Synthesis and trans-ureation of N,N’-diphenyl-4,4′-methylenediphenylene biscarbamate with diamines: a non-isocyanate route (NIR) to polyureas

Chen, Hsueh-Yung; Pan, Wen-Chen; Lin, Chao-Hsing; Huang, Chun-Ying; Dai, Shenghong A.

doi:10.1007/s10965-011-9754-8

Cited by 22 publications

(19 citation statements)

References 22 publications

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“…In addition, highly basic sodium methoxide was used for promoting the trans-esterification reactions. These deficiencies were confirmed in our laboratory [10] indicating that only low molecular weight of polyurea could be isolated due to subsequent product degradation [11].…”

Section: Introductionmentioning

confidence: 53%

Solvent-free processes to polyurea elastomers from diamines and diphenyl carbonate

Pan

Liao²,

Lin

et al. 2015

J Polym Res

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Two solvent-free processes without using volatile organic chemical (VOC) for making polyurea elastomers have been successfully developed from diamines and diphenyl carbonate (DPC) to meet stringent public demands for a high standard green alternative Anastas and Eghbali (Chem Soc Rev 39 (1): [301][302][303][304][305][306][307][308][309][310][311][312] 2010). In this new non-isocyanate route (NIR) which is an improvement over our previous process to polyurea elastomers, molten DPC are utilized as the carbonylation agents, where DPC reacts sequentially with 1,6-hexanediamine (HDA), polyether diamines of 2000 molecular weight and short chain diamines such as isophorondiamine (IPDA) or 4,4′-diaminodicyclohexylmethane (H 12 MDA). No solvent was added in the synthesis of these new non-solvent polyurea. Alternatively, the above process was modified with an 3 % addition of a water dispersant such as 3-[(2-aminoethyl)amino]-1-propane sulfonic acid sodium salt (ESA) to make waterborne polyurea elastomers to facilitate the mixing in the preparation and in the film-making steps for the final products. In both solvent-free processes, the longchained polyether diamine and the phenol generated from the displacement reaction of diphenyl carbonate were utilized as diluents to lower the viscosities of the reaction mixtures. Unexpectedly, ultra high molecular weight products were resulted particularly for the waterborne polyurea products measuring in excess of 1,000,000 g/mol in some cases. All samples were characterized by FT-IR, H-NMR, TGA, DSC, AFM and GPC. Since the polymers were prepared under mild conditions in absence of a VOC solvent, the new products were found to mostly exist in highly phase-segregated states, exhibiting high heat-resistant temperatures with T d(5%) of well over 300°C with high elongation (>600 %) for the optimized products. Thus, this solvent-free syntheses and environmentfriendly polyurea products should find usefulness in many practical applications.

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Section: Introductionmentioning

confidence: 53%

Solvent-free processes to polyurea elastomers from diamines and diphenyl carbonate

Pan

Liao²,

Lin

et al. 2015

J Polym Res

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“…“CO 2 -based routes”: condensation of CO 2 and amines, , aminolysis of linear aliphatic, , cyclic aliphatic, , and linear aromatic organic carbonates ,, “CO 2 -based routes”: condensation of CO 2 and polyamines, ,,− carbamate metathesis or aminolysis, − aminolysis of both linear aromatic carbonates and inorganic urea. , . …”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, interesting results in PU synthesis have been achieved by the strong bases catalyzed polycondensation of CO 2 derivatives, namely organic carbamates, with diamine. ,− Although organic carbamates can be achieved by the condensation reaction of amines, CO 2 , and alcohols, the main applied synthetic procedure is through the aminolysis of organic carbonates (OCs). − Therefore, a step forward for both atom economy and process simplification is the direct synthesis of PU from OCs such as linear (dimethyl, DMC) and cyclic (ethylene and propylene) aliphatic carbonates or linear aromatic carbonate (diphenyl carbonate, DPC). − Although greener, the last approaches show some drawbacks for industrial applications. First of all, OCs generally show lower reactivity if compared to isocyanates; , then, the use of both solvents (e.g., tetramethylenesulfone or toluene) and, in most of the cases, homogeneous catalytic bases (e.g., 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diaza-bicyclo[5.4.0]undec-7-ene (DBU), 2-hydroxypyridine, and potassium methoxide or tert -butoxide) cannot be avoided. ,,− ,− In this way, we could meet difficulty in handling, recovering, and reusing the catalytic system, and lastly we cannot avoid relatively high reaction temperatures.…”

Section: Introductionmentioning

confidence: 99%

Urea and Polyurea Production: An Innovative Solvent- and Catalyst-Free Approach through Catechol Carbonate

Soccio

Mazzoni

Lucarelli

et al. 2020

ACS Sustainable Chem. Eng.

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The peculiar reactivity of catechol carbonate (CC) with amines and polyamines in both solvent-and catalyst-free conditions is herein described. In all the tests performed at room temperature, CC conversion reached 100% in a few seconds leading to the selective formation of the corresponding 2hydroxyphenylcarbamate. This compound is further rapidly converted to the disubstituted urea by the consecutive nucleophilic attack of another amine. Noteworthy, the application of this approach can be successfully extended to the one-pot bioaminebased synthesis of polyurea as herein proposed for the first time in the literature. The reaction is of general purpose for primary amines, and catechol can be easily recovered by sublimation as pure crystals ready to be recycled for the synthesis of new CC. An exception is related to the reactivity of secondary amine, which leads to the selective formation of substituted phenolic carbamates (e.g., 2-hydroxyphenyl diethylcarbamate), suitable as intermediates in medicinal chemistry.

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“…Meanwhile, Tan et al synthesized phosphorus-containing nonisocyanate TPUreas from solution polycondensation of a phosphorus-containing dicarbamate with aliphatic diamines . Dai et al synthesized nonisocyanate TPUreas through solution and solution-free polycondensation of diamines with diphenyl carbonate. − …”

Section: Introductionmentioning

confidence: 99%

Crystallizable and Tough Aliphatic Thermoplastic Polyureas Synthesized through a Nonisocyanate Route

Sang

Zhao

et al. 2016

Ind. Eng. Chem. Res.

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A simple nonisocyanate route for synthesizing crystallizable and tough aliphatic thermoplastic polyureas (TPUreas) is described. Melt transurethane polycondensation of diethylene glycol bis(3-aminopropyl) ether with bis(hydroxyethyl) hexanediurethane and bis(hydroxyethyl) isophoronediurethane was conducted at 170 °C under a reduced pressure of 3 mmHg, and a series of TPUreas were prepared. The TPUreas were characterized by GPC, FT-IR, 1 H NMR, 13 C NMR, 2D 13 C− 1 H HSQC NMR, DEPT-135 13 C NMR, DSC, TGA, wide-angle X-ray scattering, atomic force microscopy, and tensile tests. The TPUreas exhibited an M n up to 12 000 g/mol, an M w up to 17 600 g/mol, T g between 2.8 and 18.1 °C, T m from 140.5 to 149.8 °C, initial decomposition temperature of over 278.4 °C, and tensile strength up to 37.81 MPa with elongation at break of 691.25%. TPUreas with high T m , good tensile strength, and good toughness were prepared through a nonisocyanate route.

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Synthesis and trans-ureation of N,N’-diphenyl-4,4′-methylenediphenylene biscarbamate with diamines: a non-isocyanate route (NIR) to polyureas

Cited by 22 publications

References 22 publications

Solvent-free processes to polyurea elastomers from diamines and diphenyl carbonate

Solvent-free processes to polyurea elastomers from diamines and diphenyl carbonate

Urea and Polyurea Production: An Innovative Solvent- and Catalyst-Free Approach through Catechol Carbonate

Crystallizable and Tough Aliphatic Thermoplastic Polyureas Synthesized through a Nonisocyanate Route

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