This application discloses linear methacrylic ABC triblock polymers in which the composition of each of the three blocks is different and wherein at least one of the blocks is hydrophobic and at least one of the blocks is hydrophilic.

BACKGROUND OF THE INVENTION 
This application discloses a linear methacrylic ABC triblock polymer, 
having at least one hydrophobic block and one hydrophilic block, in which 
the composition of each of the three blocks is different. 
A variety of ABC triblock polymers, in which the chemical constitution of 
each polymeric block differs from the other two, have been described in 
the literature. Generally, they have been prepared by anionic 
polymerization. The ABC triblock polymers of the art have been found to be 
useful as elastomeric materials, for example in design of automobile 
bumpers. Some of these ABC triblock polymers contain a hydrophilic block 
but, of these, none are prepared exclusively with methacrylates. 
Int. Application No. PCT/Fr90/00514, published on Jan. 24, 1991 as WO 
91/00874 (same as European Patent Application EP 408429, Jan. 16, 1991), 
discloses triblock ABC copolymers wherein A and C can be an acrylic, vinyl 
aromatic, methacrylic, or maleimide block, where B is an acrylic, vinyl 
aromatic or methacrylic block, and where at least one of A and C is 
selected from a different class from that of the B block. Thus, all three 
blocks cannot be methacrylic. 
U.S. Pat. No. 4,417,034, which is incorporated herein by reference, covers 
the GTP process of preparing block polymers generically; the composition 
claim is to "living" (silyl ketene acetal-ended) polymers, not the 
"quenched" block polymers of this invention. 
D. Y. Sogah, W. R. Hertler, O. W. Webster, G. M. Cohen, Macromolecules 
1987, 20, 1473 discloses an ABC triblock polymer (without a hydrophilic 
block), poly(methyl methacrylate-b-butyl methacrylate-b-allyl 
methacrylate). 
G. Reiss, M. Schlienger, S. Marti, J. Macromol. Sci.-Phys. 1980, B17, 355 
discloses a ternary blend of two homopolymers, poly(styrene) and 
poly(methyl methacrylate) and an ABC triblock polymer, 
poly(styrene-b-isoprene-b-methyl methacrylate). 
G. S. Fielding-Russell, P. S. Pillai, Polymer 1977, 18, 859 discloses an 
ABC triblock polymer with a hydrophilic block, 
poly(styrene-b-butadiene-b-2-vinyl pyridine hydrochloride). 
H. Ohnuma; T. Shimohira; H. Tanisugi; I. Kudose; T. Kotaka Bull. Inst. 
Chem. Res., Kyoto Univ. 1988, 66 (3), 283-296. Morphological studies of 
ABC triblock butadiene-styrene-4-vinylpyridine and quaternized polymers. 
R. Comeau et al., Nucl. Med. Biol. 1990, 321-329 describe "Conjugation of a 
Monoclonal Antibody with a DTPA Modified Random Copolymer of Hydroxyethyl 
Methylacrylate and Methyl Methacrylate". 
SUMMARY OF THE INVENTION 
Linear methacrylic ABC triblock polymers in which the composition of each 
of the three blocks is different and which has at least one hydrophophilic 
block and at least one hydrophobic block are disclosed. Preferably, the 
"B" block of the methacrylic ABC triblock polymer does not contain a 
significant amount of the components of the "A" and "C" blocks. Each block 
may, optionally, contain a low level of one or more monomers that have a 
specific type of functional group, e.g. acid or base. These optional 
functional groups may differ from the functional groups on the block. 
An example of the methacrylic ABC triblock polymer disclosed is where the A 
and C blocks are hydrophilic and the B block is hydrophobic or where the B 
block is hydrophilic and the A and C blocks are hydrophobic. Another is 
where two or all three of the blocks are mutually immiscible. The ABC 
polymers of the present invention may be produced by sequential 
polymerization of three different methacrylates or combinations of 
methacrylates using a living polymerization method such as anionic 
polymerization or group transfer polymerization.

DETAILED DESCRIPTION OF THE INVENTION 
Group transfer polymerization of acrylic monomers is a particularly useful 
method for producing ABC triblock polymers, especially from methacrylates. 
Although anionic polymerization can also be used to prepare ABC triblock 
polymers of methacrylates, the extremely low temperature constraints 
render the anionic process less attractive commercially than group 
transfer polymerization (GTP). Also, certain functional groups tolerated 
by GTP methodology are not tolerated during anionic polymerization, for 
example, but not limited to, primary and/or secondary amines, epoxides and 
alkyl halides. Anionic polymerization methods are described in M. Morton, 
Anionic Polymerization; Principles and Practices, Academic Press, N.Y., 
1983 and J. E. McGrath, Ed., "Anionic Polymerization: Kinetics, Mechanism 
and Synthesis", American Chemical Society, Washington, D.C., 1981, ACS 
Symposium Series No. 166. 
Each of the A, B, and C blocks of the triblock polymers of the invention 
must contain at least three units of monomer and each of the blocks may be 
a linear methacrylic homopolymer or linear methacrylic random copolymer. 
Each block can contain from 3 to 90 weight percent of the total polymer 
weight. 
The unique and useful properties of ABC triblock polymers described herein 
are achieved when the three blocks are dissimilar in nature. It is 
particularly important that the B (center) block differ from the A and C 
(end) blocks in properties, such as hydrophilicity, stiffness, glass 
transition temperature, or polarity. Thus, while the B block may be a 
methacrylic copolymer, it must not contain significant amounts of the 
monomer components of both the A and C blocks. In many of the ABC triblock 
polymers of the Examples, property differences of the blocks can be 
enhanced by, for example, conversion of a methacrylic acid block to the 
corresponding alkali metal salt, or conversion of a dimethylaminoethyl 
methacrylate block to the corresponding hydrochloride or hydrogen 
phosphate salt. Examples of triblock polymers that can be converted to 
alkali metal salts are poly(methacrylic acid-b-2-phenylethyl 
methacrylate-b-n-butyl methacrylate), poly(methacrylic 
acid-b-2-phenylethyl methacrylate-b-ethoxytriethylene glycol 
methacrylate), poly(methacrylic acid-b-2-phenylethyl 
methacrylate-b-methoxypolyethylene glycol methacrylate) and 
poly(methacrylic acid-co-methyl methacrylate-b-2-phenylethyl 
methacrylate-b-ethoxytriethylene glycol methacrylate), 
poly-.omega.-2-.beta.-hydroxyethyl isobutyrate(methoxypolyethylene glycol 
400 methacrylate)-b-2-phenylethyl methacrylate-b-ethoxytriethylene glycol 
methacrylate), poly(methacrylic acid-b-2-phenylethyl 
methacrylate-b-2-hydroxyethyl methacrylate), poly(methacrylic 
acid-b-2-phenylethyl methacrylate-b-2-ethoxyethyl methacrylate), 
poly(methacrylic acid-b-benzyl methacrylate-co-methyl 
methacrylate-b-ethoxytriethylene glycol methacrylate), and 
poly(methacrylic acid-b-benzyl methacrylate-b-ethoxytriethylene glycol 
methacrylate). 
Poly(2-dimethylaminoethyl methacrylate-co-methyl 
methacrylate-b-2-phenylethyl methacrylate-b-ethoxytriethylene glycol 
methacrylate), poly(2-dimethylaminoethyl methacrylate-co-methyl 
methacrylate-b-2-phenylethyl methacrylate-co-methacrylic 
acid-b-ethoxytriethylene glycol methacrylate) and 
poly(2-dimethylaminoethyl methacrylate-b-2-phenylethyl 
methacrylate-b-ethoxytriethylene glycol methacrylate) can be converted to 
their salts with a mineral acid. 
Additional examples of monomers which may be used to construct ABC triblock 
polymers of the invention are methyl methacrylate, ethyl methacrylate, 
2-ethylhexyl methacrylate, isobornyl methacrylate, benzyl methacrylate, 
1-ethoxy-1-propyl methacrylate, glycidyl methacrylate, 
2-trimethylsilyoxyethyl methacrylate (which may be "deprotected" after 
polymerization to form 2-hydroxyethyl methacrylate), 2,2,2-trifluoroethyl 
methacrylate, 4-(tetrahydro-2-pyranyloxy)benzyl methacrylate (which may be 
deprotected after polymerization to 4-hydroxy-benzyl methacrylate), lauryl 
methacrylate, ethoxytriethylene glycol methacrylate, butoxyethyl 
methacrylate, methoxyethoxyethyl methacrylate, sorbyl methacrylate, 
2-acetoxyethyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl 
methacrylate, octyl methacrylate, methoxypolyethylene glycol methacrylate, 
ethoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate (which may be 
deprotected after polymerization to form methacrylic acid), t-butyl 
methacrylate (which may be deprotected after polymerization to form 
methacrylic acid) and 2-dimethylaminoethyl methacrylate. 
Each block may contain a small amount of a monomer with a functional group 
such as carboxylic acid, amine, alcohol or epoxide, for specific chemical 
bonding at interfaces. (See Example 7 which has 3 COOH functional groups 
in the B block.) 
Preferred triblock polymers include poly(methacrylic acid-b-2-phenylethyl 
methacrylate-co-2-dimethylaminoethyl methacrylate-b-ethoxytriethylene 
glycol methacrylate), poly(methoxypolyethylene glycol 
methacrylate-b-2-phenylethyl methacrylate-b-ethoxytriethylene glycol 
methacrylate), poly(methacrylic acid-b-methyl 
methacrylate-b-2-dimethylaminoethyl methacrylate) and 
poly(2-dimethylaminoethyl methacrylate)-b-2-phenylethyl 
methacrylate-b-methacrylic acid. 
ABC triblock polymers of the present invention are useful for surface 
modification. ABC triblock polymers of the invention may be designed to be 
active at air-liquid interfaces, solid-solid interfaces, liquid-liquid, 
and liquid-solid interfaces. For example, certain triblock polymers are 
useful for modification of biological surfaces. ABC triblock polymers may 
also be used for modification of pigment surfaces which can result in 
stable dispersions. Triblock polymers also provide excellent dispersing 
agents for pigments in organic media, aqueous media, or mixed 
aqueous-organic media. Thus, poly(methacrylic acid-b-2-phenylethyl 
methacrylate-b-ethoxytriethylene glycol methacrylate), after 
neutralization of the methacrylic acid units with potassium hydroxide, is 
an excellent dispersant for carbon black in water or in water containing 
organic cosolvents. The interfacial activity of certain ABC triblock 
polymers of this invention also enables them to be used as compatibilizers 
for polymer blends and stabilizers for dispersion of fluids. 
EXAMPLES 
Example 1 
Preparation of poly(methacrylic acid [56mol %]-b-2-phenylethyl methacrylate 
[22 mol %]-b-n-butyl methacrylate [22 mol %]) 
A solution of 3.48 g (4.04 mL, 20 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene, 1.0 mL of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF), and 0.8 g (1.0 
mL, 6 mmol) of bis(dimethylamino)-methylsilane in 250 mL of THF was 
allowed to stand for 10 min. Then a mixture of 44.5 g (43.6 mL, 261 mmol) 
of 2-tetrahydropyranyl methacrylate (purified by passage over a column of 
basic alumina under argon) and 0.8 g (1.0 mL, 6 mmol) of 
bis(dimethylamino)methylsilane was begun. During the course of the 
addition the temperature of the reaction mixture rose to 51.degree. C. 
After all of the mixture had been added, and the temperature began to 
fall, the addition of a mixture of 19.6 g (19.4 mL, 103 mmol) of 
2-phenylethyl methacrylate (purified by passage over a column of basic 
alumina under argon), and 0.8 g (1.0 mL, 6 mmol) of 
bis(dimethylamino)methylsilane was begun. During the addition the 
temperature rose to 56.degree. C. When the addition was complete and the 
temperature began to fall, a mixture of 14.7 g (16.4 mL, 103 mmol) of 
n-butyl methacrylate (purified by passage over a column of basic alumina 
under argon), and 0.8 g (1.0 mL, 6 mmol) of bis(dimethylamino)methylsilane 
was added dropwise from an addition funnel. During the addition the 
temperature rose to 57.degree. C. Analysis of an aliquot of the solution 
by .sup.1 H nmr showed that there was no residual monomer present. After 
addition of 15 mL of methanol to quench the reaction, precipitation in 
methanol followed by drying of the precipitate under reduced pressure gave 
42.8 g of poly(tetrahydropyranyl methacrylate [56 mol %]-b- 2-phenylethyl 
methacrylate [22 mol %]-b-n-butyl methacrylate [22 mol%]). Analysis by gel 
permeation chromatography (GPC) showed M.sub.n =4310, M.sub.w =4500, 
M.sub.w /M.sub.n =1.05. The polymer was heated in a vacuum oven at 
130.degree. C. for 20 hr to decompose the tetrahydropyranyl ester groups, 
giving 30 g of poly(methacrylic acid [56 mol %]-b-2-phenylethyl 
methacrylate [22 mol %]-b-n-butyl methacrylate [22 mol%]). Analysis of the 
product by .sup.1 H NMR showed that there was no tetrahydropyranyl ester 
present. 
EXAMPLE 2 
Preparation of poly(methacrylic acid [56 mol %]-b-n-butyl methacrylate [22 
mol %]-b-2-phenylethyl methacrylate [22 mol %]) 
A solution of 3.53 g (4.1 mL, 20 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene, 1.0 mL of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF), and 0.8 g (1.0 
mL, 6 mmol) of bis(dimethylamino)-methylsilane in 250 mL of THF was 
allowed to stand for 10 min. Then a mixture of 44.5 g (43.6 mL, 261 mmol) 
of 2-tetrahydropyranyl methacrylate (purified by passage over a column of 
basic alumina under argon) and 0.8 g (1.0 mL, 6 mmol) of 
bis(dimethylamino)methylsilane was begun. During the course of the 
addition the temperature of the reaction mixture rose to 50.degree. C. 
After all of the mixture had been added, and the temperature began to 
fall, a mixture of 14.7 g (16.4 mL, 103 mmol) of n-butyl methacrylate 
(purified by passage over a column of basic alumina under argon), and 0.8 
g (1.0 mL, 6 mmol) of bis(dimethylamino)methylsilane was added dropwise 
from an addition funnel. During the addition the temperature rose from 
49.degree. C. to 55.degree. C. When the addition was complete and the 
temperature began to fall, the addition of a mixture of 19.6 g (19.4 mL, 
103 mmol) of 2-phenylethyl methacrylate (purified by passage over a column 
of basic alumina under argon), and 0.8 g (1.0 mL, 6 mmol) of 
bis(dimethylamino)methylsilane was begun. During the addition the 
temperature rose from 54.degree. C. to 57.degree. C. Analysis of an 
aliquot of the solution by .sup.1 H nmr showed that there was no residual 
monomer present. After addition of 15 mL of methanol to quench the 
reaction, precipitation in methanol followed by drying of the precipitate 
under reduced pressure gave 41.5 g of poly(tetrahydropyranyl methacrylate 
[56 mol%]-b-n-butyl methacrylate [22 mol %]-b-2-phenylethyl methacrylate 
[22 mol %]). Analysis by GPC showed M.sub.n =4600, M.sub.w =4850, M.sub.w 
/M.sub.n =1.06. The polymer was heated in a vacuum oven at 130.degree. C. 
for 20 hr to decompose the tetrahydropyranyl ester groups, giving 29 g of 
poly(methacrylic acid [56 mol %]-b-n-butyl methacrylate [22 mol 
%]-b-2-phenylethyl methacrylate [22 mol %]). Analysis of the product by 
.sup.1 H NMR showed that there was no tetrahydropyranyl ester present. 
EXAMPLE 3 
Preparation of poly(methacrylic acid [57 mol %]-b-2-phenylethyl 
methacrylate [13 mol %]-b-n-butyl methacrylate [30 mol %]) 
A solution of 1.95 g (2.26 mL, 11.2 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene, 0.5 mL of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF), and 0.8 g (1.0 
mL, 6 mmol) of bis(dimethylamino)-methylsilane in 120 mL of THF was 
allowed to stand for 10 min. Then a mixture of 11.1 g (12.4 mL, 78 mmol) 
of n-butyl methacrylate (purified by passage over a column of basic 
alumina under argon), and 0.8 g (1.0 mL, 6 mmol) of 
bis(dimethylamino)methylsilane was added dropwise from an addition funnel. 
During the course of the addition the temperature of the reaction mixture 
rose to 38.degree. C. After all of the mixture had been added, and the 
temperature began to fall, the addition of a mixture of 6.4 g (6.3 mL, 33 
mmol) of 2-phenylethyl methacrylate (purified by passage over a column of 
basic alumina under argon), and 0.8 g (1.0 mL, 6 mmol) of 
bis(dimethylamino)methylsilane was begun. During the addition the 
temperature rose from 36.5.degree. C. to 41.degree. C. When the addition 
was complete and the temperature began to fall, a mixture of 24.7 g (24.2 
mL, 145 mmol) of 2-tetrahydropyranyl methacrylate (purified by passage 
over a column of basic alumina under argon) and 0.8 g (1.0 mL, 6 mmol) of 
bis(dimethylamino)methylsilane was begun. During the addition the 
temperature rose from 40.degree. C. to 59.degree. C. Analysis of an 
aliquot of the solution by .sup.1 H nmr showed that there was no residual 
monomer present. After addition of 15 mL of methanol to quench the 
reaction, precipitation in methanol followed by drying of the precipitate 
under reduced pressure gave 34.7 g of poly(tetrahydropyranyl methacrylate 
[57 mol %]-b-2-phenylethyl methacrylate [13 mol %]-b-n-butyl methacrylate 
[30 mol%]). The polymer was heated in a vacuum oven at 138.degree. C. for 
2.5 days to decompose the tetrahydropyranyl ester groups, giving 23.7 g of 
poly(methacrylic acid [57 mol%]-b-2-phenylethyl methacrylate [13 mol 
%]-b-n-butyl methacrylate [30 mol %]). Analysis of the product by .sup.1 H 
NMR showed that there was no tetrahydropyranyl ester present. 
EXAMPLE 4 
Preparation of poly(methacrylic acid [57 mol %]-b-2-phenylethyl methacrylic 
[26 mol %]-b-ethoxytriethylene glycol methacrylic [17 mol %]) 
To a solution of 2.96 g (3.43 mL, 17 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene and 0.5 mL of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF) in 40 mL of THF 
was added dropwise 35.0 g (39.7 mL, 261 mmol) of trimethylsilyl 
methacrylate. During the course of the addition the temperature of the 
reaction mixture rose slowly to 33.degree. C. To increase the rate of 
polymerization, an additional 0.5 mL of tetrabutylammonium biacetate 
hexahydrate (0.04 M in THF) was added. After all of the monomer had been 
added, the temperature slowly rose to 47.degree. C. during 1 hr. When the 
temperature began to fall, the addition of 19.4 g (19.2 mL, 102 mmol) of 
2-phenylethyl methacrylate (purified by passage over a column of basic 
alumina under argon) was begun. An additional 0.25 mL of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF) was added. During 
the addition the temperature rose from 42.degree. C. to 44.degree. C. When 
the addition was complete and the temperature began to fall, 0.25 mL of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF) was added, and 
16.7 g (16.7 mL, 67.8 mmol) of ethoxytriethylene glycol methacrylate 
(obtained from Polysciences, Inc., Warrington, Pa.; purified by passage 
over a column of basic alumina under argon) was added dropwise from an 
addition funnel. Since little temperature change was observed, an 
additional 0.25 mL of tetrabutylammonium biacetate hexahydrate (0.04 M in 
THF) was added to insure completion of the polymerization. Analysis of an 
aliquot of the solution by .sup.1 H nmr showed that there was no residual 
monomer present. To the viscous solution of poly(trimethylsilyl 
methacrylate [57 mol %]-b-2-phenylethyl methacrylate [26 mol 
%]-b-ethoxytriethylene glycol methacrylate [17 mol %]) was added 50 mL of 
THF and 70 mL of a 0.5 volume % solution of dichloroacetic acid in aqueous 
methanol (prepared from 7.5 mL of dichloroacetic acid, 1030 mL of 
methanol, and 470 mL of water). The resulting mixture was refluxed for 4 
hr and evaporated in a rotary evaporator under reduced pressure. The 
residual polymer was dried for 48 hr in a vacuum oven at 80.degree. C. to 
give 46.5 g of poly(methacrylic acid [57 mol %]-b- 2-phenylethyl 
methacrylate [26 mol %]-b-ethoxytriethylene glycol methacrylate [17 mol 
%]). .sup.1 H NMR analysis of the product showed that no trimethylsilyl 
ester groups remained. 
EXAMPLE 5 
Poly(dimethylaminoethyl methacrylate [30.7 mol %]-co-methyl methacrylate 
[20.3 mol %]-b-2-phenylethyl methacrylate [32.6 mol %]-b-ethoxytriethylene 
glycol methacrylate [16.3 mol %]) 
To a solution of 2.61 g (3.03 mL, 15 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene and 0.2 mL of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF) in 120 mL of THF 
was added dropwise a mixture of 17.7 g (19.0 mL, 113 mmol) of 
dimethylaminoethyl methacrylate (purified by passage over a column of 
basic alumina under argon) and 7.5 g (8.0 mL, 74.8 mmol) of methyl 
methacrylate (purified by passage over a column of basic alumina under 
argon). During the course of the addition the temperature of the reaction 
mixture rose from 28.degree. C. to 38.degree. C. After all of the monomer 
had been added, the temperature began to fall. When the temperature had 
fallen to 35.degree. C., the addition of 22.8 g (22.6 mL, 120 mmol) of 
2-phenylethyl methacrylate (purified by passage over a column of basic 
alumina under argon) was begun. An additional 0.2 mL of tetrabutylammonium 
biacetate hexahydrate (0.04 M in THF) was added. During the addition the 
temperature rose from 35.degree. C. to 40.degree. C. When the addition was 
complete and the temperature began to fall, 0.2 mL of tetrabutylammonium 
biacetate hexahydrate (0.04 M in THF) was added, and 14.8 g (60.1 mmol) of 
ethoxytriethylene glycol methacrylate (purified by passage over a column 
of basic alumina under argon) was added dropwise from an addition funnel. 
Analysis of an aliquot of the solution by .sup.1 H nmr showed that there 
was no residual monomer present. The solution was evaporated in a rotary 
evaporator under reduced pressure. The residual polymer was dried for 48 
hr in a vacuum oven at 80.degree. C. to give 64 g of 
poly(dimethylaminoethyl methacrylate [30.7 mol %]-co-methyl methacrylate 
[20.3 mol %]-b-2-phenylethyl methacrylate [32.6 mol %]-b-ethoxytriethylene 
glycol methacrylate [16.3 mol %]). 
EXAMPLE 6 
Preparation of poly(methacrylic acid [25 mol %]-b-2-phenylethyl 
methacrylate [50 mol %]-b-ethoxytriethylene glycol methacrylate [25 mol 
%]) 
To a solution of 3.48 g (4.04 mL, 20 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene and 0.2 mL of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF) in 30 mL of THF 
was added dropwise 15.9 g (18 mL, 100 mmol) of trimethylsilyl 
methacrylate. During the course of the addition the temperature of the 
reaction mixture rose slowly while four 0.2 mL portions of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF) were added. The 
temperature continued to rise to 44.degree. C. after all of the monomer 
had been added. When the temperature began to fall, 50 mL of THF was 
added, and the addition of 38.1 g (37.7 mL, 200 mmol) of 2-phenylethyl 
methacrylate (purified by passage over a column of basic alumina under 
argon) was begun. When the addition was complete and the temperature began 
to fall, 24.6 g (24.6 mL, 100 mmol) of ethoxytriethylene glycol 
methacrylate (purified by passage over a column of basic alumina under 
argon) was added dropwise from an addition funnel. Analysis of an aliquot 
of the solution by .sup.1 H nmr showed that there was no residual monomer 
present. The solution of poly(trimethylsilyl methacrylate [25 mol 
%]-b-2-phenylethyl methacrylate [50 mol %]-b-ethoxytriethylene glycol 
methacrylate [25 mol%]) was refluxed for 12 hr with methanolic 
tetrabutylammonium fluoride. After evaporation in a rotary evaporator 
under reduced pressure, the residual polymer was dried for 48 hr in a 
vacuum oven at 80.degree. C. to give 58 g of poly(methacrylic acid [25 mol 
%]-b 2-phenylethyl methacrylate [50 mol %]-b-ethoxytriethylene glycol 
methacrylate [25 mol %]). .sup.1 H NMR analysis of the product showed that 
no trimethylsilyl ester groups remained. 
Additional ABC triblock polymers prepared according to the method of 
Example 6 include: 
Poly-.omega.-2-.beta.-hydroxyethyl isobutyrate methoxypolyethylene glycol 
400 methacrylate [41.7 mol %]-b-2-phenylethyl methacrylate [41.7 mol 
%]-b-ethoxytriethylene glycol methacrylate [16.6 mol %]). The hydroxyethyl 
isobutyrate end group was introduced by using the initiator 
1-trimethylsiloxy-1-(2-trimethylsiloxyethoxy)-2-methyl-1-propene, followed 
by deprotection with methanol. 
Poly(methacrylic acid [48 mol %]-b-2-phenylethyl methacrylate [37 mol 
%]-b-2-hydroxyethyl methacrylate [15 mol %]). [The 2-hydroxyethyl 
methacrylate was polymerized as the protected monomer, 
2-trimethylsiloxyethyl methacrylate.] 
Poly(methacrylic acid [48 mol %]-b-2-phenylethyl methacrylate [37 mol 
%]-b-2-ethoxyethyl methacrylate [15 mol %]) 
Poly(methacrylic acid [41.9 mol %]-b-benzyl methacrylate [22.6 mol 
%]-co-methyl methacrylate [22.6 mol %]-b-ethoxytriethylene glycol 
methacrylate [12.9 mol %]) 
Poly(methacrylic acid [48 mol %]-b-benzyl methacrylate [37 mol 
%]-b-ethoxytriethylene glycol methacrylate [15 mol %]) 
Poly(2-dimethylaminoethyl methacrylate [33.3 mol 
%]-b-2-phenylethylmethacrylate [33.3 mol %]-b-methacrylic acid [33.3 
mol%]. 
EXAMPLE 7 
Poly(dimethylaminoethyl methacrylate [30.7 % mol]-co-methyl methacrylate 
[20.3 mol %]-b-2-phenylethyl methacrylate [20.3 mol %]-co-methacrylic acid 
[12.3 mol %]-b-ethoxytriethylene glycol methacrylate [16.3 mol %]) 
To a solution of 2.61 g (3.03 mL, 15 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene and 0.2 mL of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF) in 60 mL of THF 
was added dropwise a mixture of 17.7 g (19.0 mL, 113 mmol) of 
dimethylaminoethyl methacrylate (purified by passage over a column of 
basic alumina under argon) and 7.5 g (8.0 mL, 74.8 mmol) of methyl 
methacrylate (purified by passage over a column of basic alumina under 
argon). During the course of the addition the temperature of the reaction 
mixture rose from 28.degree. C. to 37.degree. C. When 0.2 mL of 
tetrabutylammonium biacetate hexahydrate (0.04 M in THF) was added, the 
temperature rose to 42.degree. C. After all of the monomer had been added, 
the temperature began to fall. When the temperature had fallen to 
39.degree. C., the addition of a mixture of 14.1 g (14.2 mL, 75 mmol) of 
2-phenylethyl methacrylate (purified by passage over a column of basic 
alumina under argon) and 7.1 g (8.1 mL, 45 mmol) of trimethylsilyl 
methacrylate was begun. An additional 2 mL of tetrabutylammonium biacetate 
hexahydrate (0.04 M in THF) was added in 8 portions during the addition. 
When the addition was complete and the temperature began to fall, 14.8 g 
(14.8 mL, 60.1 mmol) of ethoxytriethylene glycol methacrylate (purified by 
passage over a column of basic alumina under argon) was added dropwise 
from an addition funnel. Since little temperature change was observed, an 
additional 0.6 mL of tetrabutylammonium biacetate hexahydrate (0.04 M in 
THF) was added in three portions to insure completion of the 
polymerization. Analysis of an aliquot of the solution by .sup.1 H nmr 
showed that there was no residual monomer present. To the viscous solution 
of poly(dimethylaminoethyl methacrylate [30.7 mol %]-co-methyl 
methacrylate [20.3 mol %]-b-2-phenylethyl methacrylate [20.3 mol 
%]-co-trimethylsilyl methacrylate [12.3 mol %]-b-ethoxytriethylene glycol 
methacrylate [16.3 mol %]) was added 50 mL of THF and 11 mL of methanol 
containing 0.02 g (0.05 mmol) of dichloroacetic acid. The resulting 
mixture was refluxed for 4 hr and evaporated in a rotary evaporator under 
reduced pressure. The residual polymer was dried for 48 hr in a vacuum 
oven at 80.degree. C. to give 58 g of poly(dimethylaminoethyl methacrylate 
[30.7 mol %]-co-methyl methacrylate [20.3 mol %]-b-2-phenylethyl 
methacrylate [20.3 mol %]-co-methacrylic acid [12.3 mol 
%]-b-ethoxytriethylene glycol methacrylate [16.3 mol %]). .sup.1 H NMR 
analysis of the product showed that no trimethylsilyl ester groups 
remained. 
EXAMPLE 8 
Poly(dimethylaminoethyl methacrylate [28.3 mol %]-co-methyl methacrylate 
[18.8 mol %]-b-2-phenylethyl methacrylate [37.8 mol %]-b-ethoxytriethylene 
glycol methacrylate [15.1 mol %]) 
To a solution of 15.7 g (18.2 mL, 90.2 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene and 0.3 mL of 
tetrabutylammonium biacetate (0.1 M in propylene carbonate) in 400 mL of 
THF was added dropwise a mixture of 106 g (114 mL, 677 mmol) of 
dimethylaminoethyl methacrylate (purified by passage over a column of 
basic alumina under argon) and 45 g (48.1 mL, 450 mmol) of methyl 
methacrylate (purified by passage over a column of basic alumina under 
argon). After all of the monomer had been added and the temperature began 
to fall the addition of 172 g (170 mL, 903 mmol) of 2-phenylethyl 
methacrylate (purified by passage over a column of basic alumina under 
argon) was begun. When the addition was complete and the temperature began 
to fall, 88.7 g (88.7 mL, 360 mmol) of ethoxytriethylene glycol 
methacrylate (purified by passage over a column of basic alumina under 
argon) was added dropwise from an addition funnel. Analysis of an aliquot 
of the solution by .sup.1 H nmr showed that there was no residual monomer 
present. The solution was evaporated in vacuo to give 456 g of 
poly(dimethylaminoethyl methacrylate [28.3 mol %]-co-methyl methacrylate 
[18.8 mol %]-b-2 -phenylethyl methacrylate [37.8 mol %]-b-ethoxytriethyl 
glycol methacrylate [15.1 mol %]). GPC: M.sub.n =6240, M.sub.w =7770, 
M.sub.w /M.sub.n =1.24. 
EXAMPLE 9 
Preparation of poly(methacrylic acid [48 mol %]-b-2-phenylethyl 
methacrylate [37 mol %]-b-ethoxytriethylene glycol methacrylate [15 mol 
%]) 
To a solution of 22.6 g (26.2 mL, 130 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene and 0.1 mL of 
tetrabutylammonium biacetate (0.1 M in propylene carbonate) in 300 mL of 
THF was added dropwise 268 g (304 mL, 1.69 mole) of trimethylsilyl 
methacrylate. During the course of the addition the temperature of the 
reaction mixture rose slowly to 50.degree. C. To increase the rate of 
polymerization, an additional 1.5 mL of tetrabutylammonium biacetate (0.1 
M in propylene carbonate) was added in 7 portions. After all of the 
monomer had been added, the temperature began to fall, and the solution 
was cooled with a bath to 30.degree. C. The addition of 248 g (245 mL, 1.3 
mole) of 2-phenylethyl methacrylate (purified by passage over a column of 
basic alumina under argon) was begun. An additional 0.6 mL of 
tetrabutylammonium biacetate (0.1 M in propylene carbonate) was added. 
During the addition the temperature rose 48.degree. C. When the addition 
was complete and the temperature began to fall, the solution was cooled to 
31.degree. C., 0.15 mL of tetrabutylammonium biacetate (0.1 M in propylene 
carbonate) was added, and 128 g (128 mL, 0.52 mole) of ethoxytriethylene 
glycol methacrylate (purified by passage over a column of basic alumina 
under argon) was added dropwise from an addition funnel. Since little 
temperature change was observed, an additional 0.15 mL of 
tetrabutylammonium biacetate (0.1 M in propylene carbonate) was added to 
insure completion of the polymerization. Analysis of an aliquot of the 
solution by .sup.1 H nmr showed that there was no residual monomer 
present. To the solution of poly(trimethylsilyl methacrylate [48 mol 
%]-b-2-phenylethyl methacrylate [37 mol %]-b-ethoxytriethylene glycol 
methacrylate [15 mol %]) was added 350 mL of 0.03 M tetrabutylammonium 
fluoride trihydrate in methanol. The resulting mixture was refluxed for 16 
hr and evaporated in a rotary evaporator under reduced pressure. The 
residual polymer was dried for 48 hr in a vacuum oven to give 515 g of 
poly(methacrylic acid [48 mol %]-b-2-phenylethyl methacrylate [37 mol 
%]-b-ethoxytriethylene glycol methacrylate [15 mol %]). .sup.1 NMR 
analysis of the product showed that no trimethylsilyl ester groups 
remained. 
EXAMPLE 10 
Poly(dimethylaminoethyl methacrylate [14.9 mol %]-b-2-phenylethyl 
methacrylate [37.1 mol %]-b-ethoxytriethylene glycol methacrylate [48 mol 
%]) 
To a solution of 1.57 g (1.82 mL, 9.02 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene and 0.2 mL of 
tetrabutylammonium biacetate (0.1 M in propylene carbonate) in 150 mL of 
THF was added dropwise 5.7 g (6.1 mL, 36.2 mmol) of dimethylaminoethyl 
methacrylate (purified by passage over a column of basic alumina under 
argon). After all of the monomer had been added and the temperature began 
to fall the addition of 17.2 g (17 mL, 90.25 mmol) of 2-phenylethyl 
methacrylate (purified by passage over a column of basic alumina under 
argon) was begun. When the addition was complete and the temperature began 
to fall, 28.8 g (28.8 mL, 116.9 mmol) of ethoxytriethylene glycol 
methacrylate (purified by passage over a column of basic alumina under 
argon) was added dropwise from an addition funnel. Analysis of an aliquot 
of the solution by .sup.1 H nmr showed that there was no residual monomer 
present. The solution was concentrated under reduced pressure to give 54 
g of a 70.35% solids solution of poly(dimethylaminoethyl methacrylate 
[14.9 mol %]-b-2-phenylethyl methacrylate [37.1 mol %]-b-ethoxytriethylene 
glycol methacrylate [48 mol %]). 
EXAMPLE 11 
Preparation of Poly .omega.-2-.beta.-hydroxyethyl isobutyrate 
(methoxypolyethylene glycol methacrylate 400 [36.3 mol %]-b-2-phenylethyl 
methacrylate [45.5 mol %]-b-ethoxytriethylene glycol methacrylate [18.2 
mol %]) 
To a solution of 2.4 g (8.69 mmol) of 
1-(2-trimethylsiloxyethoxy)-1-trimethylsiloxy-2-methyl-1-propene and 1.8 
mL of tetrabutylammonium biacetate (0.1 M in propylene carbonate) in 50 mL 
THF was added dropwise 31.99 g (68.35 mmol) of methoxypolyethylene glycol 
400 methacrylate (obtained from Polysciences, Inc., Warrington, Pa.; 
stored over 4 .ANG. sieves for 7 days). During the course of the addition 
the temperature rose to 40.8.degree. C. When the temperature returned to 
27.1.degree. C., the addition of 19.13 g (86.17 mmol) 2-phenylethyl 
methacrylate (purified by passage over a column of basic alumina) was 
started. During the course of the addition, the temperature rose to 
59.9.degree. C. When the temperature returned to 31.9.degree. C., the 
addition of 8.59 g (34.36 mmol) ethoxytriethylene glycol methacrylate 
(stored over 4 A sieves for 7 days) was started. During the course of the 
addition, the temperature rose to 41.9.degree. C. Analysis of an aliquot 
of the solution by 1H NMR showed that there was no residual monomer 
present. 
The poly .omega.-2-.beta.-hydroxyethyl isobutyrate-(methoxypolyethylene 
glycol methacrylate 400 [36.3 mol %]-b-2-phenylethyl methacrylate [45.5 
mol %]-b-ethoxytriethylene glycol methacrylate [18.2 mol %]) was isolated 
via precipitation from hexane, then dried 72 hours in a vacuum oven at 
50.degree. C. to give 37.74 g of product. 
EXAMPLE 12 
Poly(methacrylic acid [48 mol %]-b-2-phenylethyl methacrylate [30 mol 
%]-co-2-dimethylaminoethyl methacrylate [7 mol %]-b-ethoxytriethylene 
glycol methacrylate [15 mol %]) 
To a solution of 2.52 g (2.93 mL, 14.5 mmol) of 
1-methoxy-1-trimethylsiloxy-2-methyl-1-propene and 0.5 mL of 
tetrabutylammonium biacetate (0.1 M in propylene carbonate) in 40 mL of 
THF was added dropwise 29.8 g (33.7 mL, 189 mmol) of trimethylsilyl 
methacrylate (purified by passage over a column of basic alumina under 
argon). During the course of the addition the temperature of the reaction 
mixture rose from 26.degree. C. to 32.degree. C. When 0.5 mL of additional 
catalyst solution was added, the temperature rose to 50.degree. C. When 
the temperature had fallen to 36.degree. C., the addition of a mixture of 
22.0 g (21.8 mL, 116 mmol) of 2-phenylethyl methacrylate (purified by 
passage over a column of basic alumina under argon) and 4.6 g (4.9 mL, 29 
mmol) of 2-dimethylaminoethyl methacrylate (purified by distillation) was 
begun. An additional 0.5 mL of catalyst solution was added, and the 
temperature slowly rose from 34.degree. C. to 36.degree. C. During 30 min, 
the temperature fell to 30.degree. C. Then 14.5 g (14.5 mL, 58.2 mmol) of 
ethoxytriethylene glycol methacrylate (purified by passage over a column 
of basic alumina under argon) was added dropwise from an addition funnel. 
An additional 0.5 mL of catalyst solution was added, and during 40 min, 
the temperature rose to 32.degree. C. and then fell to room temperature. 
Analysis of an aliquot of the solution by .sup.1 H nmr showed that there 
was no residual monomer present. The solution of poly(trimethylsilyl 
methacrylate [48 mol %]-b-2-phenylethyl methacrylate [30 mol 
%]-co-2-dimethylaminoethyl methacrylate [7 mol %]-b-ethoxytriethylene 
glycol methacrylate [15 mol %]) was treated with 45 mL of 0.03 M 
methanolic tetrabutylammonium fluoride and heated at reflux for 8 hr. The 
solution was evaporated in a rotary evaporator under reduced pressure. The 
residual polymer was dried for 24 hr in a vacuum oven to give 59 g of 
poly(methacrylic acid [48 mol %]-b-2-phenylethyl methacrylate [30 mol 
%]-co-2-dimethylaminoethyl methacrylate [7 mol %]-b-ethoxytriethylene 
glycol methacrylate [15 mol% ]). .sup.1 H NMR analysis of the product 
showed that no trimethylsilyl ester groups remained. 
EXAMPLE 13 
Preparation of pigment dispersion using poly(dimethylaminoethyl 
methacrylate [28.3 mol %]-co-methyl methacrylate [18.8 mol 
%]-b-2-phenylethyl methacrylate [37.8 mol %]-b-ethoxytriethylene glycol 
methacrylate [15.1 mol %]) 
A black pigment dispersion was prepaerd using the following procedure: 
______________________________________ 
Amount 
Ingredient (parts by weight) 
______________________________________ 
FW18, Carbon black pigment 
40.0 
(Degussa Corp., 
Allendale, NJ 07041) 
Polymer obtained in Example 8, (15% solu- 
133.3 
tion, neutralized with phosphoric acid) 
Deionized water 226.7 
Total 400.0 
______________________________________ 
The above mentioned components were premixed in a plastic beaker by 
mechanical stirring until no lumps or dry clumps were visible. The mixture 
was dispersed in a microfluidizer (Microfluidics Corp., Watham, Mass.) by 
passing it through the interaction chamber 5 times under a liquid pressure 
of about 10,000 psi. The resulting pigment dispersion had 10% pigment 
concentration with an average particle size of 117 nm as determined by 
Brookhaven BI-90 particle sizer. The final pH was 4.0. 
EXAMPLE 14 
Preparation of pigment dispersion using poly(methacrylic acid [48 mol 
%]-b-2-phenylethyl methacrylate [37 mol %]-b-ethoxytriethylene glycol 
methacrylate [15 mol %]) 
A black dispersion was prepared using the following procedure: 
______________________________________ 
Amount 
Ingredient (parts by weight) 
______________________________________ 
FW18, Carbon black pigment (Degussa Corp., 
200 
Allendale, NJ 07041) 
Polymer obtained in Example 9, (10% solu- 
1,000 
tion, 10% solution, 80% neutralized with 
KOH) 
Deionized water 800 
Total 2,000 
______________________________________ 
The above mentioned components were premixed and dispersed as described in 
Example 11 to give a 10% pigment concentrate, having an average particle 
size of 114 nm as determined by Brookhaven BI-90 particle sizer. The final 
pH was 7.57. 
As many different embodiments of this invention may be made without 
departing from the spirit and scope thereof, it is to be understood that 
this invention is not limited to the specific embodiments disclosed, 
except as defined by the appended claims.