Copolymerization with cycloolefins

Copolymerization. Copolymers could be prepared from the mixtures of the norbornene derivatives. They could also be copolymerized with cycloolefins without polar group such as cyclopentene or cyclooctene. The formation of the copolymer was confirmed by elemental analysis, ir spectrum, thin layer chromatography(TLC) and differencial scanning calorimetry(DSC). 

The high oxophilicity of early transition metal catalysts (titanium, zirconium, or chromium) causes them to be poisoned by most functionalized olefins, particularly the commercially available polar comonomers. However, there are examples of copolymerizations with special substrates or with very high levels of a Lewis acid incorporated into the polymerization system to protect the polar functionality through complexation. " Alternative routes to polar copolymers involving metathesis of cyclic olefins and functionalization of the resulting unsaturated polymer or metathesis of polar cycloolefins followed by hydrogenation to remove the resulting unsaturation have been published.The cost of these multistep... 

Alternative Monomers. We have tested several other cycloolefins for copolymerization with MA(2d). Of these we have found that the following can be successfully polymerized. 5,6-Dihydrodicyclopentadiene (DDPD) copolymerizes... 

Thus, we decided to incorporate the fluoroalcohol structure into norbomene by the Diels-Alder reaction as this cycloolefin has been known to undergo alternating radical copolymerization with SO2 readily (77). 

Poly(norbornene Sulfones) by Radical Polymerization. Cycloolefins such as norbomene copolymerize with SO2 in an alternating fashion by radical initiation at room temperature or even at 50 °C, reflecting their high ceiling temperatures (77). In order to avoid the use of a pressure bottle, however, we carried out the polymerization of norbomenes with SO2 at cryogenic temperatures. A partial list of poly(norbomene sulfones) we prepared is presented in Scheme V. All the polymers were prepared readily in high conversions but some of the polymers were not very soluble (pendant carboxylic acid, for example). This paper primarily discusses about the... 

The Friedel-Crafts metathesis catalytic systems are versatile systems capable of resulting a great variety of reactions. The new routes for polymerization of cc,p-unsaturated carbonyl compounds, conjugated dicarbonyl compounds and their copolymerization with strained cycloolefins are among them. The syntheses are very... 

Jossifov, Ch., and Verpoort, F. (1999) WOCI4 + GaBr3 - An effective catalytic system for polymerization of dicarbonyl compounds and their copolymerization with strained cycloolefins. International Symposium on Olefin Metathesis and Related Chemistry ISOM 99 Rolduc, Kerkrade, The Netherlands (Programme and Abstracts), 63... 

METALLOCENE-CATALYZED ETHYLENE COPOLYMERIZATION WITH STYRENE AND CYCLOOLEFINS... 

Cycloolefins. The ability of metallocenes to controllably insert previously recalcitrant monomers is further evidenced by the homo- and copolymerization of cycloolefins such as cyclopentene. Initially, enchainment of cyclopentene was assumed (209) to proceed in normal 1,2-fashion, as shown in Figure 14a, and indeed this appears to hold true in copolymerizations with ethylene. However, later work (210) on homopoljrmers showed that isomerization following 1,2-incorporation is obligatory, presumably due to steric considerations, srielding 1,3-inserted units (Fig. 14b)... 

Dall Asta, G Mazzanti, G Reactivity of various cycloolefins in copolymerization with ethylene by using anionic coordination catalysts. Makromol. Chem. 1963,61,178-197. 

Olefin/nonconjugated diene copolymerizations can be an attractive alternative synthetic method to olefin/cycloolefin copolymerization, because homo- and copolymerizations of cycloolefins typically show low productivity. Bergemann et al. studied ethylene/l,5-HD copolymerization with the MAO-activated catalyst 11 (Figure 19.2) under a high ethylene pressure of 1500 bar. According to... 

Table 12 Copolymerization parameters r and Y2 of ethene/cycloolefin copolymerization with different metallocene/MAO catalysts.

Abstract For the first time, cyclopentene (CPE) has been copolymerized with the strained cycloolefin norbomene (NBE) using catalytic amounts of the electrochemi-cally prepared metathesis catalyst. The microstructure of polymers was determined by H NMR and NMR spectroscopy. The polymers were also characterized by differential scanning calorimehy and gel permeation chromatography (GPC) techniques. 

Late transition metal catalysts, which are more tolerant of polar functional groups than early transition metal catalysts, are most suitable and highly active for norbomene homopolymerizations or copolymerization with other cycloolefins. A range of tailor-made homo-, co-, and terpolymers based on substituted norbomenes for applications in electronic materials are produced and commercialized, but they need further development to be efficiently used in olefin-cycloolefin copolymerizations. 

Kaminsky W, Amdt-Rosenau M (2000) Homo- and copolymerization of cycloolefins by metallocene catalysts. In Scheirs J, Kaminsky W (eds) Metallocene-based polyolefins, vol 2. Wiley, Chichester, p 89 and references there in Kaminsky W, Beulich I, Arndt M (2001) Macromol Symp 173 211 Tritto I, Boggioni L, Sacchi MC, Locatelli P, Ferro DR, Provasoli A (1999) Copolymo-microstructures of ethylene norbomene copol5tmers prepared with homogeneous metallocene based catalysts. In Kaminsky W (ed) Metalorganic catalysts for synthesis and polymerization. Springer, Berlin, p 493... 

Whereas copolymers of two or more cycloolefins via Ziegler-Natta polymerization are seldom reported [2], an abundant literature covers the copolymerization of cycloolefins with linear olefins using this type of catalyst. This mode of introducing one or more acyclic repeat units into the polymer chain formed from cycloolefins will effect drastic changes in the physico-mechanical properties of these polymers, enabling them to be applied on a large scale in various areas. 

Block copolymers from cyclooolelins have been prepared by various experimental techniques [52]. Some interesting methods use living ROMP catalysts, which allow ready synthesis of new products having controllable structures and properties. Other methods apply cross-metathesis between unsaturated polymers and/or polyalkenamers [3], polymerization of cycloolelins in the presence of unsaturated polymers [4], polymerization of two or more cycloolelins of quite different reactivities with classical ROMP catalysts [4], and copolymerization of cycloolefins with other monomers, effected by changing the polymerization mechanism from ROMP to anionic, cationic, Ziegler Natta, and group transfer, and vice versa [6-8, 52]. 

Unsaturated polymers can be blocked and grafted with polyalkenamers by ring-opening copolymerization of cycloolefins in the presence of metathesis catalysts. Thus, diblock copolymers (102) consisting of the initial unsaturated chain and the newly grown polyalk-enamer can be obtained ... 

Conventional processes for preparing COCs have some common problems. The conversion of the cycloolefin may be low and further, a high amount of ethylene incorporated results in unsatisfactory low glass transition temperatures. Catalyst compositions have been developed in order to obtain materials with high glass transition temperatures (26). Examples are shown in Table 2.3. These catalysts are used for the copolymerization of ethene and norbornene. 

Within the family of cycloolefin co-polymers, the most important from a material properties standpoint, are the ethylene/norbornene co-polymers. These co-polymers, dubbed COC for cycloolefin co-polymers, are produced by Ticona and Mitsui under the tradenames Topas and Apel , respectively. An overview of properties and applications (for example, blisters for pills) can be found on Ticona s Topas homepage.607 Detailed ethylene/norbornene copolymerization studies with different 4/-symmetric and ansa-Cp-amido catalysts, with listing of co-polymerization parameters, have been published.608 611 NB is inserted exclusively in the cis-2,3-exo-modc (Scheme 25), and most of the metallocene catalysts tend to produce alternating co-polymers,609 612 due to the low reactivity of the M-NB intermediate toward further NB insertion. This mode of NB insertion prevents f3-H transfer, and thus ethylene/ norbornene co-polymers have increasing molecular masses at increasing NB content.611... 

As was the case with the polymethacrylate-based resists, the CycloOlefin-Maleic Anhydride (COMA) system attracted a great deal of attention primarily due to ease of polymer synthesis (radical copolymerization) and good lithographic performance. Various norbornene derivatives including tetracyclo-... 

To acconunodate the needs of photolithography, some polymers were developed that cross-link upon irradiation with an Ar-F excimer laser source at 193 nm [180]. To this end were synthesized cycloolefin-maleic anhydride-alternating copolymers. This material was formed by free-radical copolymerization of norbomene and maleic anhydride ... 

Recently, Ni- and Pd-based catalysts have been developed in order to copolymerize nonpolar ethylene, 1-olefins or cycloolefins with polar comonomers, such as carbon monoxide and methyl acrylate or 1-olefins, containing polar groups which are separated by at least two methylene... 

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