Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-12-10
2001-10-16
Lipman, Bernard (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S264000, C526S265000, C526S298000, C526S316000, C526S319000, C526S328000, C526S341000
Reexamination Certificate
active
06303722
ABSTRACT:
TECHNICAL FIELD
The present invention concerns novel block copolymers and a novel method for the anionic (co)polymerization of anionically (co)polymerizable monomers (preferably, of acrylic and/or methacrylic apolycid derivatives and of structurally related monomers) in the presence of phosphonium salts of resonance-stabilized nitrogen, oxygen or sulfur anions. The present (co)polymers, and (co)polymers produced by the present process, have a well-defined molecular weight and narrow molecular weight distribution.
BACKGROUND ART
The controlled polymerization of (meth)acrylates under moderate conditions has been at the center of interest of numberous research groups for a long time.
1
For instance, an example of one approach developed in the 1980s was group transfer polymerization (GTP), although this approach requires expensive initiators and catalysts.
2
Moreover, coordinating ligands such as metallated alkoxide
3
and lithium chloride
4
have been used in the anionic polymerization of MMA, with adequate control being achieved only at temperatures <−40 C. Other polymerization systems, such as catalytic chain-transfer polymerization,
1
“living” free-radical polymerization,
1,5
“metal-free,”
6
“coordinative,poly,”
7
“screened,”
8
“high-speed immortal”
9
and crown ether enhanced
4a,10
anionic polymerization reactions, have been successful to differing degrees in the preparation of PMMA of narrow molecular mass distribution at moderate temperatures. n-Butyl acrylate has been anionically polymerized at 20° C. by metal-free polymerization using tetrabutylammonium counterions,
6
which is sensitive due to the instability of the initiators. A distinct improvement on this method is constituted by the anionic polymerization in the presence of tetraphenylphosphonium counter-ions.
11
1. Review Article: Davis, T., Haddleton, D., Richards, S. J. M. S. Rev. Macromol. Chem. Phys. 1994, C34, 243.
2. (a) Webster, O., Hertler, W., Sogah, D., Farnham, W. and RajanBabu, T. J. Am. Chem. Soc. 1983, 105, 5706; (b) Sogah, D., Hertler, W., Webster, O. and Cohen, G. Macromolecules 1988, 20, 1473.
3. Lochmann, L., Muller, A. Makromol. Chem. 1990, 191, 1657.
4. Teyssie, P., Fayt, R., Hautekeer, J., Jacobs, C., Jerome, R., Leemans, L., Varshney, S. Makromol. Chem., Macromol. Symp. 1990, 32, 61; (b) Wang, J., Jerome, R., Teyssie, P. Macromolecules 1994, 27, 4902.
5. (a) Otsu, T. and Tazaki, T. Polym. Bull. 1986, 16, 277; (b) Georges, M., Vereqin, R., Kazmaier, P., Hamer, G. Macromolecules 1993, 26, 2987; (c) Druliner, J. Macromolecules 1991, 24, 6079; (d) Mardare, D. and Matyjaszewski, K. Polymer Preprints (Am. Chem. Soc., Div. Polym. Chem.) 1993, 34, 566.
6. (a) Reetz, Mpoly, Knauf, T., Minet, U. and Bingel, C. Angew. Chem. Int. Ed. Engl. 1988, 27, 1371; (b) Reetz, M., Minet, U., Bingel, C. and Vogdanis, L. Polymer Preprints (Am. Chem. Soc., Div. Polym. Chem.) 1991, 32, 296; (d) Pietzonka, T. and Seebach, D. Angew. Chem. Int. Ed. Engl. 1993, 32, 716.
7. (a) Yasuda, H., Yamamoto, H., Yokota, K., Miyake, S. and Nakamura, A. J. Am. Chem. Soc. 1992, 114, 4908; (b) Yasuda, H., Yamamoto, H., Yamashita, Mpoly., Yokotd, Kpoly., Nakamura, A., Miyake, S., Kai, Y. and Kanehisa, N. Macromolecules 1993, 26, 7134.
8. Ballard, D., Bowles, R., Haddleton, D., Richards, S., Sellens, R. and Twose, D. Macromolecules 1992, 25, 5907.
9. (a) Sugimoto, H., Kuroki, M., Watanabe, T., Kawamura, C., Aida, T. and Inoue, S. Macromolecules 1993, 26, 3403; (b) Akatsuka, M., Aida, T. and Inoue, S. Macromolecules 1994, 27, 2820.
10. (a) Varshney, S., Jerome, R., Bayard, P., Jacobs, C., Fayt, R. and Teyssie, P. Macromolecules 1992, 25, 4457; (b) Wang, J., Jerome, R., Bayard, P., Baylac, L., Patin, M. and Teyssie, P. Macromolecules 1994, 27, 4615.
11. T. Hogen-Esch and A. Zagala, U.S. patent application Ser. No. 08/398,694.
OBJECTS OF THE INVENTION
Accordingly, one object of the present invention is to provide a process for the preparation of polymers and copolymers of defined molecular mass and narrow molecular mass distribution.
It is a further object of the present invention to provide a novel method for preparing polymers and copolymers which enables maximum structural variation and, at the same time, permits controlled anionic (co)polymerization of anionically polymerizable monomers at room temperature.
It is a further object of the present invention to provide a novel method for anionically producing poly(meth)acrylate (co)polymers which provides a (co)polymer having a narrow molecular weight distribution.
It is a further object of the present invention to provide a novel method for producing poly(meth)acrylate (co)polymers by anionic polymerization which provides effective control of (co)polymer molecular weight.
It is a further object of the present invention to provide a novel method for producing poly(meth)acrylate (co)polymers by anionic polymerization which can provide effective control of (co)polymer stereoregularity (e.g., isotacticity and/or syndiotacticity).
It is a further object of the present invention to provide a novel method for producing poly(meth)acrylate (co)polymers by anionic polymerization which provides the (co)polymer in good yields.
It is a further object of the present invention to provide a novel method for producing poly(meth)acrylate (co)polymers which achieves the above objects at ambient temperatures.
These and other objects, which will become apparent in the following detailed description of the preferred embodiments, have been provided by a method for producing a (co)polymer, which comprises:
reacting an anionically polymerizable monomer of the formula:
with an initiator of the formula
(PR
6
R
7
R
8
R
9
)
+
(R
10
R
11
N)—
(PR
6
R
7
R
8
R
9
)
+
(R
12
O)—
or
(PR
6
R
7
R
8
R
9
)
+
(R
13
S)—
at a temperature of from −78° C. to 40° C., in a solvent in which the initiator at least partially dissolves and which does not quench the reaction, for a length of time sufficient to polymerize the monomer(s) and form a reaction mixture, wherein:
R
1
is selected from the group consisting of H, CN, straight-chain or branched alkyl of from 1 to 6 carbon atoms (which may be substituted with from 1 to (2n+1) halogen atoms, where n is the number of carbon atoms in the alkyl group, e.g. CF
3
), straight-chain or branched alkenyl of from 2 to 6 carbon atoms (which may be substituted with from 1 to (2n−1) halogen atoms, where n is the number of carbon atoms in thpolye alkenyl group), straight-chain or branched alkynyl of from 2 to 6 carbon atoms (which may be substituted with from 1 to (2n−3) halogen atoms, where n is the number of carbon atoms in the alkynyl group) and aryl, and
R
2
is independently selected from the group consisting of CN, C(═X)R
3
, C(═X)NR
4
R
5
and heterocyclic rings capable of stabilizing an &agr;-anion, where X is NR (R is C
1
-C
20
alkyl), O or S; R
3
is alkyl of from 1 to 20 carbon atoms, alkoxy of from 1 to 20 carbon atoms or alkylthio of from 1 to 20 carbon atoms; and R
4
and R
5
are independently alkyl of from 1 to 20 carbon atoms or are joined together to form an alkylene group of from 2 to 5 carbon atoms, thus forming a 3- to 6-membered ring;
R
6
, R
7
, R
8
and R
9
are independently alkyl of from 1 to 20 carbon atoms, aryl or aralkyl, and any pair of R
6
, R
7
, R
8
and R
9
may be joined to form a ring, including the possibility that both pairs of R
6
-R
9
may be joined to form a ring (preferably a 3- to 8-membered ring),
R
10
and R
11
are independently alkyl of from 1 to 20 carbon atoms, cycloalkyl of from 3 to 10 carbon atoms, an aryl group, a trialkylsilyl group or an electronegative group, or R
10
and R
11
may be joined together to form a heterocycle, and
R
12
is H, straight-chain or branched alkyl of from 1 to 20 carbon atoms or cycloalkyl of from 3 to 10 carbon atoms which may contain one or more remote sites of unsaturation, aryl, aralkyl or a (co)polymer radical;
R
13
is independently R
12
, straight-chain or branched alkenyl of from 2 to 20 carbon atoms, or straight-chain or branched alkyn
Hogen-Esch Thieo E.
Mehler Christof
Muller Axel
Zagala Angela
BASF - Aktiengesellschaft
Keil & Weinkauf
Lipman Bernard
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