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This research focuses on synthesis and modification of polyol precursors derived from cis-1,4-polyisoprene (PI). These new polyol precursors can be converted to high value-added polyurethane (PU). The epoxidized hydroxytelechelic PI (EHTPI) prepared by chemical modification from PI was used as starting material for polyol synthesis. 1,3-Dipolar cycloaddition between a terminal alkyne and an azide has rapidly become the most popular click reaction. We applied this reaction to couple azide-functionalized PI and alkyne-functionalized sugar for preparing polyols. For azide functionalization, 1-methyl epoxidized cyclohexane was used as a model molecule, and various conditions for epoxide ring opening of 1-methyl epoxidized cyclohexane and EHTPI were investigated. The cycloaddition of alkyne and azide was carried out in the presence of sodium ascorbate and copper sulfate. The polyol precursors obtained might be used to prepare biodegradable polyol PU.

Biodegradable polyurethane was synthesized using poly(DL-lactic acid) diol and hydroxytelechelic natural rubber as hydroxyl containing precursor, 1,4-butane diol as chain extender, isophorone diisocyanate and dibutyltin dilaurate as catalyst. Poly(DL-lactic acid) diol was prepared by condensation polymerization of DL-lactic acid using 1,4-butane diol as initiator and stannous octoate as catalyst. Hydroxyltelechelic natural rubber synthesized via oxidative degradation of natural rubber and then reduced carbonyl end group to hydroxyl group. Chemical structure of products was characterized by 1H-NMR. Molecular weight and polydispersity determined by SEC. Thermal properties was characterized by DSC and TGA. Segmented polyurethane show two Tgs and two degradation steps corresponding to natural rubber and poly(DL-lactic acid) segment. Polyurethane containing poly(lactic acid) more than 40%mol are become brittle. This result caused by brittle characteristic of PLA. Moreover, mechanical properties increased as content of PLA increased.

New photosensitive oligoisoprenes were synthesized by controlled degradation of high molecular weight cis-1,4-polyiso- prene and successive chemical modification of the chain-ends. Oligomers with diacrylate extremities were synthesized, characterized, and used in photocrosslinking reactions in different conditions. The photoinitiated polymerization of the diacrylate oligoisoprenes was carried out using 2,2-dimethyl-2-hydroxyacetophenone (Darocur 1173) as initiator and the reaction was monitored by photoca- lorimetry-DSC and real time FTIR spectroscopy. The influence of oxygen, photoinitiator concentration, light intensity, diluting agent, and oligomers molecular weight on the reaction rate was investigated. It was found that the presence of oxygen does not influence the photopolymerization kinetics of the diacrylate oligoisoprenes. Maximum conversion was obtained for a photoinitiator concentra- tion of 5% (w/w) and for a light intensity of 13.5 mW/cm 2 . Decreasing the formulation viscosity by addition of a diluent (1,6-hexa- nediol diacrylate) raised the photopolymerization rate, by increasing the reactive species mobility. V C 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 000: 000-000, 2012

Presently, the disposal of thousands of tons of waste tyres produced every year in the whole world is a major environmental problem. Since tyre rubbers do not decompose easily on account of crosslinking and stabilizers, the processing of the waste tyre rubber constitutes a significant technical challenge. This work describes the use of periodic acid for the controlled one-pot oxidative cleavage of carbonyl telechelic cis -1,4-oligoisoprenes (CTNR) and natural rubber (NR) as model compounds and the application of this method to the degradation of ground waste tyre rubber. Average molecular weight analysis of the degraded material indicates that the reaction time and the periodic acid quantity can be used to control the degree of breakdown; we obtained materials in the average molecular weight range of 700–5000 g mol −1 . The processed material shows ketone and aldehyde groups at the chain ends. Degradation studies of waste tyre rubbers were also carried out using this oxidative cleavage by periodic acid, to achieve carbonyl telechelic oligomers. Well-defined structures were obtained with an average molecular weight from 3000 to 7000 g mol −1 according to the periodic acid/waste tyres rubber ratio used.

A new type of polyurethane (PU) has been synthesized by using hydroxyl terminated liquid natural rubber (HTNR) and poly(e-caprolactone) (PCL) as a soft segment and toluene-2,4 diisocyanate (TDI) as a hard segment. This PU becomes a biodegradable and recyclable polymer. The PU samples were synthesized by solution polymerization. TDI/PCL polymerization was prepared in order to determine the appropriate NCO:OH ratio which evaluated from the molecular weight of derived PU and the ratios which were able to form a polymeric film. The suitable NCO:OH ratios were 0.84:1 – 1.20:1 and the Mn of the derived PUs was 3000-5500 g/mol determined by using GPC. PU from PCL-HTNR block copolymer was synthesized by varying molar ratio between PCL and HTNR. HTNR has been synthesized by epoxidation reaction and chain cleavage of natural rubber. The Mn of HTNR was in the range of 1700-8000 g/mol. 1H-NMR and FTIR were used to determine the functional group in order to verify the prepared HTNR and PU. Glass transition temperature and thermal decomposition of PU samples were investigated by using DSC and TGA, respectively.

A new trithiocarbonate functionalized cis-1,4-polyisoprene was obtained from oxidative degradation of natural rubber followed by reductive amination and amidation. The structure of the resulting functionalized cis-1,4-polyisoprene was confirmed by a combination of 1H NMR spectroscopy, 13C NMR spectroscopy, MALDI-TOF mass spectrometry and FTIR spectroscopy. 1H NMR spectroscopy showed that the trithiocarbonate functionality was equal to one. The well-defined trithiocarbonyl-end functionalized cis-1,4-polyisoprene was used as a macromolecular chain transfer agent (macroCTA) to mediate the RAFT polymerization of t-BA using AIBN as the initiator ([t-BA]0/[macroCTA]0/[AIBN]0 = 250/1/0.2) in toluene at 60 °C. The resulting PI-b-P(t-BA) diblock copolymer presents an unimodal SEC trace shifted toward higher molecular weight in comparison with the SEC trace of the macroCTA, indicating that the polymerization of the second block is effective. The characteristics of the copolymer were determined by SEC ( M ¯ n = 26,000 g mol−1, PDI = 1.76) and 1H NMR spectroscopy ( DP ¯ n (PI) = 62 and DP ¯ n (P(t-BA)) = 87).

A novel linker for the immobilisation of alcohols on solid support is described. This linker can be cleaved either enzymatically using penicillin amidase, or by very mild acid hydrolysis using 10% TFA.

Waterborne polyurethane (WPU) has its main applications in coatings and adhesives. Compared with the competing PU products from solvent-based processes, it has a more environmentally friendly manufacturing process. Its economic competitiveness could also be improved by the use of aromatic isocyanates that are widely available and cheaper than the currently used aliphatic isocyanates. We report on the synthesis and properties of WPU, based on natural rubber (NR) whose molecular structure has been altered, in combination with an aromatic isocyanate. The NR modification is by hydroxyl termination, with experiments using two chain lengths (HT600 and HT1000, named after molecular weight). The aromatic isocyanates used are 4,4’-Methylene bis (phenyl isocyanate) (MDI) and polymethylene polyphenyl polyisocyanate (p-MDI). The synthesized chemical structure is characterized using ATR-FTIR, while the key material properties reported here are the pH value, mean particle size and size distribution, and glass transition temperature. The WPU achieved suitable material properties, with small particles sizes and good dispersion, for applications in coatings.

We investigate the one-pot synthesis of a new α,ω-bistrithiocarbonyl-end functionalized telechelic cis-1,4-polyisoprene (Pip) via metathesis degradation from natural rubber (NR) in the presence of the Grubbs second generation catalyst (GII) and a bistrithiocarbonyl-end functionalized olefin as a chain transfer agent (CTA). When the metathesis degradation of the NR of 2 × 10 6 g mol ―1 molecular weight is performed in toluene at 25 °C using the ratio of [Ip] 0 /[GII] 0 /[CTA] 0 = 100/1/1 (Ip = isoprene units), a cis-1,4-polyisoprene of 14000 g mol ―1 after 4 h is obtained. The functionality estimated by 1 H NMR spectroscopy is equal to 1.5 ± 0.1. The structure of telechelic cis-1,4-polyisoprene was confirmed by combination of 1 H NMR. 13 C NMR spectroscopy and FTIR. The influence of the CTA concentration was investigated. It was found that using higher concentrations of CTA ([Ip] 0 /[GII] 0 /[CTA] 0 of 100/1/2 and 100/1/5) lead to form a perfectly telechelic cis-1,4-polyisoprene with a functionality of 2 with no significant difference in M n values (approximately 6400 g mol ―1 ) and in polydispersity indices (∼1.70). The new well-defined α,ω-bistrithiocarbonyl-end functionalized telechelic cis-1,4-polyisoprenes were used successfully as macromolecular chain transfer agents (macroCTAs) to mediate the RAFT polymerization of t-BA using AIBN as the initiator ([t-BA] 0 /[macroCTA] 0 /[AIBN] 0 = 500/1/0.4) in toluene at 60 °C leading to well-defined P(t-BA)-b-PIp-b-P(t-BA) triblock copolymers.

The synthesis of the first vinyltetrazine derivative is ­described. 3,6-Divinyl-1,2,4,5-tetrazine was obtained following a methodology involving cyclization from an imidate and use of 2-phenylsulfonylethyl groups as masked vinyl entities. The first properties of this unique compound are reported.

International audience; The synthesis of the first vinyltetrazine derivative is ­described. 3,6-Divinyl-1,2,4,5-tetrazine was obtained following a methodology involving cyclization from an imidate and use of 2-phenylsulfonylethyl groups as masked vinyl entities. The first properties of this unique compound are reported.