Oligomers, hydroxy terminated

Three oligomer hydroxy-terminated CTAs (HCTA) were first prepared. Their molecular weight and A and B pdnts in TFA-CH2Q2 (6 4 v/v) are in Table Xin. That is, these oligomers formed mesophases in TFA-CH2CI2 and the critical... 

Liquid organic rubbers with reactive functionality can be prepared by several methods. End-functional oligomers are preferred. Chains attached to the network at only one end do not contribute as much strength to the network as those attached at both ends [34], Urethane chemistry is a handy route to such molecules. A hydroxy-terminated oligomer (commonly a polyester or a polyether) can be reacted with excess diisocyanate, and then with a hydroxy methacrylate to form a reactive toughener [35]. The methacrylate ends undergo copolymerization with the rest of the acrylic monomers. The resulting adhesive is especially effective on poIy(vinyl chloride) shown in Scheme 2. 

A hydroxy-terminated oligomer can be converted into a carboxy-terminated one by reaction with an anhydride [37]. Such an oligomer can also be used to synthesize a methacrylated rubber as above [38]. 

Hie most representative member of this class of polyesters is the low-molar-mass (M 1000-3000) hydroxy-terminated aliphatic poly(2,2/-oxydiethylene adipate) obtained by esterification between adipic acid and diethylene glycol. This oligomer is used as a macromonomer in the synthesis of polyurethane elastomers and flexible foams by reaction with diisocyanates (see Chapter 5). Hydroxy-terminated poly(f -caprolactonc) and copolyesters of various diols or polyols and diacids, such as o-phthalic acid or hydroxy acids, broaden the range of properties and applications of polyester polyols. 

Preparation of polyfethylene oxide) (PEO) and poly(arylene ether) based hydrophilic-hydrophobic block copolymer is of special interest because PEO has been proven to be particularly reliable and versatile for the surface modification of biomaterials. The first poly(ediylene oxide)-/ /oc/c-polysulfonc (PEO-fc-PSF) copolymers were reported by Aksenov et al.217 They employed diisocyanate chemistry to link hydroxy-terminated sulfone oligomers and polyfethylene... 

Synthesis of hydrolytically stable siloxane-urethanes by the melt reaction of organo-hydroxy terminated siloxane oligomers with various diisocyanates have been reported i97,i98) -yhg polymers obtained by this route are reported to be soluble in cresol and displayed rubber-like properties. However the molecular weights obtained were not very high. A later report56) described the use of hydroxybutyl terminated disiloxanes in the synthesis of poly(urethane-siloxanes). No data on the characterization of the copolymers have been given. However, from our independent kinetic and synthetic studies on the same system 199), unfortunately, it is clear that these types of materials do not result in well defined multiphase copolymers. The use of low molecular weight hydroxypropyl-terminated siloxanes in the synthesis of siloxane-urethane type structures has also been reported 198). 

The anionic method of polymerization is most useful for the synthesis of low molecular weight hydroxy-terminated oligomers and polymers that are to be further processed. For example, the treatment of hydroxy-terminated oligomers with isocyanates has been used to obtain polyester-urethanes (9,20), while triblock copolymers (PCL-PEG-PCL) are prepared by initiating the polymerization of e-caprolactone with the disodium alcoholate from polyethylene glycol (26). 

II. B polyethylene glycol, ethylene oxide, polystyrene, diisocyanates (urethanes), polyvinylchloride, chloroprene, THF, diglycolide, dilac-tide, <5-valerolactone, substituted e-caprolactones, 4-vinyl anisole, styrene, methyl methacrylate, and vinyl acetate. In addition to these species, many copolymers have been prepared from oligomers of PCL. In particular, a variety of polyester-urethanes have been synthesized from hydroxy-terminated PCL, some of which have achieved commercial status (9). Graft copolymers with acrylic acid, acrylonitrile, and styrene have been prepared using PCL as the backbone polymer (60). 

Hydroxy-terminated PDMS, however, has disadvantages. The monofunctional ends limit the number of connections between the polymer (or oligomer) molecule and the glass network to two. This limitation raises the possibility that some PDMS molecules are not tied at both ends to the glass network if the polycondensation does not go to completion i.e. there may be "dangling" or loose PDMS chains in the final sol-gel material. This occurance of free ends would indeed be anticipated since the extent of reaction most likely is not 100%. Hence, the physical properties, specifically the mechanical behavior of the overall material, would be expected to suffer as a result of loose PDMS chains in the system. Disregarding this potential problem, the mechanical behavior of the sol-gel hybrids are, ultimately, influenced by the mechanical behavior of the modifying elastomer ... 

Ethynyl-terminated sulfone oligomers (ETS) were prepared by end-capping hydroxy-terminated sulfone oligomers with 4-ethynyl benzoyl chloride as indicated in Eq. 8 (20). The... 

Synthesis and characterization of well-defined, a,w-terminated difunctional siloxane oligomers are discussed. Detailed procedures on the preparation of primary amine- and hydroxy-terminated oligomers are given. Control of the average molecular weight (Mn) and also the possible variations in the backbone structure and composition are explained. The effect of these variations on the physical, thermal and chemical properties of the resulting materials are discussed. Characterization of these oligomers by FT-IR, NMR and UV spectroscopy, potentiometric titration and DSC are summarized. 

GPC studies. The H-NMR spectrum of the hydroxy terminated oligomer with Mn 1000 is given in Figure 2. The position of the peaks, as marked on the spectrum and the relative ratio of integrations, confirm the formation of the predicted oligomer structure. 

Hydroxy-terminated polybutadiene (8) (HTPB) has been treated with dinitrogen pentoxide in methylene chloride. The product (9) is an energetic oligomer but is unlikely to find application because of the inherent instability of /3-nitronitrates." Initial peroxyacid epoxidation of some of the double bonds of HTPB followed by reaction with dinitrogen pentoxide yields a product containing vtc-dinitrate ester groups and this product (NHTPB) is of much more interest as an energetic binder (see Section 3.10)." ... 

Polyolefins with vinyl end groups can be readily transformed into end-functionalized polyolefins by post-polymerization functionalization to yield a wide variety of end-functionalized polyolefins, which include epoxy-, amine-, and hydroxy-terminated polyolefins. Brookhart, Gibson, and co-workers reported on diimine-pyridine-ligated Fe complexes incorporating sterically less hindered alkyl substituents such as a methyl group ortho to the imine-A s, F12-1, that selectively converted ethylene to oligomers, affording linear a-olefin mixtures (>99%) (see also Section... 

For the LLA/530 PCL and LLA/2K PCL systems, the number-average molecular weight and Tg values are progressively reduced as the presence of CL is enhanced. These results stem from the increased availability of hydroxy-terminated species to initiate the polymerization of LLA as the amount of PCL oligomer is increased. In accord with this observation, while a simultaneous reduction of Tg with a decrease in number-average... 

Recently, a,co-bis-hydroxy-terminated poly(l,3-propylene succinate) has been chain-extended to yield high molecular weight poly(ester-carbonates) [44] using a bischloroformate route. Thus, using a molar ratio of 1,3-propanediol to succinic acid of 1.02, an oligomer having Mn of 2,200 and Mw of 3,000 was ob-... 

US 5,028,681 (American) 1991 Novel poly(imide siloxane) block copolymers and process for their preparation General Electric EN Peters Injection moldable block copolymers with high IV and excellent chemical/physical properties. Blends useful for impact modification Novel siloxane-imide block copolymers and a process for their preparation are covered. The method involves reacting a hydroxy-terminated polyimide oligomer with a siloxane oligomer with dimethylamino, acetyl or chlorine end-groups... 

Condensation reactions of silanols provides another method for polysiloxane synthesis. Hydroxy-terminated siloxane oligomers or polymers can be further condensed to polymers of higher molecular weight by condensation with loss of water (equation 23). This reaction is catalyzed by various metal salts tin salts have been widely used. Mixtures of two different a, co-dihydroxysiloxane oligomers may be condensed to give block copolymers. 

Hydroxy-terminated siloxane oligomers are mixed with trialkoxysUanes catalysis by Sn + leads to condensation and cross-linking through Si-O-Si bonds, with loss of ethanol (equation 25). 

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