Stable heterocumulene monomer in water; Synthesis and polymerization of (meth)acrylates having an isothiocyanate structure

Abstract

Novel methacrylate and acrylate monomers having an isothiocyanate structure, 2-isothiocyanatoethyl methacrylate (ITEMA) and 2-isothiocyanatoethyl acrylate (ITEA), were synthesized, and their radical polymerizations were examined, respectively. ITEMA and ITEA were synthesized by addition of carbon disulfide to 2-aminoethyl methacryrate or 2-aminoethyl acrylate, followed by treatment with ethyl chloroformate. Radical polymerizations of the obtained monomers (ITEMA, ITEA) were carried out methyl ethyl ketone using 2,2'-azobisisobutyronitrile (AIBN) as an initiator to obtain the corresponding polymers. The glass transition temperatures of the poly-ITEMA and poly-ITEA were determined to be 55 and 2 C by differential scanning calorimetry, respectively. The 5 wt % decomposition temperatures of the poly-ITEMA and poly-ITEA were determined to be 277 and 269 C by thermogravimetric analysis, respectively. Isothiocyanato groups in the monomers did not react with water in acetone solution at 60 C for 24 h to be tolerable to water.

Selective nucleophilic additions to poly(methacrylate)s containing isothiocyanate moieties in the side chains and their application in cross-linking

“…Polymer 1 was prepared from compound 6 according to the reported procedures . 2,2′‐Azobis(isobutyronitrile) (AIBN) was purchased from Wako Pure Chemical Industry (Osaka, Japan) and purified by recrystallization from methanol.…”

“…Recently, we reported synthesis and polymerization of methacrylic, acrylic, and styrene monomers having an isothiocyanato structure, 2‐isothiocyanatoethyl methacrylate ( ITEMA , 6 ), 2‐isothiocyanatoethyl acrylate ( ITEA ), and 4‐vinylbenzyl isothiocyanate ( VBIT ) to obtain the corresponding homopolymers, poly‐ITEMA ( 1 ), poly‐ITEA, or poly‐VBIT . We examined the reactivity of isothiocyanates and found that isothiocyanate is less reactive toward water, alcohol, and carboxylic acid than the corresponding isocyanate.…”

Synthesis of polydithiourethanes and their thermal, optical, and mechanical properties originated from monomers structure

“…On the other hand, the diisothiocyanates, which are less reactive toward several nucleophilic agents and more stable in ambient moisture and air atmosphere than that of the diisocyanate, can be used for the polyaddition of various diols, diamines, and dithiols as well as the diisocyanates . The polyaddition of diisothiocyanates with diols and/or diamines affords polythiourethanes and/or polythioureas, which are especially utilized as the optical materials due to high refractive index and transparency .…”

Synthesis and polymerization of styrene monomer carrying isothiocyanate moiety and its copolymerization with HEMA based on chemo-selectivity to nucleophiles

“…There are some report for the polymer bearing isothiocyanate, and the synthesis and polymerization of 4‐(isothiocyanate) styrene was reported in litaratures . This monomer can be synthesized from 4‐amino styrene by the use of CS 2 or thiophosgene which is not desirable from the environmental standpoint .…”