Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2003-03-21
2004-06-08
Zalukaeva, Tatyana (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S135000, C526S147000, C526S204000, C526S220000, C525S308000, C525S314000, C549S200000, C549S429000, C549S482000, C549S483000, C549S498000, C548S225000
Reexamination Certificate
active
06747104
ABSTRACT:
FIELD OF THE INVENTION
The present invention provides photoiniferters for radical polymerization processes and telechelic polymers made thereby.
BACKGROUND
In conventional radical polymerization processes, the polymerization terminates when reactive intermediates are destroyed or rendered inactive; radical generation is essentially irreversible. It is difficult to control the molecular weight and the polydispersity (molecular weight distribution) of polymers produced by conventional radical polymerization, and difficult to achieve a highly uniform and well-defined product. It is also often difficult to control radical polymerization processes with the degree of certainly necessary in specialized applications, such as in the preparation of end functional polymers, block copolymers, star (co)polymers, and other novel topologies.
In a controlled radical polymerization process radicals are generated reversibly, and irreversible chain transfer and chain termination are absent. There are four major controlled radical polymerization methodologies: atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), nitroxide-mediated polymerization (NMP) and iniferters, each method having advantages and disadvantages.
The term “iniferter”, or “photoiniferter” as it is also known, refers to a chemical compound that has a combined function of being a free radical initiator, transfer agent, and terminator, the term “iniferter” being a word formed by the underlined portions of the terms identifying these functions. The photo portion of the term indicates that the polymerization is photolytically induced. This term and its use in the production of block copolymers is well known, particularly because of the work of Takayuki Otsu of the Department of Applied Chemistry, Osaka City University, Osaka, Japan. This work is discussed, for example, in an article by Otsu et al entitled “Living Radical Polymerizations in Homogeneous Solution by Using Organic Sulfides as Photoiniferters”, Polymer Bulletin, 7, 45-50 (1982), an article by Otsu et al entitled “Living Mono-and Biradical Polymerizations in Homogeneous System Synthesis of AB and ABA Type Block Copolymers”, Polymer Bulletin, 11, 135-142 (1984), Otsu entitled “Iniferter Concept and Living Radical Polymerization”, J. Polymer Science, Pat A, vol. 38, 2121-2136 (2000), and in European Patent Application No. 88303058.7, Publication No. 0 286 376, publication date Oct. 12, 1988.
There is a need for a radical polymerization process which provides (co)polymers having a predictable molecular weight and a narrow molecular weight distribution (low “polydispersity”). A further need is strongly felt for a radical polymerization process which is sufficiently flexible to provide a wide variety of products, but which can be controlled to the degree necessary to provide highly uniform products with a controlled structure (i.e., controllable topology, composition, stereoregularity, etc.). There is further need for a controlled radical polymerization process which provides telechelic (co)polymers capable of entering into further polymerization or functionalization through reactive end-groups, particularly electrophilic end groups.
SUMMARY OF THE INVENTION
The present invention provides photoiniferters for controlled radical polymerization processes that comprise compounds of the formula:
wherein
R
1
and R
2
are each independently selected from H, an alkyl group, a nitrile group, a cycloalkyl group, a heterocyclic group, an arenyl group and an aryl group, or R
1
and R
2
taken together with the carbon to which they are attached form a carbocyclic ring; R
3
and R
4
are each independently selected from an alkyl group, a cycloalkyl group, an aryl group, an arenyl group, or R
3
and R
4
taken together with the carbon to which they are attached form a carbocyclic ring;
R
5
and R
6
are each independently selected from an alkyl group, a cycloalkyl group, an aryl group, an arenyl group, or R
5
and R
6
taken together with the nitrogen to which they are attached form a heterocyclic ring, R
5
and R
6
are optionally substituted with phosphate, phosphonate, sulfonate, ester, halogen, nitrile, amide, and hydroxy groups; R
5
and R
6
may optionally be substituted with one or more caternary heteroatoms, such as oxygen, nitrogen or sulfur;
Q is a linking group selected from a covalent bond, an arenyl group, an aryl group (—CH
2
—)
o
, —CO—O—(CH
2
)
o
—, —CO—O—(CH
2
CH
2
O)
o
—, —CO—NR
8
—(CH
2
)
o
—, —CO—S—(CH
2
)
o
—, where o is 1 to 12, and R
8
is H, an alkyl group, a cycloalkyl group, an arenyl group or an aryl group; and
n is 0 or 1.
The present invention also provides photoiniferters that comprise the ring-opened reaction product of the photoiniferters of Formula I and a reactive compound, such as an aliphatic compound, having one or more nucleophilic groups. Such photoiniferters have the general formula:
wherein
R
1
and R
2
are each independently selected from H, a nitrite group, an alkyl group, a cycloalkyl group, an arenyl group, a heterocyclic group and an aryl group or R
1
and R
2
taken together with the carbon to which they are attached form a carbocyclic ring;
R
3
and R
4
are each independently selected from an alkyl group, a cycloalkyl group, an aryl, an arenyl group, or R
3
and R
4
taken together with the carbon to which they are attached form a carbocyclic ring;
R
5
and R
6
are each independently selected from an alkyl group, a cycloalkyl group, an aryl group, an arenyl group, or R
5
and R
6
taken together with the nitrogen to which they are attached form a heterocyclic ring, R
5
and R
6
are optionally substituted with phosphate, phosphonate, sulfonate, ester, halogen, nitrite, amide, and hydroxy groups; R
5
and R
6
may optionally be substituted with one or more caternary heteroatoms, such as oxygen, nitrogen or sulfur;
n is 0 or 1;
Z is O, S or NR
8
, wherein R
8
is H, an alkyl group, a cycloalkyl group, an arenyl group, a heterocyclic group or an aryl group;
R
7
is an organic or inorganic moiety and has a valency of m, R
7
is the residue of a mono- or polyfunctional compound of the formula R
7
(ZH)
m
;
Q is a linking group selected from a covalent bond, an aryl group, an arenyl group, (—C
2
—)
o
, —CO—O—(CH
2
)
o
—, —CO—O—(CH
2
CH
2
O)
o
—, —CO—NR
8
—(CH
2
)
o
—, —CO—S—(CH
2
)
o
—, where o is 1 to 12, and R
8
is H, an alkyl group, a cycloalkyl group, an aryl group, an arenyl group, a heterocyclic group or an aryl group;
m is an integer of at least 1, preferably at least 2.
The photoiniferters of the present invention provide (co)polymers having a predictable molecular weight and a narrow molecular weight distribution. Advantageously, the photoiniferters provide novel multireactive addition polymers having first and second terminal reactive groups that may be used for further functionalization. The present invention further provides a controlled radical polymerization process useful in the preparation of terminal-functionalized (telechelic) (co)polymers, block copolymers, star (co)polymers, graft copolymers, and comb copolymers. The process provides these (co)polymers with controlled topologies and compositions.
The control over molecular weight and functionality obtained in this invention allows one to synthesize numerous materials with many novel topologies for applications in coatings, surface modifications, elastomers, sealants, lubricants, pigments, personal care compositions, composites, inks, adhesives, water treatment materials, hydrogels, imaging materials, telechelic materials and the like.
In another aspect, the invention provides a method for polymerization of one or more olefinically unsaturated monomers comprising addition polymerizing one or more olefinically unsaturated monomers using the photoiniferter comprising the azlactone photoiniferters, or the ring-opened azlactone photoiniferter.
It is to be understood that the recitation of numerical ranges by endpoints includes all numbers and fractions subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and
Fansler Duane D.
Gaddam Babu N.
Heilmann Steven M.
Lewandowski Kevin M.
Wendland Michael S.
3M Innovative Properties Company
Kokko Kent S.
Zalukaeva Tatyana
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