Biobased non-isocyanate poly(carbonate-urethane)s of exceptional strength and flexibility

Wołosz, Dominik; Parzuchowski, Paweł G.

doi:10.1016/j.polymer.2022.125026

Cited by 12 publications

(9 citation statements)

References 56 publications

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“…In our previous studies, we proved that urea-free aliphatic and alicyclic NIPCUs could be obtained from bis(2-hydroxyalkyl carbamate)s devoid of urea groups. Moreover, the presence of OCD in the reaction mixture enabled the transformation of the urea groups into urethane ones, which was evidenced using model reactions [ 6 , 32 ]. However, here, the BHAC monomer with the 2-hydroxyethyl- or 4-hydroxybutyl carbamate groups and a high concentration of urea groups was used for the transurethane polycondensation.…”

Section: Resultsmentioning

confidence: 99%

“…Carbamates are commonly synthesized via the methoxycarbonylation of aliphatic/aromatic diamines with dimethyl carbonate [ 28 , 29 , 30 ] or aminolysis of ethylene carbonate using aliphatic diamines [ 6 , 22 , 31 , 32 ]. The products of these reactions are bis(methyl carbamate)s (BMC) or bis(2-hydroxyalkyl carbamate)s, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…The type of α,ω-diol, used during transurethanization with BMC, affects the reaction process, determines the possible occurrence of side reactions, and defines the structure of hard segments and properties of the NIPUs [ 6 , 19 , 32 , 38 ]. On one hand, the application of shorter α,ω-diol (e.g., 1,2-ethanediol) facilitates the further diffusion of low-molar-mass products during transurethane polycondensation due to its lower boiling point.…”

Section: Introductionmentioning

confidence: 99%

“…On one hand, the application of shorter α,ω-diol (e.g., 1,2-ethanediol) facilitates the further diffusion of low-molar-mass products during transurethane polycondensation due to its lower boiling point. However, the presence of 2-hydroethyl carbamate moieties accelerates the formation of urea groups via back-biting side reactions [ 6 , 31 , 32 ]. The increase in the chain length of α,ω-diol decreases the tendency to form urea groups [ 38 ].…”

Section: Introductionmentioning

confidence: 99%

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Non-Isocyanate Aliphatic–Aromatic Poly(carbonate-urethane)s—An Insight into Transurethanization Reactions and Structure–Property Relationships

Wołosz¹

2022

IJMS

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This study reveals insights into the transurethanization reactions leading to the aliphatic–aromatic non-isocyanate poly(carbonate-urethane)s (NIPCUs) and their structure–property relationships. The crucial impact of the alkyl chain length in 4,4′‑diphenylmethylene bis(hydroxyalkyl carbamate) (BHAC) on the process of transurethanization reactions was proved. The strong susceptibility of hydroxyethyl‑ and hydroxybutyl carbamate moieties to the back-biting side reactions was observed due to the formation of thermodynamically stable cyclic products and urea bonds in the BHACs and NIPCUs. When longer alkyl chains (hydroxypentyl-, hydroxyhexyl-, or hydroxydecyl carbamate) were introduced into the BHAC structure, it was not prone to the back‑biting side reaction. Both 1H and 13C NMR, as well as FT-IR spectroscopies, confirmed the presence of carbonate and urethane (and urea for some of the samples) bonds in the NIPCUs, as well as proved the lack of allophanate and ether groups. The increase in the alkyl chain length (from 5 to 10 carbon atoms) between urethane groups in the NIPCU hard segments resulted in the increase in the elongation at break and crystalline phase content, as well as the decrease in the Tg, tensile strength, and hardness. Moreover, the obtained NIPCUs exhibited exceptional mechanical properties (e.g., tensile strength of 40 MPa and elongation at break of 130%).

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Non-Isocyanate Aliphatic–Aromatic Poly(carbonate-urethane)s—An Insight into Transurethanization Reactions and Structure–Property Relationships

Wołosz¹

2022

IJMS

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“…Metal oxides, Lewis acids, and organic bases were mainly used in carbomations or transesterifications since they are able to improve the electrophilicity or nucleophilicity of carbonates or esters. [33][34][35][36][37][38][39] A catalyst screening is done in the alcoholysis of DBU with DDO (see Table 1). The polymerization was performed at 150 or 170 °C, and 40 mol% of LiCl was used to assist melting of DBU.…”

Section: Synthesis Of Pusmentioning

confidence: 99%

Non‐Isocyanate Polyurethanes by Alcoholysis of Alkyl Bisurea with Li Salt‐Assisted Melting: Synthesis and Properties

Yang

Xie

Tang

2023

Macro Chemistry & Physics

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Alcoholysis of bisureas (BUs) would be of great potential among the non-isocyanate routes for preparing polyurethanes, if the issue of the high melting temperature and the poor solubility for BUs can be solved. In this study, it is proposed to introduce Li salt to assist the melting of BUs via a eutectic system. It is found that the melting point of BUs indeed can be reduced to 170 °C or even lower by adding 40 mol% of LiCl or LiBr. In the polymerizations of BUs with diols, it is found that ZnO nanoparticles (30 ± 10 nm) are the most efficient catalyst in the catalyst screening study. Four polyurethanes are successfully synthesized and the glass transition temperature of them is detected to be 34-45 °C. PU1010 is tougher than other polymers so that it is able to be molded. The Young's modulus of PU1010 is 195.1 MPa, while the strength and the elongation at break are 36.4 MPa and 280%, respectively. The toughness calculated is 67.3 J cm −3 . This Li salt-assisted melting strategy not only realizes the synthesis of polyurethanes through alcoholysis of BUs, but can also be extended to the synthesis of other high performance polymers.

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Hybrids and Non‐Epoxy Platforms

2024

Applied Coatings

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Biobased non-isocyanate poly(carbonate-urethane)s of exceptional strength and flexibility

Cited by 12 publications

References 56 publications

Non-Isocyanate Aliphatic–Aromatic Poly(carbonate-urethane)s—An Insight into Transurethanization Reactions and Structure–Property Relationships

Non-Isocyanate Aliphatic–Aromatic Poly(carbonate-urethane)s—An Insight into Transurethanization Reactions and Structure–Property Relationships

Non‐Isocyanate Polyurethanes by Alcoholysis of Alkyl Bisurea with Li Salt‐Assisted Melting: Synthesis and Properties

Hybrids and Non‐Epoxy Platforms

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