Reactive Polymers Containing Hydroxyl Groups

Although amine functionalized polymers are restricted mainly to polyamides in the literature, reactive polymers containing hydroxyl groups offer more flexibility as shown in Table 2.7. Hydroxyl terminated PET and PBT have been utilized in compatibilizing a 

Polymer Reactive group Blends Reaction type Properties Reference 

PA66 Terminal amine PA66/SEBS Imidation Impact 141, 143 

PAll Terminal amine PAll/SAA Amidation Crystallization 209 

PA12 Terminal amine PA12/PS Imidation Interface 168 

---

Cross-Linked Polymers. In the 1980s, not only glass and BPA-PC but also uv-curable cross-linked polymers, eg, epoxy resins, were used as substrate material for optical mass storage disks with laige diameters (12 in., 14 in.) (219). The epoxy resins consisted of compounds containing one or several highly reactive epoxy or hydroxyl groups. The common epoxy resins (EP) mainly are reaction products of bisphenol A and epichlorohydrin ... 

The concept of PO macroinitiators centers on the introduction of an initiation moiety into an olefinic polymer chain for polymerization. The most effective route for preparing PO macroinitiators is by employing functional polyolefins containing hydroxyl groups or other reactive groups. These functional POs are prepared by copolymerization of olefins with functional monomers and post-polymerization reaction, as mentioned above. In the case where an initiation moiety was at the chain-end of the polyolefins, a block type copolymer is produced. It has been reported that thiol-terminated PP was used as polymeric chain transfer agent in styrene and styrene/acrylonitrile polymerization to form polypropylene-b/odc-polystyrene (PP-b-PS) and polypropylene-btock-poly(styrene-co-acrylonitrile) (PP-b-SAN) block copolymer [19]. On the other hand, polymer hybrids with block and graft structures can be produced if initiation moieties are in the polymer chain. 

Recently, Fossum et al. prepared several phosphine-oxide-containing monomers (Scheme 6.23).163 These monomers were used to prepare hyperbranched polymers in a typical aromatic nucleophilic substitution. However, only oligomers with M lower than 2500 g/mol were obtained. These results did not surprise us, since our previous work demonstrated that the para-hydroxyl group of the phosphonyl group is not very reactive and would require higher reaction temperatures.11... 

Another approach uses reactive alkyl halogen compounds containing a terminal carboxylate group on the other end to form spacer arms off the dextran polymer from each available hydroxyl. In this manner, Brunswick et al. (1988) used chloroacetic acid to modify the hydroxyl groups to form the carboxymethyl derivative. The carboxylates then were aminated with ethylene diamine to create an amine-terminal derivative (Inman, 1985). Finally, the amines were modified with iodoacetate to form a sulfhydryl-reactive polymer (Figure 25.14). 

Phenoxy resins can also be used for the modification of PET and PBT. Phe-noxy resins such as Paphen PKFE (Inchem Corporation) are polyhydroxyether materials with pendant hydroxyl groups that can react with the PET. Paphen phenoxy resins are reactive modifiers that can modify and upgrade brittle polymers. Such resins contain 6 % of secondary hydroxyl groups. The latter serve as reactive sites for reaction with polyesters, polyamides, polycarbonates, epoxies and phenolics. 

For example, XI will copolymerize with styrene to give a copolymer containing carbonate groups in the main polymer chain (20). Ifydrolysis gives the oligomeric polystyrene capped with reactive hydroxyl groups (2). 

There are, however, other possible routes to block copolymers successive addition of units of the reactive monomer to the polymer already present, Reaction 5 termination reactions between polymer molecules —side reactions of unknown nature lead to loss of reactive hydroxyl groups (18) possible reactions are ortho carbon-carbon coupling followed by dimerization, addition of amine or water to the ketal intermediate, etc. Block copolymers might even be formed by polymer-polymer redistribution assuming that such redistribution in polymers of greatly different reactivities (such as DMP and DPP), takes place almost exclusively in one type of polymer sequence—that is, that bond scission in a "mixed ketal such as IV occurs always in the same direction—to produce the aryloxy radical corresponding to the more reactive monomer. None of these possible sources of block copolymer can be ruled out on the basis of available evidence. All could produce homopolymer in addition to block copolymer. All of the polymers produced in this work, except for those characterized as completely random copolymers, probably contained at least small amount of one or both homopolymers. 

---