Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2003-07-18
2004-06-08
Pezzuto, Helen L (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S193000, C526S204000, C526S217000, C526S219600, C526S222000, C526S250000, C526S260000, C526S264000, C526S330000, C526S347000
Reexamination Certificate
active
06747111
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention generally relates to a free radical polymerization process and particularly relates to a free radical polymerization process utilizing chain transfer agents (CTAs) and to polymers made therefrom.
There is increasing interest in developing polymerization processes that can be predictably controlled to produce polymers having specifically desired structures. One of the means for achieving such results is through a process of living polymerization. Such a process provides a higher degree of control during the synthesis of polymers having predictably well defined structures and properties as compared to polymers made by conventional polymerization processes.
Certain xanthate and dithiocarbamate derivatives of the following formula 1:
where Q=O(alkyl) or N(alkyl)
2
, respectively have been shown to confer some of the characteristics of living polymerization when used as photoinitiators in polymerization processes (see for example Otsu et al., U.S. Pat. No. 5,314,962). Such a process where radicals are generated by direct photolysis of the xanthate or dithiocarbamate derivative do not form part of this invention. See also Niwa et al. (
Makromol. Chem
., 189, 2187 (1988)) and Otsu et al. (
Macromolecules
19, 287 (1986)).
Free radical polymerizations in the presence of chain transfer agents (CTAs) represented by formula 1 (where Q=Z′ and R are as defined herein) have been disclosed by Le et al. in Int. Patent Application WO 98/01478, which discloses, that since dithiocarbamate and xanthate derivatives disclosed therein have very low transfer constants they are therefore ineffective in conferring living characteristics on a free radical polymerization. However, we have surprisingly found that by appropriate selection of substituents (Q) or the monomer these agents have high chain transfer constants and are effective in conferring living characteristics to a free radical polymerization. The CTAs of the present invention can also advantageously introduce novel end group functionalities into the resulting polymers.
STATEMENT OF THE INVENTION
The present invention is directed to a process for producing a polymer, said process comprising polymerizing a monomer mix into said polymer in the presence of a source of free radicals and a chain transfer agent having a transfer constant in the range of from 0.1 to 5000, said chain transfer agent having the following formula:
wherein when D is D1 of the following formula:
then p is in the range of from 1 to 200, E is Z′ and said transfer agent is of the following formula:
wherein when D is D2 of the following formula:
then p is in the range of from 1 to 200, E is E1 or E2 and said transfer agent is of the following formula:
wherein when D is D3 of the following formula:
then p′ is in the range of from 2 to 200, E is Z, E1 or E2 and said transfer agent is of the following formula:
wherein when D is D4 of the following formula:
—S—R′
then E is E3 or E4 and said transfer agent is of the following formula:
where in an of the above:
R is a p-valent moiety derived from a moiety selected from the group consisting of substituted or unsubstituted alkane, substituted or unsubstituted alkene, substituted or unsubstituted arene, unsaturated or aromatic carbocyclic ring, unsaturated or saturated heterocyclic ring, an organometallic species, and a polymer chain, R• being a free radical leaving group resulting from R that initiates free radical polymerization;
R* and R′ are monovalent moieties independently selected from the group consisting of a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, unsaturated or aromatic carbocyclic ring, unsaturated or saturated heterocyclic ring, substituted or unsubstituted alkylthio, substituted or unsubstituted alkoxy, substituted or unsubstituted dialkylamino, an organometallic species, and a polymer chain, R*• being a free radical leaving group resulting from R* that initiates free radical polymerization;
X is selected from the group consisting of a substituted or unsubstituted methine, nitrogen, and a conjugating group;
Z′ is selected from the group consisting of E1, E2, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylthio, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted —COOR″, carboxy, substituted or unsubstituted —CONR″
2
, cyano, —P(═O)(OR″)
2
, —P(═O)R″
2
;
R″ is selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkaryl, and a combination thereof;
Z″ is a p′-valent moiety derived from a moiety selected from the group consisting of a substituted or unsubstituted alkane, substituted or unsubstituted alkene, substituted or unsubstituted arene, substituted or unsubstituted heterocycle, a polymer chain, an organometallic species, and a combination thereof;
Z is selected from the group consisting of a halogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylthio, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted —COOR″, carboxy, substituted or unsubstituted —CONR″
2
, cyano, —P(═O)(OR″)
2
, —P(═O)R″
2
;
E1 is a substituent functionality derived from a substituted or unsubstituted heterocycle attached via a nitrogen atom, or is of the following formula:
wherein G and J are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted acyl, substituted or unsubstituted aroyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted alkylphosphonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted arylphosphonyl;
E2 is of the following formula:
wherein G′ is selected from the group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl;
E3 is of the following formula
wherein p′″ is between 2 and 200, G″ is Z″ and J′ is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted acyl, substituted or unsubstituted aroyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted alkylphosphonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted arylphosphonyl or is joined to G″ so as to form a 5-8 membered ring; and
E4 is of the following formula
wherein p′″ is between 2 and 200 and G′″ is Z″.
The present invention is also directed to polymers made by the process of the current invention. One of the embodiment is the polymer is of the following formula:
where n is a positive integer in the range of from 1 to 100,000 and wherein A is of the following formula:
when D is D1 and E is Z′;
A is of the following formula:
when D is D2 and E is E1; or
A is of the following formula:
when D is D2 and E is E2; and
and Q″ is a repeat unit derived from
Chiefari John
Mayadunne Roshan Tyrrel
Moad Graeme
Rizzardo Ezio
Thang San Hoa
Deshmukh Sudhir G.
E. I. du Pont de Nemours and Company
Pezzuto Helen L
LandOfFree
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