Facile synthesis of novel HTPBs and EHTPBs with high cis-1,4 content and extremely low glass transition temperature

Zhou, Qinzhuo; Jie, Suyun; Li, Bo‐Geng

doi:10.1016/j.polymer.2015.04.078

Cited by 50 publications

(47 citation statements)

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“…Starting from the previously reported aldehyde‐terminated polybutadiene (ATPB), which has controllable molecular weight and high cis ‐1,4 content, CTPB was now prepared by selective oxidation. Several oxidants, such as H 5 IO 6 /PCC, were tested, but the oxidation of CC double bonds was inevitable.…”

Section: Resultsmentioning

confidence: 99%

“…The controlled degradation of polydienes by oxidative chain scission or by metathesis of butadiene rubber and natural rubber provided another approach for the preparation of telechelic liquid rubber . In our previous studies, various HTPBs characterized by high cis ‐1,4 content, controllable molecular weight and extremely low glass transition temperature have been prepared by selective oxidolysis of commercial cis ‐polybutadiene rubber followed by reduction …”

Section: Introductionmentioning

confidence: 99%

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Facile access to carboxyl‐terminated polybutadiene and polyethylene fromcis‐polybutadiene rubber

Dai

Wang

et al. 2018

J of Applied Polymer Sci

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Carboxyl-terminated polybutadiene (CTPB) is a widely used telechelic liquid rubber, which is mainly prepared by anionic or free-radical polymerization of 1,3-butadiene. It is known that the microstructure of liquid polybutadiene rubber largely affects its processability and mechanical properties. However, it is hard to control its microstructure in the free radical or anionic polymerization. In this study, a series of CTPB with high cis-1,4 content has been prepared for the first time via the oxidolysis and selective oxidation of cis-polybutadiene rubber (BR). Hydrogenation of their C C double bonds with p-toluenesulfonyl hydrazide/tri-n-propylamine (TSH/TPA) reagents afforded carboxyl-terminated polyethylenes (CTPE). For comparison, commercial CTPB (FCTPB), prepared by free-radical polymerization of 1,3-butadiene, was also hydrogenated and gave FCTPE with more ethyl branches. Linear CTPE (L-CTPE) was synthesized by ring-opening metathesis polymerization of 1,5-cyclooctadiene in the presence of maleic acid and subsequent hydrogenation. The microstructure of the polymers was established by FT-IR, 1 H NMR, 13 C NMR, and GPC and their thermal properties were determined by DSC and TGA.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Facile access to carboxyl‐terminated polybutadiene and polyethylene fromcis‐polybutadiene rubber

Dai

Wang

et al. 2018

J of Applied Polymer Sci

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“…Dispersed second phase particles lead to a lower crosslinking density of DGEBA–EDA and therefore the decrease in storage modulus at lower temperature and some similar reports support these results – . In addition, EDA is a small molecule amine, the chain movement of DGEBA/EDA is more sensitive to the temperature elevation and thus fast decline in storage modulus upon heating; AMALPB is also aliphatic amine while it possesses much larger molecular weight (as shown in Figure ), the chemical bond between the interface of AMALPB and DGEBA/EDA restricts the mobility of interfacial zones surrounding rubber particles, and therefore slows down the decline in their storage moduli upon heating to temperature above 60 °C. Accordingly, these macromolecular chain movements with temperatures called primary α relaxation are more clearly observed in their loss factor (tan δ) against temperature diagram as presented in Figure (b) .…”

Section: Resultsmentioning

confidence: 99%

Preparation and characterizations of RTV epoxy blends using amide maleic anhydride‐g‐liquid polybutadience as both reactive toughening and curing components

Wang

2017

J of Applied Polymer Sci

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Amide maleic anhydride‐g‐liquid polybutadience (AMALPB) was synthesized using maleic anhydride‐g‐liquid polybutadience (MALPB) with ethylenediamine (EDA), and its structure was confirmed by FTIR and 1H‐nuclear magnetic resonance spectra, respectively. It was then used as a reactive toughening agent to make blends with diglycidyl end‐capped poly(bisphenol‐A‐co‐epichlorohydrin epoxy cured at room temperature. Their thermal decomposing behaviors did not show much difference because both EDA and AMALPB possessed similar aliphatic groups. All their glass transition temperatures (Tg) increased more than 10 °C than that of the neat epoxy, and with the addition of AMALPB, the blends were greatly strengthened upon heating as show from their storage moduli. When AMALPB was added at 10 wt %, its elongation at break increases to a maximum of 8.8% which was about two times higher than that of the neat epoxy, and its tensile strength also increased. However, the excessive addition of AMALPB resulted in an apparent decline in their tensile strength at content above 20%. The simultaneous improvements in both tensile strength and strain were attributed to the existence of well‐dispersed rubber particles in the continuous matrices performing plastic deformation that resulted from the chemical bonds of interfaces among the rubber particles and matrix, and meanwhile, inducing the deflection of the cracks. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45985.

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“…[1]. However, up until now, most crosslinking reactions of polybutadienes still focus on the polyurethane reaction between hydroxyl terminal polybutadiene (HTPB) and isocyanate compounds [2,3]. However, the reaction typically comes with some disadvantages, such as the sensitivity to water and stringent reaction conditions, which easily raise defective network structures and adversely affect their mechanical properties [4].…”

Section: Introductionmentioning

confidence: 99%

Preparation, Characterization of Propargyl Terminal Polybutadiene and Its Crosslinked Elastomers Properties

2020

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Propargyl terminal Polybutadiene (PTPB) was successfully prepared through hydroxyl terminal polybutadiene (HTPB) end-capping modification. The FTIR and 13 C NMR results indicated that the HTPB terminal hydroxyl was thoroughly replaced and yielded the target product, PTPB, with a theoretical propargyl content of 0.66 mmol g −1 . In comparison with HTPB, PTPB has a lower viscosity. Using 1,6-diazide hexane as a curing agent, polytriazole crosslinked polybutadiene (PT ri PB) elastomers with various functional molar ratios (R) were prepared by CuAAC reaction, and the glass transition temperatures of the resultant PT ri PB elastomers were approximately −75 • C, measured by differential scanning calorimetry (DSC), nearly independent of elastomer R values. Mechanical tests indicated, that with the increase in R, the mechanical properties of PT ri PB elastomers exhibit a parabolic dependence on R. In addition, the thermal stability of PT ri PB elastomers were also studied. The findings revealed some fundamental features of polytriazole crosslinking elastomer prepared by CuAAC reaction.Polymers 2020, 12, 748 2 of 11 complex of CuBr and PMDETA (n,n,n ,n ,n -pentamethyldiethylenetriamine) as a catalyst. Under a nitrogen atmosphere, the mixture solution was stirred at ambient temperature for 1.5 h, achieving a hydroxyl-containing double-chain polymer [10]. Similarly, Shingu first dissolved CuBr and PMDETA in DMF (dimethylformamide) solvent, and then a solution of triazido-triethynyl-containing polymer in DMF was added into the solution, using a syringe pump, at an extremely slow rate, at 100 • C, under a nitrogen atmosphere. By the intramolecular CuAAC reaction, a µ-ABC tricyclic miktoarm star polymer was prepared [11].Unlike solution reactions, conventional cuprous catalysts for CuAAC reactions are not fit for the polymer bulk reaction. Moszner mixed multifunctional azides, alkynes and copper (II) acetate together and realized CuAAC bulk step-growth copolymerization in virtue of copper (II) acetate photoreduction under the light irradiation [12]. Schubert directly used CuOAc as the catalyst, and bulk polymerized multifunctional alkynes and azides through CuAAC reaction, and obtained a series of step-growth polymers [13]. However, these polymers contain a great quantity of triazole ring structure with a high glass transition temperature and cannot be used as elastomers. Reshmi used a little amount of cuprous iodide (CuI) solution of acetonitrile as a catalyst and prepared a CuAAC end-crosslinked propargyl terminated polytetramethylene oxide elastomer, using glycidyl azide polymer as a cross-linker [14]. Nevertheless, the strong toxicity of acetonitrile seriously restricts its application scope.We envisioned that some cuprous organic complexes could meet the demand of miscibility with prepolymer and proper chemical stability and would be effective catalysts to bulk prepare triazole crosslinked elastomer. Moreover, we found that a copper(I) hexafluoroacetylacetonate cyclooctadiene complex can decrease the activation energy of ...

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Facile synthesis of novel HTPBs and EHTPBs with high cis-1,4 content and extremely low glass transition temperature

Cited by 50 publications

References 35 publications

Facile access to carboxyl‐terminated polybutadiene and polyethylene fromcis‐polybutadiene rubber

Facile access to carboxyl‐terminated polybutadiene and polyethylene fromcis‐polybutadiene rubber

Preparation and characterizations of RTV epoxy blends using amide maleic anhydride‐g‐liquid polybutadience as both reactive toughening and curing components

Preparation, Characterization of Propargyl Terminal Polybutadiene and Its Crosslinked Elastomers Properties

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