Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-01-09
2004-01-13
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...
C526S171000, C526S226000, C526S237000, C526S259000, C526S262000, C526S280000, C526S282000, C526S284000
Reexamination Certificate
active
06677418
ABSTRACT:
This is a nationalization of PCT/GB00/02548 filed Jul. 10, 2000 and published in English.
The present invention relates to a process for the polymerisation of olefins, novel polymerisable olefins, curable compositions thereof, the products thereof and their use in the preparation of shaped products, coatings and the like. More particularly the invention relates to a process for the copolymerisation of monofunctional and bifunctional strained bicyclic olefin monomers, novel monofunctional and bifunctional strained bicyclic olefin monomers, and their associated compositions, products and uses.
The polymerisation of dicyclopentadiene (DCPD) has long been known and commercially operated for the production of shaped thermoset cross linked products which are extremely bard. The products are particularly useful since they undergo surface oxidation allowing them to be painted, and rendering them odorless. The catalysts employed are air sensitive and functional group sensitive, complicating the process, and limiting the reaction in terms of monomer variation.
Polymerisation of derivatives is known from the literature. In particular a number of publications (Ciba Geigy) relate to novel (“Grubbs”) catalysts for use in polymerising strained olefins and their derivatives. The catalysts are disclosed as suited for the polymerisation of a vast range of polymerisable monofunctional monomers and difunctional bridged monomers, by virtue of their excellent moisture tolerance. However polymerisation of only a limited number of the disclosed monomer and dimer classes is described. WO 97/38036 describes ring opening metathesis polymerisation of an at least 3 membered alicyclic cycloolefin with a specific ruthenium catalyst. Cycloolefin ring substituents are inert and do not adversely affect the chemical and thermal stability of the catalyst. WO 96/20235 describes the corresponding polymerisation of dicyclopentadiene (DCPD) optionally with an at least 3 membered alicyclic cycloolefin. WO 96/16008 describes the corresponding polymerisation of a bridged cycloolefin as a dimer, trimer or the like.
We have now surprisingly found that by selection of particular classes of novel and known polymerisable monofunctional monomers and difunctional bridged monomers and combinations thereof, and polymerising with a class of transition metal catalyst, a novel type of product may be obtained which exhibits excellent properties in terms of controlling cross-linking density, and associated product modulus and glass transition temperature (Tg), allowing novel uses as elastomers, plastics and composites. Particularly advantageous performance is obtained with use of the known “Grubbs” catalysts.
In its broadest aspect the present invention provides a process for the catalytic copolymerisation of strained (poly)cyclic olefins substituted by at least one carbon skeletal group, wherein the olefins comprise a monofunctional monomer and a difunctional monomer.
Accordingly there is provided according to the present invention a process for the catalytic copolymerisation of strained activated cyclic olefins comprising contacting a strained mono (poly)cyclic olefin monomer of formula
with at least 1 wt % of a strained di (poly)cyclic olefin monomer of formula
in the presence of a catalyst or an initiating agent wherein the group
represents a strained (poly)cyclic olefin, tail Y and spacer X comprise preferably electron withdrawing and property modulating groups
whereby the monomers form a copolymer comprising the repeating unit
and at least 1 wt % of the unit
which is adapted for subsequent cross linking of respective copolymer chains in the presence of heat and catalyst to form an amount of a cross linked copolymer comprising the unit,
wherein groups are as hereinbefore defined.
The process of the invention provides for preparation of polymeric materials having tailored properties, whereby monofunctional monomer tail Y and difunctional monomer spacer X may be selected to have desired properties in terms of stiffness or flexibility, mobility or immobility, in terms of tail or spacer length. spatial orientation, and may be combined in any given ratio of monomers and the like.
Without being limited to this theory it is thought that the strained (poly)cyclic olefins of the invention may in fact be substituted by any nature of substituent which allows variation in “softness” and “hardness” or the like and regulation of crosslinking of polymeric material. The most convenient form allowing gradation of properties is that of a carbon skeleton which may be varied in length. The substituent according to the invention is also normally linked to the olefin by an electron withdrawing group, for reasons of ease of synthesis and the like. Other linking groups may be envisaged such as simple hydrocarbon, phenyl, or alkoxyl (electron donating), whereby the process of the invention may however be carried out with use of any combination of mono and difunctional monomer as hereinafter defined
Reference herein to a monofunctional monomer, hereinafter CnM, and a difunctional monomer, hereinafter CmD, is to compounds comprising respectively one and two strained (poly)cyclic olefin functional units.
The cyclic olefin is preferably a monocyclic olefin, more preferably norbornene, substituted in the 5 and/or 6 positions by exo- and/or endo-normally electron withdrawing group(s) and property modulating tail Y and spacer X as hereinbefore defined.
Preferably an electron withdrawing group is a carbonyl group.
Preferably the monofunctional and difunctional monomer are of formulae I and II:
wherein at least one R
1
is a group Y and comprises a preferably electron withdrawing group, facilitating ROMP reaction with monomer II, and X comprises a 2, 3 or 4-valent or two 2-valent optionally substituted hydrocarbon spacer group(s) adapted to bridge adjacent crosslinked chains and which provides for controllable uniformity and degree of cross linking, providing controlled modulus and Tg.
Preferably at least one R
1
is independently selected from COOR
2
, CONR
2
, COR
2
and the like
in which R
2
is selected from straight chain and branched, saturated and unsaturated C
1-12
hydrocarbon optionally substituted by one or more hydroxy, halo, aryl, cyclo C
1-8
alkyl, bisphenol such as bisphenol A, bisphenol F, phenol, hydroquinone and the like, and optionally including at least one heteroatom such as O, P;
and one or more of the remaining groups R
1
may be selected from H, C
1-3
alkyl, halo such as F and the like;
or two groups R
1
together form a cyclic amide or anhydride —(CH
2
)
p
CONR
3
CO—; —(CH
2
)
p
COOCO—
in which p is 0-4, and is 0 when the two groups form a fused structure or 1-4 when the two groups form a spiro structure;
R
3
is as hereinbefore defined for R
2
and is a bridging unit; and
X is a linear or fused bridging moiety as hereinbefore defined.
Preferably X is a linear bridging group —COOR
2
COO— wherein R
2
is as hereinbefore defined, substituting the cyclic olefin at the 5 positions and the 6 positions are unsubstituted or substituted by H, C
1-3
alkyl, halo such as F and the like; or
X is a fused bridging group —(CO)
2
NR
3
N(CO)
2
— in which —(CO)
2
N forms a 5 membered cyclic ring with the 5 and 6 positions of each cyclic olefin,
and wherein R
3
is as hereinbefore defined.
Monomers may be exo-, endo- or a mixture thereof. The process of the invention allows the option to select isomers for desired Tg (endo is stiffer than exo) and % trans isomer in the product. Preferably monomers are exo-, which are generally more reactive, than endo- although resulting in lower product Tg.
Preferably the process comprises dissolving the difunctional monomer in the monofunctional monomer and adding initiator in monomer solution. The process conditions may be controlled by selection of monomer ratio and isomer type to provide well ordered living polymerisation or otherwise. It is a particular advantage that the process provides substantially complete cure.
The process of the invention provides as polymeric product of the reaction of I and II
Feast William James
Khosravi Ezat
Leejarkpai Thanawadee
Jacobson & Holman PLLC
Pezzuto Helen L.
University of Durham
LandOfFree
Process for polymerization of cycloolefins and polymerizable... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Process for polymerization of cycloolefins and polymerizable..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for polymerization of cycloolefins and polymerizable... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3205126