Design, Synthesis and Actual Applications of the Polymers Containing Acidic P–OH Fragments: Part 1. Polyphosphodiesters
Abstract
:1. Introduction
2. Design and Synthesis of Polyphosphodiesters
2.1. Synthetic Approaches to Polyphosphodiesters: An Overview
2.2. Polycondensation and Related Methods
2.2.1. Reactions of H3PO4 with Diols and Polyols
- The reaction starts by the relatively slow dimerization of H3PO4 with a formation of H4P2O7 (and higher polyphosphoric acids) at 100 °C within 40 h, during this stage the water was removed either in the stream of neutral gas or azeotropically with heptane.
- After the addition of EG at 100 °C, H4P2O7 transformed to H3PO4 immediately, and the first phosphorylation reaction within additional 80 h was the formation of HOCH2CH2OP(O)(OH)2 and (HOCH2CH2O)2P(O)OH, triesters were formed in minimal amounts.
- Activation of the monophosphate esters (end groups) at any polymerization degree with H3PO4 proceeds via conversion of monoesters into pyrophosphoric acid esters –OCH2CH2OP(O)(OH)–OP(O)(OH)2 that represent reactive acidic sites.
- The polycondensation product is mostly linear with a structure of PEPA –(OCH2CH2OP(O)(OH))n–.
- Some branch points (triesters) are formed only at high temperature and prolonged polycondensation time.
2.2.2. The Reaction of Dichlorophosphates with Diols
2.2.3. Reaction of Dialkyl (or Diaryl) Phosphonates with Diols and Post-Modification
2.2.4. Polycondensation of (ω-Hydroxyalkyl)phosphonic Acids
2.3. ROP of Cyclic Phosphorus-Containing Monomers and Post-Modification
2.3.1. Synthesis of Cyclic Phosphorus-Containing Monomers
2.3.2. ROP of Cyclic Phosphorus-Containing Monomers
2.3.3. Post-Modification of the Poly(alkylene phosphonate)s
2.3.4. Post-Modification of Poly(alkylene phosphate)s
- Loss of control over polymer architecture and MWD: sterically non-hindered cyclic phosphates can form highly branched poly(alkylene phosphate)s. Switching between the ‘living’ (linear polymer, ĐM~1) and ‘immortal’ (transesterification of the polymer chain, branched polymer, ĐM > 1) ROP modes can occur at elevated temperatures and/or in case of wrong catalyst’ choice. Moreover, even in the presence of ‘good’ catalysts, complete conversion of the monomer greatly increases the risk of subsequent transesterification.
- This is why better chain control can be achieved when using sterically hindered cyclic phosphates, e.g., tBuOEP, despite its minor synthetic accessibility and very low reactivity that limits the use of this monomer in the synthesis of stat- and block-copolymers.
- The use of cyclic phosphonates eliminates the problem of branching and DPn control, but severe oxidation of the P–H bond at the final stage puts the end to a convenient option to introduce biomolecules or usable functional groups at the stages of ROP initiation or termination.
- The nature of the catalytic ROP imposes severe restrictions on the nature of the side substituent R in the molecule of cyclic phosphate (Scheme 16). So, for example, the –CH2CH2CN group, widely used in automated (!) synthesis of DNA analogs [103] and in synthesis of PCPAs with the use of ring-opening metathesis polymerization (ROMP) [104], has not found application in the ROP/deprotection approach to PCPAs, despite the fact that the synthesis of six-membered cyclic phosphate with this substituent was synthesized by Lapienis and Penczek back in 1977 [66].
- Additionally, in general, between fundamental studies of the ROP/deprotection approach to PCPAs in the late 1970s–1980s (conducted for the most part by the Penczek’ group) and relatively recent works (scientific groups of Wooley, Wurm, Iwasaki, Nifant’ev), a two-decades gap in investigations is clearly visible, which affected the progress in this scientific direction.
2.4. Metathesis Polycondensation
2.5. Other Synthetic Approaches to Polyphosphodiesters
2.5.1. The Use of Unsaturated 2-Cyanoethyl Phosphates
2.5.2. Bis(methacrylate) Phosphonates and Their Post-Modification
2.5.3. Hydrolytic Polymerization of Spiro(acylpentaoxy)phosphoranes
2.5.4. Thiol-Ene Polyaddition
2.5.5. Chain-End Vinyl Functionalization
2.5.6. The Use of Bridged Cyclic Phosphates
2.5.7. Post-Modification of Polyphosphodiesters
2.6. Sequence-Defined Oligophosphodiesters
3. Properties and Applications of Polyphosphodiesters
3.1. Physico-Chemical Characteristics of Polyphosphodiesters
3.1.1. Physical State and Mechanical Properties of Polyphosphodiesters
3.1.2. Solution and Colloidal Behavior
3.1.3. Chemical Stability of Polyphosphodiesters
3.2. Metal Complexation of the Polyphosphodiesters and Polymer-Inorganic Hybrids
3.2.1. Complexation of Polyphosphodiesters with Metal Ions
3.2.2. Effects of the Polyphosphodiesters on Crystal Growth and Morphology
3.2.3. Hybrid Nanoparticle Formation by Polyphosphodiesters
3.3. Biomedical Applications of Polyphosphodiesters
3.3.1. Polyphosphodiesters and Cell Viability/Metabolism
3.3.2. Polyphosphodiesters and Cell Differentiation
3.3.3. Polyphosphodiesters and Nucleic Acids, Proteins and Other Substances in the Body
3.3.4. Biocompatibility and Inflammatory Effect of Polyphosphodiesters
3.3.5. Bone Affinity of Polyphosphodiesters and Their Prospects for Bone Surgery
3.3.6. Drug Delivery and Drug Release with the Use of Polyphosphodiesters
- compatibilization effect of copolymers, containing polyester and PEPA block, on formation and properties of polyester/HAp composites.
- influence of PEPA on drug absorption and release by polymer/HAp composite.
3.4. Other Applications of Polyphosphodiesters
Polyphosphodiesters as Flame Retardants
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Entry | Monomer | Catalyst | Reaction Conditions/Conversion, % | Mn, kDa | DPn a | ÐM | Refs. |
---|---|---|---|---|---|---|---|
1 | iBu3Al | CH2Cl2, 20 °C | - | - | - | [65] | |
2 | iBu3Al | CH2Cl2, –20 °C, 6 h/80 | [50] | ||||
3 | iBu3Al | CH2Cl2, from 0 to 20 °C | 90 | 740 | - | [22,76] | |
4 | tBuOK | THF, 20 °C, several days/99 | - | - | - | [77] | |
5 | tBuOK | C6H6, 20 °C, several days/99 | - | - | - | [72] | |
6 | iBu3Al | CH2Cl2, from –20 to 20 °C | 30–100 | - | - | [22] | |
Et2Mg | CH2Cl2, from –20 to 20 °C | 30–100 | - | - | [22,67] | ||
DBU/TU | CH2Cl2, 20 °C, 15 min/83 | 9.2 | 68 | 1.17 | [62] | ||
DBU/TU | CH2Cl2, 0 °C, 1.4 h/92 | - | 97 | - | [78] | ||
Mg1 | CH2Cl2, –20 °C, 5 min/99 | 9.5 | 70 | 1.35 | [62] | ||
TBD/BnOH | CH2Cl2, –20 °C, 5 min/99 | 9.3 | 68 | 1.24 | [62] | ||
TBD/BnOH | CH2Cl2, 1 eqiv. TMP, –20 °C, 5 min/99 | 6.4 | 47 | 1.13 | [79] | ||
DBU/Cholesterol | CH2Cl2, 20 °C, 5 h/ | [80,81] | |||||
7 | DBU/EtOH DBU/MeOH | 9:1 comonomer ratio, CH2Cl2/– - | - - | 38, 85, 127 73 | - - | [82] [83] | |
8 | iBu3Al | CH2Cl2, 0 °C | 25 | 119 | - | [50] | |
9 | DBU/TU BnOH | toluene, 0 °C, 10 min/80 | - | - | - | [84] | |
DBU/TU mPEG5000 | toluene, 0 °C, 10 min/80 | 7.5 | 16 | <1.2 | [85] | ||
10 | Et2Mg | C6H6, 40 °C, 10 h/80 | 25 | 139 | - | [71] | |
Mg1 | CH2Cl2, 20 °C, 18 h | 6.4 | 36 | 1.19 | [62] | ||
Mg1 | CH2Cl2, 20 °C, 18 h | – | 63 | – | [86] | ||
Mg2/mPEG5000 | CH2Cl2, 20 °C, 30 h | 3.6 | 13 | 1.45 | [87] | ||
CH2Cl2, 20 °C, 30 h | 8.1 | 49 | 1.48 | [87] | |||
11 | iBu3Al | 1:10 comonomer ratio, bulk/69.3 | 6.0–7.0 | - | - | [70] | |
TBD/BnOH TBD/ Cholesterol | 5:95–20:80 comonomer ratio, toluene 4:96 and 17:83 comonomer ratios, CH2Cl2 | 9.5–11.9 4.6; 6.4 | - - | 1.45–1.62 1.3; 1.2 | [88] [89] | ||
12 | Et2Mg | C6H6, 40 °C, 10 h/90 | 25 | 139 | n.d. | [71] | |
13 | TBD/BnOH | CH2Cl2, 0 °C, 1 min/99 | 13 | 72 | 1.17 | [90] | |
14 | Et3Al/H2O | C6H6, 40 °C/50 | - | - | - | [71] |
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Nifant’ev, I.E.; Ivchenko, P.V. Design, Synthesis and Actual Applications of the Polymers Containing Acidic P–OH Fragments: Part 1. Polyphosphodiesters. Int. J. Mol. Sci. 2022, 23, 14857. https://doi.org/10.3390/ijms232314857
Nifant’ev IE, Ivchenko PV. Design, Synthesis and Actual Applications of the Polymers Containing Acidic P–OH Fragments: Part 1. Polyphosphodiesters. International Journal of Molecular Sciences. 2022; 23(23):14857. https://doi.org/10.3390/ijms232314857
Chicago/Turabian StyleNifant’ev, Ilya E., and Pavel V. Ivchenko. 2022. "Design, Synthesis and Actual Applications of the Polymers Containing Acidic P–OH Fragments: Part 1. Polyphosphodiesters" International Journal of Molecular Sciences 23, no. 23: 14857. https://doi.org/10.3390/ijms232314857