Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Patent
1996-01-26
1998-11-03
Smith, Jeffrey T.
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
526297, 5263031, 5263183, 526316, 526291, 558462, 560205, 562595, 562598, 564204, C08F 2212, C08F 1400, C08F 2042, C08F 2054, C08F 2004, C08F 1636, C07C25500
Patent
active
058309667
DESCRIPTION:
BRIEF SUMMARY
This invention relates to new cyclopolymerisation monomers and to polymers and copolymers derived from such monomers. More specifically, the invention relates to new 4,4-disubstituted 1,6-diene monomers which are capable of undergoing polymerisations via an alternating intramolecular-intermolecular chain propagation. Polymers and copolymers derived from these monomers are also new and form a part of the invention.
Accordingly the present invention provides compounds of the general formula (I) ##STR2## wherein R.sup.1 and R.sup.2 are independently selected from the group consisting of COOR, CN, aryl, substituted aryl, COOH, halogen, C(O)NHR.sup.4, C(O)NR.sup.5 R.sup.6 ; COOR, CN, R.sup.3 CO--, C(O)NHR.sup.4, C(O)NR.sup.5 R.sup.6, P(O)(OR.sup.7).sub.2 and SO.sub.2 R.sup.8 ; with the proviso that X and Y are not both H when R.sup.1 and R.sup.2 are both COOCH.sub.3 or both phenyl; or X and Y together with the carbon atom to which they are attached form a carbocyclic or heterocyclic ring system which may contain oxygen, sulfur or nitrogen atoms; C.sub.2 to C.sub.18 alkenyl; C.sub.2 to C.sub.12 alkynyl; C.sub.5 to C.sub.8 cycloalkyl; or any of the above substituted with a substituent selected from the group consisting of hydroxy, amino, azido, cyano, nitro, aldehyde, thioether, sulfonyl, cyanato, isocyanato, thiocyanato, isothiocyanato, epoxy, silyl, silyloxy, aziridine, acyloxy, carboxy, ester, carbamoyl, carbonyldioxy, urethane, ureylene, carbonyl, C.sub.1 to C.sub.6 dialkoxyphosphoryl, C.sub.1 to C.sub.6 dialkoxythiophosphoryl, tri(C.sub.1 to C.sub.6 alkoxy)silyl, C.sub.1 to C.sub.6 alkoxy, phenyl; combinations of any of the above groups; any of which groups or combinations may be reacted upon in a pre- or post-polymerisation step to further modify their functionality; substituted aryl group; C.sub..about. alkyl, C.sub.2 to C.sub.18 alkenyl, C.sub.2 to C.sub.12 alkynyl, C.sub.5 to C.sub.8 cycloalkyl; or any of the above substituted with a substituent selected from the group consisting of hydroxy, amino, azido, cyano, cyanato, isocyanato, epoxy, silyl, silyloxy, carboxy, ester, carbamoyl, C.sub.1 to C.sub.6 alkoxy, phenyl, substituted aryl and halogen; or any combinations of any of the above groups; any of which groups or combinations may be reacted upon in a pre- or post-polymerisation step to further modify their functionality; alkyl, C.sub.3 to C.sub.8 cycloalkyl, aralkyl and alkylaryl; alkyl; and aryl or substituted aryl.
When X and Y form a ring system, suitable ring systems include a dimedone ring, a 1,3-dioxan-4,6-dione ring, a barbituric acid ring, a 3-alkyl-isoxazol-5(4H)-one ring or a 3-aryl-isoxazol-5(4H)-one ring.
The term "substituted aryl" is used herein to mean an aryl group that contains one or more substituents that do not interfere with the polymerisation process. Such substituents include alkyl, hydroxy, amino, ester, acid, acyloxy, amide, nitrile, haloalkyl, alkoxy, silyl or silyloxy groups.
Preferably the aryl group is a phenyl group. The preferred halogen atoms are Cl and Br. X.dbd.Y.dbd.H; R.sup.1 .dbd.R.sup.2 .dbd.COOCH.sub.3 ! is known and has been studied under free radical cyclopolymerisation conditions by Marvel et al. (see: C. S. Marvel, R. D. Vest, J. Amer. Chem. Soc., 1957, 79, p.5771). Recently, Choi et al. have reported the cyclopolymerisation of the parent compound using group-transfer polymerisation (see: S. K. Choi et al., Macromolecules, 1991, 24, p.5006-8). The synthetic route to the parent compound therein is quite difficult but it has been prepared by a multi-step synthesis in a moderate (about 50%) yield.
In contrast to this, the synthetic method to compounds of formula (I), as defined above, is very straightforward and all compounds can be synthesised from readily available starting materials, and in high yields.
The compounds of Formula (I) when R.sup.1 and R.sup.2 are the same may be optimally synthesised by reaction of a compound of formula (V) with two or more molar equivalents of a compound of formula (VI) in the presence of an organic or inorganic base. ##STR3##
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Moad Graeme
Rizzardo Ezio
Thang San Hoa
Cheng Wu C.
Commonwealth Scientific & Industrial Research Organisation
Costello James A.
E. I. Du Pont de Nemours and Company
Smith Jeffrey T.
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