Norbornene sulfonamide polymers

Details Norbornene sulfonamide polymers Norbornene sulfonamide polymers

2000-02-03

2002-07-16

Henderson, Christopher (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S259000, C526S268000, C526S271000, C526S281000, C526S283000

Reexamination Certificate

active

06420503

ABSTRACT:

BACKGROUND OF THE INVENTION
Certain phenyl sulfonamide polymers have been known at least since the late 1960's. R. W. Angelo et al., in IBM Technical Disclosure Bulletin, vol. 11, No. 7 (December 1968), disclosed condensing m-benzene disulfonyl chloride with hexamethylene diamine to form a phenyl sulfonamide polymer. Said publication further disclosed crosslinking polystyrene with then sulfonamide linkages which in turn can be treated to form the corresponding sulfonic acid or acid chloride which, when treated with a diamine such as hexamethylene diamine, forms a polystyrene sulfonamide.
European Patent Application published on Sep. 11, 1996, EP 0 731 388 A2, discloses styryl and methacryl-based sulfornamide-containing polymers. T. X. Neenan et al., Microelectronics Technology, ACS Symposium Series 614, (April 2-6, 1995), pp. 194-206, also discuss styrylmethylsulfonamides. These specific polymers are said to be useful as photoresists, but they are deficient because they are not easily soluble in photoresist compatible solvents, such as propyleneglycol methyl ether acetate. PCT Patent Application published Sep. 12, 1997, WO 97/33198, discloses addition-type polymers of norbornene-type monomers, some containing functional groups such as carboxyl groups or esters, that may be obtained by polymerizing such monomers in the presence of Group VIII metal catalysts. European Patent Application published Aug. 13, 1997, EP 0 789 278 A2, discloses ROMP polymers obtained by polymerizing norbornene-type monomers that may contain functional substituents other than sulfonamides, by using well known metathesis catalysts. European Patent Application published Sep. 10, 1997, EP 0 794 458 A2, discloses the preparation of cyclic olefin copolymers, such as a norbornene/maleic anhydride and norbornene/maleic anhydride/acrylate, using free radical polymerization. None of the above mentioned publications disclose NB sulfonamides.
The preparation of fluorine-containing sulfonamide norbornenes is described by A. O. Kas'yan et al., Ukr. Gos. Khim-Tekhnol. Univ., Dnepropetrovsk, Ukraine, Zh. Org. Khim. (1995), 357-64. CODEN:ZORKAE; ISS 0514-7492. CAN 124:145481.
SUMMARY OF THE INVENTION
It is a general object of the invention to provide novel sulfonamide norbornene (NB) polymer compositions. Such polymers may be NB sulfonamide homopolymers or copolymers of at least one NB sulfonamide with at least one other comonomer such as NB, ethylene, an acrylate, maleic anhydride, CO, SO
2
, and the like.
It is another object of the invention to provide certain novel NB sulfonamide monomers.
The addition homopolymers and copolymers of this invention may be prepared employing a single or multicomponent catalyst system, each containing a Group VIII metal ion source. Copolymers of an NB sulfonamide and maleic anhydride or SO
2
or maleic anhydride and an acrylate may be prepared employing a standard free radical catalyst. NB sulfonamide ROMP polymers may be prepared employing known ROMP catalysts and thereafter preferably hydrogenating the resulting polymer.
DETAILED DISCLOSURE
The polycyclic copolymers of the present invention comprise repeating units copolymerized from at least one polycycloolefin monomer wherein at least a portion of which contain a pendant sulfonamide group. As stated herein the terms “polycycloolefin,” “polycyclic,” and “norbornene-type” monomer are used interchangeably and mean that the monomer contains at least one norbornene-type moiety as shown below:
In the formula above, x represents oxygen, nitrogen with a substituent being hydrogen or C
1-10
alkyl, linear or branched, sulfur or a methylene group of the formula —(CH
2
)
n′
— wherein n′ is an integer of 1 to 5.
The simplest polycyclic monomer of the invention is the bicyclic monomer, bicyclo[2.2.1]hept-2-ene, commonly referred to as norbornene. The term norbornene-type monomer is meant to include substituted and unsubstituted norbornene-type monomers, and any substituted and unsubstituted higher cyclic derivatives thereof so long as the monomer contains at least one norbornene-type or substituted norbornene-type moiety. The substituted norbornene-type monomers and higher cyclic derivatives thereof contain a pendant hydrocarbyl substituent(s) or a pendant functional substituent(s) containing a heteroatom such as oxygen or nitrogen.
The sulfonamide functional norbornene-type monomers are represented by the structure below:
wherein x represents oxygen, nitrogen with hydrogen or C
1-10
alkyl substituent, sulfur or a methylene group of the formula —(CH
2
)
n′
—; n is an integer of 0, 1 or more, preferably 0 to 5, and more preferably 0, 1, or 2; and R
1
and R
4
independently represent hydrogen, linear or branched linear and branched C
1
-C
20
alkyl (preferably C
1-10
); R
2
and R
3
independently represent hydrogen, linear and branched C
1
-C
20
alkyl or a sulfonamide group, with the proviso that at least one of R
2
and R
3
is a pendant sulfonamide group of the formulae:
 —A—NR′SO
2
R″ and —A—SO
2
NR′R′″
or a cyclic sulfonamide group formed by combining R
2
and R
3
together with the two ring carbon atoms to which they are attached to form a heterocyclic ring of the formula:
wherein in the above structures m is an integer from 1 to 3;
R′ represents hydrogen, linear and branched tri(C
1
-C
10
) alkylsilyl, —C(O)CF
3
, —C(O)OR, and —OC(O)OR, wherein R is lnear and branched C
1
-C
10
alkyl, preferably t-butyl, linear and branched C
1
-C
10
haloalkyl, substituted and unsubstituted C
6
-C
14
aryl, and substituted and unsubstituted C
7
-C
20
aralkyl. As used here and throughout the specification the term substituted cycloalkyl, aryl (e.g., phenyl), and aralkyl means that the respective rings can contain monosubstitution or multisubstitution and the substituents are independently selected from linear and branched C
1
-C
5
alkyl, linear and branched C
1
-C
5
haloalkyl, substituted and unsubstituted phenyl, and halogen, preferably, chlorine and fluorine;
R″ represents linear and branched C
1
-C
10
alkyl, linear and branched C
1
-C
10
haloalkyl, —(CHR′)
n″
—COOR, —(CHR
1′
)
n″
—OR, —(CHR
1′
)
n″
—C(O)R, substituted and unsubstituted C
3
to C
8
cycloalkyl(as defined above), —(CHR′)
n″
cyclic esters (lactones) containing 2 to 8 carbon atoms (not counting the carbonyl carbon), —(CHR′)
n″
cyclic ketones containing 4 to 8 carbon atoms (not counting the carbonyl carbon), cyclic ethers and cyclic diethers containing 4 to 8 carbon atoms, wherein R, R
1′
, and n″ are as defined above;
R′″ represents hydrogen, linear and branched C
1
-C
10
alkyl, linear and branched C
1
-C
10
haloalkyl, —C(O)OR, —(CHR
1′
)
n″
—OR, —(CHR
1′
)
n″
—C(O)R, substituted and unsubstituted C
3
to C
8
cycloalkyl(as defined above), —(CHR′)
n″
cyclic esters (lactones) containing 2 to 8 carbon atoms (not counting the carbonyl carbon), —(CHR′)
n″
cyclic ketones containing 4 to 8 carbon atoms (not counting the carbonyl carbon), cyclic ethers and cyclic diethers containing 4 to 8 carbon atoms, wherein R, R
1′
, and n″ are as defined above
Monomers containing the foregoing group can be represented by Formula I(a) below:
In Formula I(a) x, R
1
, R
4
, n and m are as defined previously above. In Formula Ia R
1
and, R
4
are preferably hydrogen.
In the formulae above —A— is a divalent radical selected from —(CR
1′
R
2′
)
n″
—; —(CHR
1′
)
n″
O(CHR
1′
)
n″
—; —(CHR
1′
)
n″
C(O)O(CHR
1′
)
n″
—; —(CHR
1′
)
n″
C(O)(CHR
1′
)
n″
—; C
3
-C
8
cycloalkyl; C
6
-C
14
aryl; cyclic ethers and cyclic diethers containing 4 to 8 carbon atoms, wherein n″ represents an integer from 1 to 10, and R
1′
and R
2′
independently represent hydrogen, linear and branched C
1
-C
10
alkyl and halogen, preferably chlorine and fluorine. Divalent radical —A— represent

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