block copolymerization of M2 and M1,
[M2]/[M1]/[G1] = 75/25/1. COOMeCOOMeCOOMeMeOOCOOOOCOOMeMeOOCOOOOG1,THF, RT, 4h
n
nm
Block
10h
G1, THF, RT, 4h Monomer 1 Monomer 2 Copolymer 22 Scheme 33 Procedure:
[0097] M2 (0.084g,
4.01·10-4 mol) was dissolved in deoxygenated THF (~5ml) and then the solution of G1 (0.0044g,
5.34·10-6 mol) in THF (0.7 ml) was added to the solution of M2 with constant stirring. The
reaction mixture was stirred for 4h and then solution of M1 (0.022g, 1.34·10-4 mol) in THF was
added dropwise. The reaction mixture was stirred during for 10h and then stopped by adding of
vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated into hexane (10fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product Copolymer 22
was dried under reduced pressure for 40h at 35°C (yield 70% after the second precipitation). 1H
NMR shows the content of M1 and M2 in the Copolymer 22 18% and 82%, respectively.
Product specification Copolymer 22 has pale yellow color. Soluble in THF, DMF, DCM and
chloroform, soluble in ethanol or methanol if left for a long time.
54
Example 34 Ring-opening metathesis block copolymerization of M2 and M1,
[M2]/[M1]/[G1] = 50/50/1. COOMeCOOMeCOOMeMeOOCOOOOCOOMeMeOOCOOOOG1,THF, RT, 4h
n
nm
Block
10h
G1, THF, RT, 4h Monomer 1 Monomer 2 Copolymer 23 Scheme 34 Procedure:
[0098] M2 (0.11g,
5.34·10-4 mol) was dissolved in deoxygenated THF (~5ml) and then the solution of G1 (0.0044g,
5.34·10-6 mol) in THF (0.7 ml) was added to the solution of M2 with constant stirring. The
reaction mixture was stirred for 4h and then solution of M1 (0.088g, 5.34·10-4 mol) in THF was
added dropwise. The reaction mixture was stirred during for 10h and then stopped by adding of
vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated into hexane (10fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product Copolymer 23
was dried under reduced pressure for 40h at 35°C (yield 86% after the second precipitation). 1H
NMR shows the content of M1 and M2 in the Copolymer 23 41% and 59%, respectively.
Product specification Copolymer 23 has pale yellow color. Soluble in THF, DMF and acetone.
Soluble in ethanol or methanol if left for a long time.
55
Example 35 Ring-opening metathesis block copolymerization of M2 and M1,
[M2]/[M1]/[G1]= 25/75/1. COOMeCOOMeCOOMeMeOOCOOOOCOOMeMeOOCOOOOG1,THF, RT, 4h
n
nm
Block
10h
G1, THF, RT, 4h Monomer 1 Monomer 2 Copolymer 24 Scheme 35 Procedure:
[0099] M2 (0.028g,
1.34·10-4 mol) was dissolved in deoxygenated THF (~10ml) and then the solution of G1
(0.0044g, 5.34·10-6 mol) in THF (0.7 ml) was added to the solution of M2 with constant stirring.
The reaction mixture was stirred for 4h and then solution of M1 (0.066g, 4.01·10-4 mol) in THF
was added dropwise. The reaction mixture was stirred during for 10h. The gel was formed during
the reaction. The reaction was stopped by adding of vinylethyl ether (0.1 ml) and stirring for 30
min. The polymer was precipitated into hexane (10-fold excess) containing hydroquinone
(around 0.1g as an inhibitor). The product Copolymer 24 was dried under reduced pressure for
40h at 35°C (yield 92%). 1H NMR shows the content of M1 and M2 in the Copolymer 24 66%
and 34%, respectively. Product specification Copolymer 24 has pale yellow color. Insoluble in
THF, DMF, DCM and chloroform
56
Example 36 Ring-opening metathesis block copolymerization of M2 and M3,
[M2]/[M3]/[G1] = 50/50/1. COOMeCOOMeG1,THF,RT
MeOOC COOMe
O
COOMe
COOMe
n 4h
MeOOC COOMe
O
COOMe
COOMe
nm
Monomer 3
10h
G1, THF, Monomer 2 Copolymer 25 Scheme 36 Procedure: [00100] M2 (0.056g, 2.67·10-4 mol) was
dissolved in deoxygenated THF (~5ml) and then the solution of G1 (0.0044g, 5.34·10-6 mol) in
THF (0.7 ml) was added to the solution of M2 with constant stirring. The reaction mixture was
stirred for 4h and then solution of M3 (0.056g, 2.67·10-4 mol) in THF was added dropwise. The
reaction mixture was stirred during for 10h and then stopped by adding of vinylethyl ether (0.1
ml) and stirring for 30 min. The polymer was precipitated into hexane (10-fold excess)
containing hydroquinone (around 0.1g as an inhibitor). The product Copolymer 25 was dried
under reduced pressure for 40h at 35°C (yield 96% after the second precipitation). 1H NMR
shows the content of M2 and M3 in the Copolymer 25 53% and 47%, respectively. Product
specification Copolymer 25 has pale yellow color. Soluble in THF, DMF, DCM and chloroform.
57
Example 37 Ring-opening metathesis polymerization (ROMP) and copolymerization
(ROMCP) in the presence of Grubbs ruthenium initiator 2nd generation (G2) Materials for
all ROMP and ROMCP reactions in the presence of G2 initiator: [00101] Grubbs ruthenium
initiator 2nd generation (G2, Aldrich), hydroquinone (Aldrich) and hexane (Fisher) were used as
received. THF (Fisher) was deoxygenated before use. Monomer 1, Monomer 2 and Monomer 3
were obtained as described above. The reactions were carried out under a nitrogen atmosphere.
ROMP of Monomer 1 (M1). OOOOOOOOG1, G2 or G2m
THF, RT
m
G2, THF, RT Polymer 8 Monomer 1 Scheme 37 Procedure:
[00102] M1 (1g, 0.006mol) was
dissolved in deoxygenated THF (~10ml) and then the solution of G2 (0.051g, 6.02·10-5mol) in
THF (1 ml) was added to the solution of M1 (mole ratio [M]/[Ru] = 100) with constant stirring.
The reaction was stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min.
Polymer 8 was precipitated into hexane (10-fold excess) containing hydroquinone (around 0.1g
as an inhibitor). The product Polymer 8 was dried under reduced pressure for 40h at 35°C (yield
97% after the second re-precipitation). Product specification: Polymer 8 has pale yellow color.
Soluble in THF, DMF and ethanol if left for a long time.
58
Example 38 ROMP of Monomer 2 (M2). COOMeCOOMeG2,THF,RTMeOOCCOOMeScheme 38 Polymer 9
Monomer 2 Procedure: [00103] M2 (0.64g, 0.003 mol) was dissolved in deoxygenated THF
(~5ml) and then the solution of G2 (0.025g, 3.0·10-5mol) in THF (1 ml) was added to the
solution of M2 (mole ratio [M]/[Ru] = 100) with constant stirring. The reaction was stopped after
12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated
into hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product
Polymer 9 was dried under reduced pressure for 40h at 35°C (yield 92%). Product
specification: Polymer 9 is quit rubbery and has pale pink color. Soluble in THF, acetone,
CHCl3.
59
Example 39 ROMP of Monomer 3 (M3). OCOOMeCOOMeG2,THF,RTOCOOMeCOOMeMonomer 3 Scheme
39 Polymer 10 Procedure: [00104] M3 (0.53g, 0.0025 mol) was dissolved in deoxygenated THF
(~5ml) and then the solution of G2 (0.021g, 2.5·10-5mol) in THF (1 ml) was added to the
solution of M3 (mole ratio [M]/[Ru] = 100) with constant stirring. The reaction was stopped after
12h by adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated
into hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product
Polymer 10 was dried under reduced pressure for 40h at 35°C (yield 97%). Product
specification: Polymer 10 is quit rubbery and has pale pink color. Soluble in THF, acetone,
CHCl3.
60
Example 40 Ring-opening metathesis random copolymerization of M2 and M1
[M2]/[M1]/[G2] = 75/25/1. COOMeCOOMeCOOMeMeOOCOOOOOOOOG2Monomer 1 Monomer 2
Copolymer 25 ,THF, RT, 15h
nm+
G2, THF, RT Scheme 40 Procedure:
[00105] Mixture of M1 (0.07g, 4.5·10-4 mol) and M2 (0.19g,
8.85·10-4 mol) was dissolved in deoxygenated THF (~10ml) and then the solution of G2 (0.01g,
1.18·10-5 mol) in THF (0.7 ml) was added to the solution of monomers mixture with constant
stirring. The reaction was stopped after 12h by adding of vinylethyl ether (0.1 ml) and stirring for
30 min. The copolymer was precipitated into hexane (10-fold excess) containing hydroquinone
(around 0.1g as an inhibitor). The product Copolymer 25 was dried under reduced pressure for
40h at 35°C (yield 94% after second precipitation). 1H NMR shows the content of M1 and M2 in
the Copolymer 25 44% and 56%, respectively. Product specification: Copolymer 25 has pale
yellow color. Soluble in THF, DMF, DCM and chloroform, soluble in ethanol or methanol if left
for a long time.
61
Example 41 Ring-opening metathesis random copolymerization of M2 and M1,
[M2]/[M1]/[G2] = 50/50/1. COOMeCOOMeCOOMeMeOOCOOOOOOOOG2,THF, RT, 15h
nm+
Procedure: [00106] Mixture of M1
(0.098g, 5.9·10-4 mol) and M2 (0.125g, 5.9·10-4 mol) was dissolved in deoxygenated THF
(~10ml) and then the solution of G2 (0.01g, 1.18·10-5 mol) in THF (0.7 ml) was added to the
solution of monomers mixture with constant stirring. The reaction was stopped after 12h by
adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The copolymer was precipitated into
hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product
Copolymer 26 was dried under reduced pressure for 40h at 35°C (yield 95% after second
precipitation). 1H NMR shows the content of M1 and M2 in the Copolymer 26 42% and 58%,
respectively. Product specification: Copolymer 26 has pale yellow color. Soluble in THF,
acetone and DMF, soluble in ethanol or methanol if left for a long time.
62
Example 42 Ring-opening metathesis random copolymerization of M2 and M1,
[M2]/[M1]/[G2] = 25/75/1. COOMeCOOMeCOOMeMeOOCOOOOOOOOG2Monomer 1 Monomer 2
G2, THF, RT Monomer 1 Monomer 2 Copolymer 26 Scheme 41
Copolymer 27 ,THF, RT, 15h
nm+
G2, THF, RT Scheme 42 Procedure:
[00107] Mixture of M1 (0.147g, 8.85·10-4 mol) and M2
(0.062g, 2.95·10-4 mol) was dissolved in deoxygenated THF (~5ml) and then the solution of G2
(0.01g, 1.18·10-5 mol) in THF (0.7 ml) was added to the solution of monomers mixture with
constant stirring. The reaction was stopped after 12h by adding of vinylethyl ether (0.1 ml) and
stirring for 30 min. The polymer was precipitated into hexane (10-fold excess) containing
hydroquinone (around 0.1g as an inhibitor). Received Copolymer 27 is not soluble completely in
THF after reprecipitation in to hexane. The product Copolymer 27 was dried under reduced
pressure for 40h at 35°C (yield 98% after second precipitation). 1H NMR shows the content of
M1 and M2 in the Copolymer 27 82% and 18%, respectively. Product specification:
Copolymer 27 has pale yellow color. Soluble in THF, acetone and DMF, soluble in ethanol or
methanol if left for a long time.
63
Example 43 Ring-opening metathesis random copolymerization of M3 and M1,
[M3]/[M1]/[G2] = 75/25/1. Copolymer 28 Monomer 3
OCOOMeCOOMeG2,THF,RTOCOOMeCOOMeOOOO+OOOOnmMonomer 1 Scheme 43 Procedure: [00108] Mixture of
M1 (0.07g, 4.5·10-4 mol) and M3 (0.19g, 8.85·10-4 mol) was dissolved in deoxygenated THF
(~5ml) and then the solution of G2 (0.01g, 1.18·10-5 mol) in THF (0.7 ml) was added to the
solution of monomers mixture with constant stirring. The reaction was stopped after 12h by
adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated into
hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product
Copolymer 28 was dried under reduced pressure for 40h at 35°C (yield 95% after second
precipitation). The chemical shifts of two monomer units are overlapping and hence difficult to
define the composition by 1H NMR Product specification: Copolymer 28 has pale yellow color.
Soluble in THF, DMF, DCM and chloroform, soluble in ethanol or methanol if left for a long
time.
64
Example 44 Ring-opening metathesis random copolymerization of M3 and M1,
[M3]/[M1]/[G2] = 50/50/1. Copolymer 29 Monomer 3
OCOOMeCOOMeG2,THF,RTOCOOMeCOOMeOOOO+OOOOnmMonomer 1 Scheme 44 Procedure: [00109] Mixture of
M1 (0.098g, 5.88·10-4 mol) and M3 (0.124g, 5.88·10-4 mol) was dissolved in deoxygenated THF
(~5ml) and then the solution of G2 (0.01g, 1.17·10-5 mol) in THF (0.7 ml) was added to the
solution of monomers mixture with constant stirring. The reaction was stopped after 12h by
adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated into
hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor). The product
Copolymer 29 was dried under reduced pressure for 40h at 35°C (yield 93% after second
precipitation). The chemical shifts of two monomer units are overlapping and hence difficult to
define the composition by 1H NMR. Product specification: Copolymer 29 has pale yellow
color. Soluble in THF, acetone and DMF, soluble in ethanol or methanol if left for a long time.
65
Example 45 Ring-opening metathesis random copolymerization of M3 and M1,
[M3]/[M1]/[G2]= 25/75/1. Copolymer 30 Monomer 3
OCOOMeCOOMeG2,THF,RTOCOOMeCOOMeOOOO+OOOOnmMonomer 1 Scheme 45 Procedure: [00110] Mixture of
M1 (0.147g, 8.85·10-4 mol) and M3 (0.062g, 2.95·10-4 mol) was dissolved in deoxygenated THF
(~5ml) and then the solution of G2 (0.01g, 1.18·10-5 mol)in THF (0.7 ml) was added to the
solution of monomers mixture with constant stirring. The reaction was stopped after 12h by
adding of vinylethyl ether (0.1 ml) and stirring for 30 min. The polymer was precipitated into
hexane (10-fold excess) containing hydroquinone (around 0.1g as an inhibitor). Received
Copolymer 30 is not soluble completely in THF after reprecipitation in to hexane. The product
Copolymer 30 was dried under reduced pressure for 40h at 35°C (yield 97% after second
precipitation). The chemical shifts of two monomer units are overlapping and hence difficult to
define the composition by 1H NMR. Product specification: Copolymer 30 has pale yellow
color.
66
Example 46 Ring-opening metathesis random copolymerization of M3 and M2,
[M3]/[M2]/[G2] = 50/50/1.
OCOOMeCOOMeCOOMeCOOMeOOMeOOMeOCOOMeMeOOC+Monomer 2 Monomer 3 Scheme 46
G2,THF, RT, 15h
nm
G2, THF, RTCopolymer 31 Procedure: [00111] Mixture of M2 (0.123g, 5.9·10-4 mol) and M3
(0.125g, 5.9·10-4 mol) was dissolved in deoxygenated THF (~6ml) and then the solution of G2
(0.0044g, 4.76·10-6 mol) in THF (0.7 ml) was added to the solution of monomers mixture with
constant stirring. The reaction was stopped after 12h by adding of vinylethyl ether (0.1 ml) and
stirring for 30 min. The Copolymer 31 was precipitated into hexane (10-fold excess) containing
hydroquinone (around 0.1g as an inhibitor). The product Copolymer 31 was dried under reduced
pressure for 40h at 35°C (yield 98% after second precipitation). The chemical shifts of two
monomer units are overlapping and hence difficult to define the composition by 1H NMR.
Product specification: Copolymer 31 has pale yellow color. Soluble in THF, acetone, CHCl3,
CH2Cl2 and DMF. Example 47 Hydrogenation of synthesized homo- and copolymers.
Materials for all hydrogenation reactions: [00112] Polymers and copolymers were
synthesized as described above, p-toluene sulphonylhydrazide (p-TSH, Aldrich), DMF (Aldrich).
67
Hydrogenation of Copolymer 2 MeOOCCOOMeOOOOnmRandompTSHMeOOCCOOMeOOOOnmRandomDMFCopolymer 2 Copolymer 2.1. Scheme 47 Procedure: [00113]
Copolymer 2 (0.2g, 9.52·10-4 mol), p-TSH (0.02g, 1.19·10-4 mol) and DMF (5ml) were placed in
a one necked, round bottomed flask (50ml) fitted with a condenser and stirrer bar and then
heated with stirring to 140oC for 12h. The hot solution was added dropwise to vigorously stirring
methanol (150ml) to give a precipitate, which was isolated by filtration. The resulting polymer
(yield 96%) was a yellowish powder insoluble in DMF. Example 48 Hydrogenation of
Copolymer 5
O
COOMe
COOMe
O
O
OO
nm
Random
p-TSH O
COOMe
COOMe
O
O
OO
nm
Random
DMF
Copolymer 5 Copolymer 5.1. Scheme 48 Procedure:
[00114] Copolymer 5 (0.2g, 9.52·10-4 mol), pTSH (0.02g, 1.19·10-4 mol) and DMF (5ml) were placed in a one necked, round bottomed flask
(50ml) fitted with a condenser and stirrer bar and then heated with stirring to 140oC for 12h. The
hot solution was added dropwise to vigorously stirring
68
methanol (150ml) to give a precipitate, which was isolated by filtration. The resulting polymer
(yield 93%) was a yellowish powder insoluble in DMF. Example 49 Hydrogenation of
Copolymer 8 OOOOCOOMeMeOOCOOOOOOCOOMeMeOOCnmp-TSH, DMF RandomScheme 49
Copolymer 8 Copolymer 8.1. Procedure: [00115] Copolymer 8 (0.2g, 9.52·10-4 mol), p-TSH (0.02g,
1.19·10-4 mol) and DMF (5ml) were placed in a one necked, round bottomed flask (50ml) fitted
with a condenser and stirrer bar and then heated with stirring to 140oC for 12h. The hot solution
was added dropwise to vigorously stirring methanol (150ml) to give a precipitate, which was
isolated by filtration. The resulting polymer (yield 93%) was a yellowish powder insoluble in
DMF.
69
Example 50 Hydrogenation of Copolymer 11 MeOOCCOOMeOOOOnmBlockpTSHMeOOCCOOMeOOOOnmBlockDMFCopolymer 11 Copolymer 11.1. Scheme 50 Procedure: [00116]
Copolymer 11 (0.2g, 9.52·10-4 mol), p-TSH (0.02g, 1.19·10-4 mol) and DMF (5ml) were placed
in a one necked, round bottomed flask (50ml) fitted with a condenser and stirrer bar and then
heated with stirring to 140oC for 12h. The hot solution was added dropwise to vigorously stirring
methanol (150ml) to give a precipitate, which was isolated by filtration. The resulting polymer
(yield 97%) was a yellowish powder insoluble in DMF. Example 51 Hydrogenation of
Copolymer 14
O
COOMe
COOMe
O
O
OO
nm
Block
p-TSH O
COOMe
COOMe
O
O
OO
nm
Block
DMF
Copolymer 14 Copolymer 14.1. Scheme 51 Procedure:
[00117] Copolymer 14 (0.2g, 9.52·10-4 mol),
p-TSH (0.02g, 1.19·10-4 mol) and DMF (5ml) were placed in a one necked, round bottomed flask
70
(50ml) fitted with a condenser and stirrer bar and then heated with stirring to 140oC for 12h. The
hot solution was added dropwise to vigorously stirring methanol (150ml) to give a precipitate,
which was isolated by filtration. The resulting polymer (yield 93%) was a yellowish powder
insoluble in DMF. Example 52 Hydrogenation of Copolymer 17
OOOOCOOMeMeOOCOOOOOOCOOMeMeOOCnmp-TSH, DMF RandomScheme 52 Copolymer 17
Copolymer 17.1. Procedure: [00118] Copolymer 17 (0.2g, 9.52·10-4 mol), p-TSH (0.02g, 1.19·10-4
mol) and DMF (5ml) were placed in a one necked, round bottomed flask (50ml) fitted with a
condenser and stirrer bar and then heated with stirring to 140oC for 12h. The hot solution was
added dropwise to vigorously stirring methanol (150ml) to give a precipitate, which was isolated
by filtration. The resulting polymer (yield 93%) was a yellowish powder insoluble in DMF.
71
Example 53 Hydrogenation of Polymer 8 Polymer 8.1. Scheme 53 OOOOOOOOmptoluenesulfonylhydrazideDMF, 1400CmPolymer 8 Procedure: [00119] Polymer 8 (0.2g, 1.2·10-3
mol), p-TSH (1.12g, 6.02·10-3 mol) and DMF (5ml) were placed in a one necked, round
bottomed flask (50ml) fitted with a condenser and stirrer bar and then heated with stirring to
140oC for 12h. The hot solution was added dropwise to vigorously stirring methanol (150ml) to
give a precipitate, which was isolated by filtration. The resulting polymer (yield 96%) was a
yellowish powder insoluble in DMF. Example 54 Hydrogenation of Copolymer 26
RandomRandom
MeOOC COOMe
O
O
OO
n m p-TSH
MeOOC COOMe
O
O
OO
nm
DMF
Copolymer 26 Copolymer 26.1. Scheme 54 Procedure:
[00120] Copolymer 26 (0.2g, 9.52·10-4 mol),
p-TSH (0.89g, 4.76·10-3 mol) and DMF (5ml) were placed in a one necked, round bottomed flask
(50ml) fitted with a condenser and stirrer bar and then heated with stirring to
72
140oC for 12h. The hot solution was added dropwise to vigorously stirring methanol (150ml) to
give a precipitate, which was isolated by filtration. The resulting polymer (yield 96%) was a
yellowish powder insoluble in DMF. Example 55 Hydrogenation of Copolymer 29
OCOOMeCOOMeOOOOnmRandomp-TSHOCOOMeCOOMeOOOOnmRandomDMFCopolymer 29 Copolymer 29.1.
Scheme 55 Procedure: [00121] Copolymer 29 (0.2g, 9.52·10-4 mol), p-TSH (0.89g, 4.76·10-3 mol)
and DMF (5ml) were placed in a one necked, round bottomed flask (50ml) fitted with a
condenser and stirrer bar and then heated with stirring to 140oC for 12h. The hot solution was
added dropwise to vigorously stirring methanol (150ml) to give a precipitate, which was isolated
by filtration. The resulting polymer (yield 96%) was a yellowish powder insoluble in DMF.
Example 56 Base hydrolysis of synthesized polymers and copolymers Materials for all base
hydrolysis reactions: [00122] NaOH (Aldrich) was used as received. Demineralised water was
supplied from the Department. Copolymer 1 – Copolymer 13 were obtained as described above.
The reactions were carried out on the air.
73
Base hydrolysis of Polymer 4. **On COONaNaOOC**On COOMeMeOOCNaOH, waterPolymer
4.2 Polymer 4 Scheme 56 Procedure: [00123] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water
(5ml) and added to a flask containing solid Polymer 4 (0.17g, 8.09·10-4 mol) and stirred 2h. At
the start the Polymer 4 was floated on the surface but eventually dissolved in the water as the
reaction proceeded with time. The color of the solution during the reaction changed from
colorless to white. Polymer 4.2. was kept in the solution. However, Polymer 4.2 can be
precipitated in ethanol and dried under reduced pressure. Example 57 Base hydrolysis of
Copolymer 1. RandomRandom
MeOOC COOMe
O
O
OO
n m NaOH, water
NaOOC COONa
O
NaOOC COONa
nm
Copolymer 1 Copolymer 1.2. Scheme 57 Procedure:
[00124] NaOH (0.065g, 1.61·10-3 mol) was
dissolved in water (5ml) and added to a flask containing solid Copolymer 1 (0.17g, 8.09·10-4
mol) and stirred 2h. At the start the Copolymer 1 was floated on the surface but eventually
dissolved in the water as the reaction proceeded with time. The
74
color of the solution during the reaction changed from colorless to greenish. Copolymer 1.2. was
kept in the solution. However, Copolymer 1.2. can be precipitated in ethanol and dried under
reduced pressure. Example 58 Base hydrolysis of Copolymer 2.
MeOOCCOOMeOOOOnmRandomNaOH,waterNaOOCCOONaONaOOCCOONanmRandomCopolymer 2 Copolymer 2.2.
Scheme 58 Procedure: [00125] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml) and
added to a flask containing solid Copolymer 2 (0.17g, 8.09·10-4 mol) and stirred 2h. At the start
the Copolymer 2 was floated on the surface but eventually dissolved in the water as the reaction
proceeded with time. The color of the solution during the reaction changed from colorless to
greenish. Copolymer 2.2. was kept in the solution. However, Copolymer 2.2. can be precipitated
in ethanol and dried under reduced pressure.
75
Example 59 Base hydrolysis of Copolymer 3.
MeOOCCOOMeOOOOnmRandomNaOH,waterNaOOCCOONaONaOOCCOONanmRandomCopolymer 3 Copolymer 3.2.
Scheme 59 Procedure: [00126] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml) and
added to a flask containing solid Copolymer 3 (0.17g, 8.09·10-4 mol) and stirred 2h. At the start
the Copolymer 3 was floated on the surface but eventually dissolved in the water as the reaction
proceeded with time. The color of the solution during the reaction changed from colorless to
greenish. Copolymer 3.2. was kept in the solution. However, Copolymer 3.2. can be precipitated
in ethanol and dried under reduced pressure (yield 98% after precipitation). Example 60 Base
hydrolysis of Copolymer 4. Copolymer 4 Copolymer 4.2.
O
COOMe
COOMe
O
O
OO
nm
Random
NaOH, water O
COONa
COONa
O
NaOOC COONa
nm
Random
Scheme 60 Procedure:
[00127] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml) and
added to a flask containing solid Copolymer 4 (0.17g, 8.09·10-4 mol) and
76
stirred 2h. At the start the Copolymer 4 was floated on the surface but eventually dissolved in the
water as the reaction proceeded with time. The color of the solution during the reaction changed
from colorless to greenish. Copolymer 4.2. was kept in the solution. However, Copolymer 4.2.
can be precipitated in ethanol and dried under reduced pressure. Example 61 Base hydrolysis of
Copolymer 5. OCOOMeCOOMeOOOOnmRandomNaOH,waterOCOONaCOONaONaOOCCOONanmRandomCopolymer
5 Copolymer 5.2. Scheme 61 Procedure: [00128] NaOH (0.065g, 1.61·10-3 mol) was dissolved in
water (5ml) and added to a flask containing solid Copolymer 5 (0.17g, 8.09·10-4 mol) and stirred
2h. At the start the Copolymer 5 was floated on the surface but eventually dissolved in the water
as the reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 5.2. was kept in the solution. However, Copolymer 5.2. can be
precipitated in ethanol and dried under reduced pressure.
77
Example 62 Base hydrolysis of Copolymer 6.
OCOOMeCOOMeOOOOnmRandomNaOH,waterOCOONaCOONaONaOOCCOONanmRandomCopolymer 6 Copolymer
6.2. Scheme 62 Procedure: [00129] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 6 (0.17g, 8.09·10-4 mol) and stirred 2h. At the
start the Copolymer 6 was floated on the surface but eventually dissolved in the water as the
reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 6.2. was kept in the solution. However, Copolymer 6.2. can be
precipitated in ethanol and dried under reduced pressure. Example 63 Base hydrolysis of
Copolymer 7.
OO
OO
COOMe MeOOC
O
OO
COONa NaOOC
COONa NaOOC
nm
Random
NaOH, water
nm
Random
Copolymer 7 Scheme 63 Copolymer 7.2. Procedure:
[00130] NaOH (0.065g, 1.61·10-3 mol) was
dissolved in water (5ml) and added to a flask containing solid Copolymer 7 (0.17g, 8.09·10-4
mol) and stirred 2h. At the start the Copolymer 7 was floated on the surface but eventually
dissolved in the water as the reaction proceeded with time. The
78
color of the solution during the reaction changed from colorless to greenish. Copolymer 7.2. was
kept in the solution. However, Copolymer 7.2. can be precipitated in ethanol and dried under
reduced pressure. Example 64 Base hydrolysis of Copolymer 8.
OOOOCOOMeMeOOCOOOCOONaNaOOCCOONaNaOOCnmRandomNaOH, waternmRandom Copolymer 8
Scheme 64 Copolymer 8.2. Procedure:
[00131] NaOH (0.065g, 1.61·10-3 mol) was dissolved in
water (5ml) and added to a flask containing solid Copolymer 8 (0.17g, 8.09·10-4 mol) and stirred
2h. At the start the Copolymer 8 was floated on the surface but eventually dissolved in the water
as the reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 8.2. was kept in the solution. However, Copolymer 8.2. can be
precipitated in ethanol and dried under reduced pressure.
79
Base hydrolysis of Copolymer 9. Example 65
OOOOCOOMeMeOOCOOOCOONaNaOOCCOONaNaOOCnmRandomNaOH, waternmRandomCopolymer 9
Scheme 65 Copolymer 9.2. Procedure:
[00132] NaOH (0.065g, 1.61·10-3 mol) was dissolved in
water (5ml) and added to a flask containing solid Copolymer 9 (0.17g, 8.09·10-4 mol) and stirred
2h. At the start the Copolymer 9 was floated on the surface but eventually dissolved in the water
as the reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 9.2. was kept in the solution. However, Copolymer 9.2. can be
precipitated in ethanol and dried under reduced pressure. Example 66 Base hydrolysis of
Copolymer 10. Procedure: [00133] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 10 (0.17g, 8.09·10-4 mol) and stirred 10h. At the
start the Copolymer 10 was floated on the surface, then formed a gel but eventually dissolved in
the water as the reaction proceeded BlockBlock
NaOH, water
NaOOC COONa
O
NaOOC COONa
nm
MeOOC COOMe
O
O
OO
nm
Copolymer 10 Scheme 66 Copolymer 10.2.
80
with time. The color of the solution during the reaction changed from colorless to greenish.
Copolymer 10.2. was kept in the solution. However, Copolymer 10.2. can be precipitated in
ethanol and dried under reduced pressure. Example 67 Base hydrolysis of Copolymer 11.
MeOOCCOOMeOOOOnmBlockNaOH,waterNaOOCCOONaONaOOCCOONanmBlockCopolymer 11 Scheme 67
Copolymer 11.2. Procedure: [00134] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 11 (0.17g, 8.09·10-4 mol) and stirred 10h. At the
start the Copolymer 11 was floated on the surface, then formed a gel but eventually dissolved in
the water as the reaction proceeded with time. The color of the solution during the reaction
changed from colorless to greenish. Copolymer 11.2 was kept in the solution. However,
Copolymer 11.2. can be precipitated in ethanol and dried under reduced pressure.
81
O
Example 68 Base hydrolysis of Copolymer 12.
MeOOCCOOMeOOOOnmBlockNaOH,waterNaOOCCOONaONaOOCCOONanmBlockCopolymer 12 Scheme 68
Copolymer 12.2. Procedure: [00135] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 12 (0.17g, 8.09·10-4 mol) and stirred 10h. At the
start the Copolymer 12 was floated on the surface, then formed a gel but eventually dissolved in
the water as the reaction proceeded with time. The color of the solution during the reaction
changed from colorless to greenish. Copolymer 12.2. was kept in the solution. However,
Copolymer 12.2. can be precipitated in ethanol and dried under reduced pressure.
Example 69 Base hydrolysis of Copolymer 13.
Copolymer 13 Copolymer 13.2. Scheme 69 Procedure:
[00136] NaOH (0.065g, 1.61·10-3 mol) was
dissolved in water (5ml) and added to a flask containing solid Copolymer 13 (0.17g, 8.09·10-4
mol) and
82
stirred 10h. At the start the Copolymer 13 was floated on the surface, then formed a gel but
eventually dissolved in the water as the reaction proceeded with time. The color of the solution
during the reaction changed from colorless to greenish. Copolymer 13.2. was kept in the
solution. However, Copolymer 13.2. can be precipitated in ethanol and dried under reduced
pressure.
Example 70 Base hydrolysis of Copolymer 14.
OCOOMeCOOMeOOOOnmBlockNaOH,waterOCOONaCOONaONaOOCCOONanmBlockCopolymer
Scheme 70 Procedure:
14 Copolymer 14.2.
[00137] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml) and
added to a flask containing solid Copolymer 14 (0.17g, 8.09·10-4 mol) and stirred 10h. At the
start the Copolymer 14 was floated on the surface, then formed a gel but eventually dissolved in
the water as the reaction proceeded with time. The color of the solution during the reaction
changed from colorless to greenish. Copolymer 14.2. was kept in the solution. However,
Copolymer 14.2. can be precipitated in ethanol and dried under reduced pressure.
83
Example 71 Base hydrolysis of Copolymer 15.
OCOOMeCOOMeOOOOnmBlockNaOH,waterOCOONaCOONaONaOOCCOONanmBlockCopolymer
15 Copolymer 15.2.
Scheme 71 Procedure:
[00138] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml) and
added to a flask containing solid Copolymer 15 (0.17g, 8.09·10-4 mol) and stirred 10h. At the
start the Copolymer 15 was floated on the surface, then formed a gel but eventually dissolved in
the water as the reaction proceeded with time. The color of the solution during the reaction
changed from colorless to greenish. Copolymer 15.2. was kept in the solution. However,
Copolymer 15.2. can be precipitated in ethanol and dried under reduced pressure.
Example 72 Base hydrolysis of Copolymer 17.
Copolymer 16 Scheme 72 Copolymer 16.2. Procedure: [00139] NaOH (0.065g, 1.61·10-3 mol) was
dissolved in water (5ml) and added to a flask containing solid Copolymer 16 (0.17g, 8.09·10-4
mol) and stirred 2h. At the start the Copolymer 16 was floated on the surface but
84
eventually dissolved in the water as the reaction proceeded with time. The color of the solution
during the reaction changed from colorless to greenish. Copolymer 16.2. was kept in the
solution. However, Copolymer 16.2. can be precipitated in ethanol and dried under reduced
pressure.
Example 73 Base hydrolysis of Copolymer 18.
OOOOCOOMeMeOOCOOOCOONaNaOOCCOONaNaOOCnmBlockNaOH, waternmBlock Copolymer 17
Scheme 73 Copolymer 17.2. Procedure:
[00140] NaOH (0.065g, 1.61·10-3 mol) was dissolved in
water (5ml) and added to a flask containing solid Copolymer 17 (0.17g, 8.09·10-4 mol) and
stirred 2h. At the start the Copolymer 17 was floated on the surface but eventually dissolved in
the water as the reaction proceeded with time. The color of the solution during the reaction
changed from colorless to greenish. Copolymer 17.2. was kept in the solution. However,
Copolymer 17.2. can be precipitated in ethanol and dried under reduced pressure.
85
Example 74 Base hydrolysis of Copolymer 19.
MeOOCCOOMeOOOOnmRandomNaOH,waterNaOOCCOONaONaOOCCOONanmRandomCopolymer 19 Copolymer
19.2. Scheme 74 Procedure: [00141] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 19 (0.17g, 8.09·10-4 mol) and stirred 2h. At the
start the Copolymer 19 was floated on the surface but eventually dissolved in the water as the
reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 19.2. was kept in the solution. However, Copolymer 19.2. can
be precipitated in ethanol and dried under reduced pressure. Example 75 Base hydrolysis of
Copolymer 20. MeOOC COOMe
O
O
OO
nm
Random
NaOH, water
NaOOC COONa
O
NaOOC COONa
nm
Random
Copolymer 20 Copolymer 20.2. Scheme 75 Procedure:
[00142] NaOH (0.065g, 1.61·10-3 mol) was
dissolved in water (5ml) and added to a flask containing solid Copolymer 20 (0.17g, 8.09·10-4
mol) and stirred 2h. At the start the Copolymer 20 was floated on the surface but
86
eventually dissolved in the water as the reaction proceeded with time. The color of the solution
during the reaction changed from colorless to greenish. Copolymer 20.2. was kept in the
solution. However, Copolymer 20.2. could be precipitated in ethanol and dried under reduced
pressure. Example 76 Base hydrolysis of Copolymer 21.
MeOOCCOOMeOOOOnmRandomNaOH,waterNaOOCCOONaONaOOCCOONanmRandomCopolymer 21 Copolymer
21.2. Scheme 76 Procedure: [00143] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 21 (0.17g, 8.09·10-4 mol) and stirred 2h. At the
start the Copolymer 21 was floated on the surface but eventually dissolved in the water as the
reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 21.2. was kept in the solution. However, Copolymer 21.2. can
be precipitated in ethanol and dried under reduced pressure (yield 98% after precipitation).
87
Example 77 Base hydrolysis of Copolymer 22.
MeOOCCOOMeOOOOnmBlockNaOH,waterNaOOCCOONaONaOOCCOONanmBlockCopolymer 22 Scheme 77
Copolymer 22.2. Procedure: [00144] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 22 (0.17g, 8.09·10-4 mol) and stirred 10h. At the
start the Copolymer 22 was floated on the surface, then formed a gel but eventually dissolved in
the water as the reaction proceeded with time. The color of the solution during the reaction
changed from colorless to greenish. Copolymer 22.1. was kept in the solution. However,
Copolymer 22.1. can be precipitated in ethanol and dried under reduced pressure.
Example 78 Base hydrolysis of Copolymer 23.
MeOOC COOMe
O
O
OO
nm
Block
NaOH, water
NaOOC COONa
O
NaOOC COONa
nm
Block
Copolymer 23 Scheme 78 Copolymer 23.2. Procedure:
[00145] NaOH (0.065g, 1.61·10-3 mol) was
dissolved in water (5ml) and added to a flask containing solid Copolymer 23 (0.17g, 8.09·10-4
mol) and
88
stirred 10h. At the start the Copolymer 23 was floated on the surface, then formed a gel but
eventually dissolved in the water as the reaction proceeded with time. The color of the solution
during the reaction changed from colorless to greenish. Copolymer 23.2. was kept in the
solution. However, Copolymer 23.2. can be precipitated in ethanol and dried under reduced
pressure.
Example 79 Base hydrolysis of Copolymer 24.
MeOOCCOOMeOOOOnmBlockNaOH,waterNaOOCCOONaONaOOCCOONanmBlockCopolymer 24 Scheme 79
Copolymer 24.2. Procedure: [00146] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 24 (0.17g, 8.09·10-4 mol) and stirred 10h. At the
start the Copolymer 24 was floated on the surface, then formed a gel but eventually dissolved in
the water as the reaction proceeded with time. The color of the solution during the reaction
changed from colorless to greenish. Copolymer 24.2. was kept in the solution. However,
Copolymer 24.2. can be precipitated in ethanol and dried under reduced pressure.
89
Example 80 Base hydrolysis of Polymer 8. OOOOOOOONaNaOmm-+-+Scheme 80 Polymer 8
Polymer 8.2. Procedure: [00147] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml) and
added to a flask containing solid Polymer 8 (0.17g, 8.09·10-4 mol) and stirred 10h. At the start
the Polymer 8 was floated on the surface, then formed a gel but eventually dissolved in the water
as the reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Polymer 8.2. was kept in the solution. However, Copolymer 8.2. can be
precipitated in ethanol and dried under reduced pressure. Example 81 Base hydrolysis of
Copolymer 25. RandomRandom
MeOOC COOMe
O
O
OO
n m NaOH, water
NaOOC COONa
O
NaOOC COONa
nm
Copolymer 215 Copolymer 25.2. Scheme 81 Procedure:
[00148] NaOH (0.065g, 1.61·10-3 mol) was
dissolved in water (5ml) and added to a flask containing solid Copolymer 25 (0.17g, 8.09·10-4
mol) and stirred 2h. At the start the Copolymer 25 was floated on the surface but eventually
dissolved in the water as the reaction proceeded with time. The
90
color of the solution during the reaction changed from colorless to greenish. Copolymer 25.2.
was kept in the solution. However, Copolymer 25.2. can be precipitated in ethanol and dried
under reduced pressure.
Example 82 Base hydrolysis of Copolymer 26.
MeOOCCOOMeOOOOnmRandomNaOH,waterNaOOCCOONaONaOOCCOONanmRandomCopolymer 26 Copolymer
26.2. Scheme 82 Procedure: [00149] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 26 (0.17g, 8.09·10-4 mol) and stirred 2h. At the
start the Copolymer 26 was floated on the surface but eventually dissolved in the water as the
reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 26.2. was kept in the solution. However, Copolymer 26.2. can
be precipitated in ethanol and dried under reduced pressure.
91
Example 83 Base hydrolysis of Copolymer 27.
MeOOCCOOMeOOOOnmRandomNaOH,waterNaOOCCOONaONaOOCCOONanmRandomCopolymer 27 Copolymer
27.2. Scheme 83 Procedure: [00150] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 27 (0.17g, 8.09·10-4 mol) and stirred 2h. At the
start the Copolymer 27 was floated on the surface but eventually dissolved in the water as the
reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 27.2. was kept in the solution. However, Copolymer 27.2. can
be precipitated in ethanol and dried under reduced pressure (yield 98% after precipitation).
Example 84 Base hydrolysis of Copolymer 29. O O
O
COOMe MeOOC
O
O
COONa NaOOC
COONa NaOOC
nm
Random
NaOH, water
nm
Random
Copolymer 29 Scheme 84 Copolymer 29.2. Procedure:
[00151] NaOH (0.065g, 1.61·10-3 mol) was
dissolved in water (5ml) and added to a flask containing solid Copolymer 29 (0.17g, 8.09·10-4
mol) and stirred 2h. At the start the Copolymer 29 was floated on the surface but
92
eventually dissolved in the water as the reaction proceeded with time. The color of the solution
during the reaction changed from colorless to greenish. Copolymer 29.2. was kept in the
solution. However, Copolymer 29.2. can be precipitated in ethanol and dried under reduced
pressure (yield 98% after precipitation).
Example 85 Base hydrolysis of Copolymer 2.1.
MeOOCCOOMeOOOOnmRandomNaOH,waterNaOOCCOONaONaOOCCOONanmRandomCopolymer 2.1. Copolymer
2.3. Scheme 85 Procedure: [00152] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 2.1. (0.17g, 8.09·10-4 mol) and stirred 2h. At the
start the Copolymer 2.1. was floated on the surface but eventually dissolved in the water as the
reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 2.3. was kept in the solution. However, Copolymer 2.3. can be
precipitated in ethanol and dried under reduced pressure.
93
Example 86 Base hydrolysis of Copolymer 5.1.
OCOOMeCOOMeOOOOnmRandomNaOH,waterOCOONaCOONaONaOOCCOONanmRandomCopolymer 5.1. Copolymer
5.3. Scheme 86 Procedure: [00153] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 5.1. (0.17g, 8.09·10-4 mol) and stirred 2h. At the
start the Copolymer 5.1. was floated on the surface but eventually dissolved in the water as the
reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 5.3. was kept in the solution. However, Copolymer 5.3. can be
precipitated in ethanol and dried under reduced pressure. Example 87 Base hydrolysis of
Copolymer 11.1. Procedure:
MeOOC COOMe
O
O
OO
nm
Block
NaOH, water
NaOOC COONa
O
NaOOC COONa
nm
Block
Copolymer 11.1. Copolymer 11.3. Scheme 87 [00154]
NaOH (0.065g, 1.61·10-3 mol) was dissolved in
water (5ml) and added to a flask containing solid Copolymer 11.1. (0.17g, 8.09·10-4 mol) and
stirred 2h. At the start the Copolymer 11.1. was floated on the surface
94
but eventually dissolved in the water as the reaction proceeded with time. The color of the
solution during the reaction changed from colorless to greenish. Copolymer 11.3. was kept in the
solution. However, Copolymer 11.3. can be precipitated in ethanol and dried under reduced
pressure. Example 88 Base hydrolysis of Copolymer 14.1.
OCOOMeCOOMeOOOOnmBlockNaOH,waterOCOONaCOONaONaOOCCOONanmBlockCopolymer 14.1 Copolymer
14.3. Scheme 88 Procedure: [00155] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Copolymer 14.1. (0.17g, 8.09·10-4 mol) and stirred 2h. At
the start the Copolymer 14.1. was floated on the surface but eventually dissolved in the water as
the reaction proceeded with time. The color of the solution during the reaction changed from
colorless to greenish. Copolymer 14.3. was kept in the solution. However, Copolymer 14.3. can
be precipitated in ethanol and dried under reduced pressure.
95
Example 89 Base hydrolysis of Polymer 7.1. Scheme 89 OOOOOOOONaNaOmm-+-+Polymer
8.1. Polymer 8.3. Procedure: [00156] NaOH (0.065g, 1.61·10-3 mol) was dissolved in water (5ml)
and added to a flask containing solid Polymer 8.1. (0.17g, 8.09·10-4 mol) and stirred 10h. At the
start the Polymer 8.1. was floated on the surface, then formed a gel but eventually dissolved in
the water as the reaction proceeded with time. The color of the solution during the reaction
changed from colorless to greenish. Polymer 8.3. was kept in the solution. However, Polymer
8.3. can be precipitated in ethanol and dried under reduced pressure. [00157] While a number of
embodiments of this invention have been represented, it is apparent that the basic construction
can be altered to provide other embodiments that utilize the invention without departing from the
spirit and scope of the invention. All such modifications and variations are intended to be
included within the scope of the invention as defined in the appended claims rather than the
specific embodiments that have been presented by way of example.