Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2000-06-16
2003-11-04
Pezzuto, Helen L. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S244000, C525S260000, C526S193000, C526S217000, C526S219600, C526S204000, C526S222000, C526S262000, C526S288000
Reexamination Certificate
active
06642318
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.
Other process is disclosed in EP 0592 283 A1. The process is directed to synthesizing hydroxylated telechelic polymers obtained in the presence of thiuram sulfide, which acts as an initiator, chain transfer agent and a termination agent. Such agents are commonly referred to as iniferters.
Another process is disclosed in EP 0286 376 A2. The process is directed to synthesizing ABA type block copolymers through photodecomposition of dithiocarbamate group-contaning polymeric intermediates.
Yet another process is disclosed in EP 0349 232 A2. The process is directed to synthesizing acrylic block copolymers by using an iniferter.
Still another process is disclosed in EP 0449 619 A2. The process is directed to synthesizing adhesives by using radiation curable photoiniferters.
Another process is disclosed in EP 0421 149 A1. The process is directed to synthesizing chloroprene polymers having dithiocarbamate groups at both termini of the chloroprene polymeric chain.
Chem. Abstract 74:87665 Apr. 4, 1971) and JP-B-45034804 disclose thiocarbamate iniferter as a polymerization catalyst.
Another Chem. Abstract 72:53948 Mar. 3, 1970) and Agr. Biol. Chem. (1969), 33 (12), 1691-1699 disclose the use of thiocarbonates as herbicides.
Yet another Chem. Abstract 125:276423 Nov. 11, 1996) and J. Am. Chem. Soc. (1996), 118 (38), 9190-9191 disclose a process for synthesizing deoxygenerated sugar derivatives obtained by heating a variety of carbohydrate xanthate containing electron withdrawing ester groups in cyclohexane.
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 all 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 aryl, substituted or unsubstituted alkoxycarbonyl, 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 unsubs
Chiefari John
Mayadunne Roshan Tyrrel
Moad Graeme
Rizzardo Ezio
Thang San Hoa
Deshmukh Sudhir G.
E. I. du Pont de Nemours and Company
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