Poly adipate block copolymers

Synthetic biodegradable polymers. Poly (8)-caprolactone), used in the manufacture of seeding pots, is susceptible to hydrolysis of the ester linkage by microbes. Other materials in this category include poly(tetramethylene adipate), block copolymers of poly(ethylene succinate) and poly(ethylene glycol), and block copolymers of poly(tetramethylene glycol) and poly(ethylene succinate). Copolymers based on lactic acid have also been synthesised. 

Polyaddition reactions based on isocyanate-terminated poly(ethylene glycol)s and subsequent block copolymerization with styrene monomer were utilized for the impregnation of wood [54]. Hazer [55] prepared block copolymers containing poly(ethylene adipate) and po-ly(peroxy carbamate) by an addition of the respective isocyanate-terminated prepolymers to polyazoesters. By both bulk and solution polymerization and subsequent thermal polymerization in the presence of a vinyl monomer, multiblock copolymers could be formed. 

Recently, various polyesters such as poly(ethylene adipate), poly(tetramethylene adipate), poly(caprolac-tone), and poly(aliphatic carbonate), having terminal hydroxyl groups, were reacted with ACPC to give corresponding macroazoesters and their thermal behaviors were observed by DSC [14]. The block copolymers of these polycondensation polymers with addition polymers such as PSt and PMMA were synthesized [14]. 

While all previous examples employ enzymatic ROP, there are two reports on block copolymer synthesis employing enzymatic poly condensation. The first one was published by Sharma et al. and describes the synthesis and solid-state properties of polyesteramides with poly(dimethylsiloxane) (PDMS) blocks [21]. The polycondensation was carried out with various ratios of dimethyl adipate. 

HMX HMX HMX HMX HMX HMX HMX HMX HMX HMX HMX HMX HNS NTO NTO/HMX NTO/HMX NTO/HMX PETN PETN PETN PETN PETN PETN PETN PETN PETN PETN RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX RDX TATB/HMX Cariflex (thermoplastic elastomer) Hydroxy-terminated polybutadiene (polyurethane) Hydroxy-terminated polyester Kraton (block copolymer of styrene and ethylene-butylene) Nylon (polyamide) Polyester resin-styrene Polyethylene Polyurethane Poly(vinyl) alcohol Poly(vinyl) butyral resin Teflon (polytetrafluoroethylene) Viton (fluoroelastomer) Teflon (polytetrafluoroethylene) Cariflex (block copolymer of butadiene-styrene) Cariflex (block copolymer of butadiene-styrene) Estane (polyester polyurethane copolymer) Hytemp (thermoplastic elastomer) Butyl rubber with acetyl tributylcitrate Epoxy resin-diethylenetriamine Kraton (block copolymer of styrene and ethylene-butylene) Latex with bis-(2-ethylhexyl adipate) Nylon (polyamide) Polyester and styrene copolymer Poly(ethyl acrylate) with dibutyl phthalate Silicone rubber Viton (fluoroelastomer) Teflon (polytetrafluoroethylene) Epoxy ether Exon (polychlorotrifluoroethylene/vinylidine chloride) Hydroxy-terminated polybutadiene (polyurethane) Kel-F (polychlorotrifluoroethylene) Nylon (polyamide) Nylon and aluminium Nitro-fluoroalkyl epoxides Polyacrylate and paraffin Polyamide resin Polyisobutylene/Teflon (polytetrafluoroethylene) Polyester Polystyrene Teflon (polytetrafluoroethylene) Kraton (block copolymer of styrene and ethylene-butylene)... 

Figure 12.3 Poly(dimethyl siloxane) polyester amide block copolymers by enzymatic polycondensation of (diaminopropyl)polydimethylsiloxanes, diethyl adipate, and 1,8-octanediol [11].

Simionescu et al. [104] used poly(ethylene oxide adipate) having tosylate groups at both ends as macroinitiators for the cationic polymerization of MeOZO to produce ABA-type block copolymers. Miyamoto et al. [105] further explored the concept and prepared block copolymers consisting of poly(propylene oxide) and poly(MeOZO) by using poly(propylene oxide)-p-nitrobenzene sulfonate as a... 

PBS Copolymerization has been used to improve its properties, such as poly(ethylene terephthalate-c< -l, 4-butylene succinate) block copolymers Darwin et al. (2003), Jin et al. (2000b, c, d, 2001) Generally blended with other polyesters and compounds, such as PLA, PEO, protein, starch (TPS), and adipate copolymers Aamcr et al. (2008), (Jiua et al. (2003), Harada et al. (2007), U et al. (2008a, b)... 

Hergenrother and Ambrose have prepared butadiene-imide and butadiene-caprolactam(73,74)block copolymers using polybutadiene capped on each terminus by isocyanate groups. Poly(ethylene-propylene adipate-b-methyl methacrylate) was prepared by heating hydroxy terminated poly(methyl methacrylate) with the isocyanate terminated reaction products of hydroxy terminated poly(ethylene-propylene... 

Parent homopolymers were successfully separated from various block copolymers, for example PMMA-6-poly( -propyl methacrylate), PMMA-6-poly(n-butyl acrylate), PMMA-6-poly( -pentyl methacrylate), poly(lactic acid)-i-poly(butylene terephthalate-s /at-butylene adipate), PS-6-poly(methyl acrylate), poly(Af-virtyl pyrollidone)-6-poly(caprolactone) and others. 

Common SS include polyethers, polyesters and polyalkyl glycols with glass transition temperatures in the range of -70°to -30°C. Commonly used macrodiols in the PUs synthesis are polyalkyl-diols, such as polyisobutylene diol [70], polybutadiene (PBU) [20, 71], or oligo-butadiene diols [72] as well as hydrogenated polybutadiene diol [20] polyether diols polytetrahydrofuran (PTHF or PTMO) [50-52], polyethylene glycol (PEG) or (PEO) [73], polypropyleneoxide (PPO) [73] or mixed blocks of them PEO-PPO-PEO [74] and PPO-THF [54] polyester diols poly(ethylene adipate) (PEA) [4,20], poly(butylene adipate) (PBA) [20, 73], and latterly polycaprolactone diol (PCL or PCD) [75], polyalkylcarbonate polyol [20] or mixed blocks of them, for example poly(carbonate-co-ester)diol [76], poly(hexamethylene-carbonate)diol [77], as well as poly(hexamethylene-carbonate-co-caprolactone)diol [78] and a mixed block copolymer of polyether and polyester blocks PCL-b-PTHF-b-PCL [79]. Examples schemes of macrodiols are shown in Eig. 1.9. 

Fig. 5.27 Melting temperature against composition for block copolymers of poly(ethylene terephthalate) with ethylene succinate(l) ethylene adipate(2) diethylene adipate(3) ethylene azelate(4) ethylene sebacate(5) ethylene phthalate(6) and ethylene isoph-thalate(7). For comparative purposes, data from random copolymers with ethylene adipate and with ethylene sebacate also are given. (From Kenney (189))...

Fig. 5.28 Plot of melting temperature as a function of time for a poly(ethylene adipate), urethane linked, block copolymer heated at 250 °C. (From Iwakura, et al. (190))...

Fig. 4.5. Melting-temperature-composition relations for block copolymers of poly (ethylene terephthalate) with (1) ethylene succinate, (2) ethylene adipate, (3) diethylene adipate, (4) ethylene azelate, (5) ethylene sebacate, (6) ethylene phthalate, and (7) ethylene isophthalate. For comparative purposes data for random copolymers with ethylene adipate and with ethylene sebacate are also given. (Reproduced with permission from [16], copyright 1968, Polymer Engineering and Science.)...

Linear block copolymers of the ABA type have been prepared using hydroxyl-terminated polyoxyethylenes as starter molecules and polymerizing epsilon-caprolactone onto each end of the molecules (185). Similar ABA block, polyester/poly(alkylene oxide)/polyester copolymers were synthesized by growing polyester blocks onto preformed polyoxyethylene by means of condensation polymerization (186). The polyester blocks included 1,6-hexanediol and 1,10-decanediol adipates and azelates. 

---