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The majority of such compounds are based on polyesters and polyamides. In contrast, their phosphorus\u2010containing counterparts are much less studied, in spite of their potential precise degradation profile and biocompatibility. Herein, the first library of poly(phosphorodiamidate)s (PPDAs) with two P\u2212N bonds forming the polymer backbone and a pendant P\u2212OR group is prepared through acyclic diene metathesis polymerization. They are designed to vary in their hydrophilicity and are compared with the structural analogues poly(phosphoester)s (PPEs) with respect to their thermal properties and degradation profiles. The degradation of PPDAs can be controlled precisely by the pH: under acidic conditions the P\u2212N linkages in the polymer backbone are cleaved, whereas under basic conditions the pendant ester is cleaved selectively and almost no backbone degradation occurs. The PPDAs exhibit distinctively higher thermal stability (from thermogravimetric analysis (TGA)) and higher glass transition and\/or melting temperatures (from differential scanning calorimetry (DSC)) compared with analogous PPEs. This renders this exotic class of phosphorus\u2010containing polymers as highly promising for the development of future drug carriers or tissue engineering scaffolds.<\/jats:p>","DOI":"10.1002\/chem.201603990","type":"journal-article","created":{"date-parts":[[2016,10,26]],"date-time":"2016-10-26T04:23:09Z","timestamp":1477455789000},"page":"17329-17338","source":"Crossref","is-referenced-by-count":42,"title":["Poly(phosphorodiamidate)s by Olefin Metathesis Polymerization with Precise Degradation"],"prefix":"10.1002","volume":"22","author":[{"given":"Mark","family":"Steinmann","sequence":"first","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Polymerforschung  Ackermannweg 10 55128 Mainz Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Manfred","family":"Wagner","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Polymerforschung  Ackermannweg 10 55128 Mainz 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