Synthesis of polyphosphazenes with isothiocyanato, thiourethane, and thiourea side groups

Allcock, Harry R.; Rutt, J. Steven

doi:10.1021/ma00010a033

Cited by 11 publications

(7 citation statements)

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“…These incorporate primary alkyl-or arylamines, imidazole, isothiocyanates, thiourethanes, thioureas, pyrrole, or pyridine side units. [18][19][20][21][22][23][24][25] However, phosphazenes with aliphatic tertiary amines, specifically -OCH 2 -CH 2 N(CH 3 ) 2 , in the side group structure have been limited to mixed-substituent materials with less than 20% of the side groups bearing the tertiary amine, and this undoubtedly disguised some of the problems that became apparent in the present work. 26,27 The incorporation of tertiary amino units into the side groups of polyphosphazenes can, in principle, be accomplished through reaction of a chlorophosphazene such as 2 with an alkoxide, aryloxide, primary amine, or secondary amine that bears a tertiary amino residue, typically at the terminus of the reagent.…”

Section: Introductionmentioning

confidence: 86%

“…A wide range of nitrogen-functionalized phosphazenes have been designed and synthesized in recent years. These incorporate primary alkyl- or arylamines, imidazole, isothiocyanates, thiourethanes, thioureas, pyrrole, or pyridine side units. − However, phosphazenes with aliphatic tertiary amines, specifically −OCH 2 CH 2 N(CH 3 ) 2 , in the side group structure have been limited to mixed-substituent materials with less than 20% of the side groups bearing the tertiary amine, and this undoubtedly disguised some of the problems that became apparent in the present work. , …”

Section: Introductionmentioning

confidence: 87%

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Functionalized Polyphosphazenes: Polymers with Pendent Tertiary Trialkylamino Groups

et al. 1998

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Attempts have been made to synthesize polyphosphazenes with pendent tertiary amino side units via macromolecular substitution. Incorporation of -OCH2CH2N(CH3)2, -OCH2CH2OCH2-CH2N(CH3)2, and -NHCH2CH2N(CH3)2 groups was studied. Polymers in which all the side groups consisted of one type of aliphatic tertiary amino-containing unit and species that also contained 2,2,2-trifluoroethoxy or phenoxy groups as cosubstituents were examined. Related phosphazene cyclic trimers were also prepared as small molecule model systems to examine synthetic variables, characterization techniques, and hydrolytic behavior. Those phosphazenes in which the tertiary amino-containing side groups are linked to the skeleton through an aliphatic oxygen-phosphorus bond are sensitive to hydrolysis induced by the basicity of the terminal amino group. However, species in which the tertiary aminocontaining units are linked to the backbone through an alkyl nitrogen-phosphorus bond are stable to water and are candidate materials for use in a range of membrane and surface applications. Small molecule model studies also identified reactions of P-Cl bonds in (NPCl2)3 with N,N-dimethylbutylamine to form dialkylamino-substituted phosphazenes and hydrolysis products.

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Section: Introductionmentioning

confidence: 86%

Section: Introductionmentioning

confidence: 87%

Functionalized Polyphosphazenes: Polymers with Pendent Tertiary Trialkylamino Groups

et al. 1998

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“…A rough measure of polymerization reactivity can be obtained from the minimum temperature needed to generate polymer within a specific time (say 12 hours). These values are 300-350<>C for (NPF 2 )3 (34), 220<>C for (NPBr 2 )3 (39, 40), and 145°C for [NP(NCS) 2 ] 3 (37,41)f compared to about 240°C for (NPC1 2 )3.…”

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confidence: 93%

“…Cyclic phosphazenes are known that bear fluoro-(11), bromo-(12) , iodo-, isothiocyano-(13), and phosphazo (14,15) side groups. With the exception of the iodo-derivatives, which decompose on heating, all of these different classes of cyclophosphazenes undergo ring-opening polymerization to the appropriate high polymer (33)(34)(35)(36)(37)(38). However, the polymerization rates vary markedly with the type of side groups.…”

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confidence: 99%

Mechanisms and Catalysis in Cyclophosphazene Polymerization

Allcock

1992

ACS Symposium Series

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Ring-opening polymerization is one of the main access routes to heteroatom polymers such as polyphosphazenes or polysiloxanes.In the case of polyphosphazenes, a key reaction is the thermal ring-opening polymerization of (NPCl 2 ) 3 to poly(dichorophosphazene), (NPCl 2 ) n , which is the starting point for a wide range of macromolecular substitution reactions that yield stable and useful organophosphazene high polymers. The mechanism of polymerization of (NPCl 2 ) 3 is discussed, together with an extension of the polymerization to organophosphazene trimers and to heterocyclic monomers that contain carbon or sulfur as well as phosphorus and nitrogen in the ring.The broadest emphasis in polymer synthesis in the past 50 years has been placed on the polymerization of petrochemical monomers to organic polymers. However, the emerging field of inorganic-organic polymers is gaining increased attention because it provides an essential bridge between organic polymers and the broader areas of inorganic materials such as ceramics, metals, semiconductors, and superconductors.Prominent among these newer polymer systems is the growing field of phosphazene macromolecules (7). These polymers have the general structure shown in 1. They can be considered as being related to the older area of polysiloxanes (2) (2) and stucturally to polyethers such as polyaldehydes or polyketones (3).Polyphosphazenes are unique macromolecules in a number of ways. First, the inorganic backbone provides an unusually high degree of molecular flexibility (comparable to polysiloxanes). Second, the presence of equi-elemental amounts of phosphorus and nitrogen in these polymers provides a built-in resistance to burning. Third, the backbone is transparent from the near infrared to 220 mu in the ultraviolet. Fourth, the methods of synthesis allow an almost unprecedented range of organic, organometallic, or inorganic side groups to be linked to the skeleton. Different side groups alter the solubility, solvent resistance, crystallinity, glass transition temperature, optical absorption, electrical conductivity, biomedical compatibility, refractive index, and non-linear-optical response. Thus, the opportunities for

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“…On the other hand, our target poly(thiourethane) may be used as a reactive polymer4 bearing the thiol groups which are sensitive to radical sources and applied to optical materials. [5][6] In this paper, we report both the synthesis of bifunctional dithiocarbonates 5 and the polyaddition of 5 with diamines 6.…”

mentioning

confidence: 99%

Polyaddition of Bifunctional Dithiocarbonates Derived from Epoxides and Carbon Disulfide. Synthesis of Novel Poly(thiourethanes)

Moriguchi¹,

Endo²

1995

Macromolecules

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Synthesis of polyphosphazenes with isothiocyanato, thiourethane, and thiourea side groups

Cited by 11 publications

References 11 publications

Functionalized Polyphosphazenes: Polymers with Pendent Tertiary Trialkylamino Groups

Functionalized Polyphosphazenes: Polymers with Pendent Tertiary Trialkylamino Groups

Mechanisms and Catalysis in Cyclophosphazene Polymerization

Polyaddition of Bifunctional Dithiocarbonates Derived from Epoxides and Carbon Disulfide. Synthesis of Novel Poly(thiourethanes)

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