Poly terpolymer synthesis

An allyl samarocene catalyst, [(CMe2C5H4)2SmCl(C3H5)MgCl2(THF)4, was employed for the synthesis of trans-Vl-b-VCL copolymers and poly(fra s-isoprene-co-hex-l-ene)-fr-PCL terpolymers [111]. The copolymerizations... 

The triblock terpolymer polypropylene oxide)-h-poly[2-(dimethylami-no)ethyl methacrylate]-b-poly[oligo(ethylene glycol) methacrylate], PPO-fc-PDMAEMA-fc-POEGMA, was prepared using the PPO macroinitiator followed by the addition of CuCl, HMTETA, and DMAEMA for the polymerization of the second block and finally OEGMA for the synthesis of the final product (Scheme 54) [128]. 

By utilizing a combination of RAFT and cationic ROP, the synthesis of [poly(methyl methacrylate)][poly(l,3-dioxepane)][polystyrene] miktoarm star terpolymers was achieved [182], The approach involved the synthesis of PS functionalized with a dithiobenzoate group by RAFT polymerization and subsequent reaction with hydroxyethylene cinnamate (Scheme 98). The newly created hydroxyl group was then used for the cationic ring opening polymerization of 1,3-dioxepane (DOP). The remaining dithiobenzoate group was used for the RAFT polymerization of methyl methacrylate. 

Copolymeirization provides an unique approach to the synthesis of polyfunctional stabilizers. E.g. terpolymers of 4-isopropenyl-2,6-di-terr-butylphenol, methyl methacrylate and 2-(2-hydroxy-5-isopropenyl)-2H-benzotriazole or poly[4-(2,2,6,6-tetramethylpiperidyl) methacrylate-co-4-hydroxy-3,5-di-tert-butyl-benzyl methacrylate] (96), having M 5,400, posses properties of AO and LS [108]. 

Polymerization Catalysed by Acids and Bases. Carbonium ions and carbanions respectively are carriers of the chain transfer in cationic and anionic polymerizations respectively. Ionic polymerization mechanism was exploited for the synthesis of polymeric stabilizers in comparison with the free-radical polymerization only exceptionally. The cationic process was used for the synthesis of copolymers of 2,6-di-tert-butyl-4-vinylphenol with cyclopentadiene and/or for terpolymers with cyclopentadiene and isobutylene [109]. System SnCWEtsAlCla was used as an initiator. Poly(lO-vinylphenothiazin) was prepared by means of catalysis with titanium chlorides [110]. Polymers of 4-[a-(2-hydroxy-3,5-dimethylphenyl)ethyl]-vinylbenzene [111] and 3-allyl-2-hydroxyacetophenone [112] were also prepared under conditions of cationic polymerization. 

Scheme IV. Synthesis of poly(ether-imide-siloxane) elastoplastic terpolymers.

Catalysts based on the Hf pyridyl amine complexes 126-128 have been used for the preparation of ethylene/ propylene co-polymers as well as of ethylene/propylene/l-octene terpolymers. These co-polymers are characterized by having at least 60 wt% propylene units, Mw around 300000, and Mw/Mn in the range 2.0-2.4. The NMR analysis of these co-polymers showed that the propylene sequences are remarkably isotactic mm > 90%) and showed the presence of regioirregularly inserted propylene units(<0.5% mol). The most interesting property of catalysts based on 126-128 is their high thermal stability.1119 Using modifications of isospecific bis(phenoxy-amine)-based catalysts, such as complex 164, the controlled synthesis of iPP- /orjf-poly/E-co-P) diblock co-poly-mers has been achieved. This is a remarkable result since iPP and PE are both polymeric materials of extreme industrial relevance.1206... 

Star terpolymers of the ABC2, ABC4 and AB2C2 were synthesized, where A, B and C are PS, PI and poly(Q -methylstyrene)(PaMeS), respectively. As an example, the reactions used for the synthesis of one of the most complex star architectures, (PS)(PI)2(P(zMeS)2, are given in Scheme 96. 

Kawaguchi and coworkers at Teijin have prepared a series of polymers based on poly(diallyl amine), its copolymer with sulfur dioxide, and various terpolymers.39 The chemistry of this polymer synthesis is shown below. The patent description shows the diallylamine polymers to be polypiperidine (six-membered ring) derivatives, but there are a number of publications that show this monomer to produce preferably polypyrrolidine (five-membered ring) structures ... 

Materials. The synthesis of poly[ (trifluoroethoxy) (octafluoropent-oxy)(X)phosphazene] (X = crosslink site) terpolymer has been described in previous publications (1,14). Bis(8-oxyquinolate)zinc(II) was synthesized according to the procedure described in an earlier publication (5). 

In contrast, the order of monomer addition is critical among monomers with different reactivities. As described in Section 5.1, a more-reactive chain-end anion is produced by a less-reactive monomer, and vice versa. Accordingly, less-reactive monomers should first be polymerized, followed by the polymerization of more-reactive monomers. In the block copolymer of styrene and MMA, for instance, it is necessary first to polymerize styrene, after which MM A is polymerized to prepare the second block, as the chain-end enolate anion produced by MMA cannot initiate the polymerization of styrene. Similarly, and for the same reason, the synthesis of P(2)-b-PMMA is possible only by the addition of 2-vinylpyridine first, and then MMA. For the successful design and synthesis of block copolymers, the pJ values of the conjugated acids of chain-end anions, as well as the e- and a-values of monomers (as mentioned above) are valuable guides. The details of almost all block copolymers synthesized to date, using living anionic polymerization, have been summarized by Quirk and Hsieh [190]. With the monomer addition order in mind, ABC triblock terpolymers composed of PS (A), PB (B), and PMMA (C), as well as PS (A), poly(2-vinylpyridine) (P(2VP)) (B), and P BMA (C), could be successfully... 

The synthesis of a cydic triblock terpolymer, polystyrene-b-polyisoprene-b-poly(methyl methacrylate), was achieved by an end-to-end intramolecular amidation reaction of the corresponding linear a,o)-amino acid precursor [S-b-I-b-Methyl methacrylale (MMA)] under high-dilution conditions. The linear precursor was synthesized by the sequential anionic polymerization of styrene, isoprene, and MMA with 2,2,5,5-tetramethyl-l-(3-lithiopropyl)-l-aza-2,5-disilacydopentane as an initiator and 4-bromo-l,l,l-trimethoxybutane as a terminator. The separation of the unreaaed linear polymer from the cydic terpolymer was fadli-tated by the transformation of the tmreacted spedes into high-molar-mass polymers under high-concentration conditions. The SEC-estimated yield for the final cyclic terpolymer of molar mass of about lOOOOgmor was 90%. 

Park et al, reported the synthesis and application of terpolymer bearing cyclic carbonate and cinnamoyl groups. The syntheses of photopolymer with pendant cinnamic ester and cyclic carbonate groups was achieved by the addition reaction of poly(glycidyl methacrylate-co-styrene) with CO2 and then with cinnamoyl chloride. Quaternary ammonium salts showed good catalytic activity for this synthesis. Photochemical reaction experiments revealed that terpolymer with cinnamate and cyclic carbonate groups has good photosensitivity, even in the absence of sensitizer. In order to expand the application of the obtained terpolymer, polymer blends with poly(methyl methacrylate) were also prepared. 

The synthesis and characterization of polystyrene-6-poly(ethylene oxide)-6-poly(e-caprolactone) triblock terpolymers in a linear or star shaped fashion is very interesting because they combine in the same molecule a glassy amorphous block, polystyrene a biocompatible crystalhzable poly(ethylene oxide) block, and a crystalUzable poly(e-caprolactone) block, which is biodegradable and exhibits miscibility with a variety of polymers. 

Zoulalian V, Zurcher S, Tosatti S, et al. Self-assembly of poly(ethylene glycol)-poly(aIkyl phosphonate) terpolymers on titanium oxide surfaces synthesis, interface characterization, investigation of nonfouling properties, and long-term stability. Langmuir January 2010 26(l) 74-82. 

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