Rheological properties of phosphorus-containing oligoester(meth)acrylate for processing by vacuum infusion

Objectives. To obtain polymer composite materials (PCM) with enhanced physicomechanical properties using the vacuum assisted resin transfer molding (VaRTM) method, binders must have a viscosity of up to 500 mPa∙s. In some cases, this leads to restrictions on the use of certain materials or requires the use of temporary diluents. This is closely related to the deterioration of other required composite characteristics, such as increased flammability. Three phosphorus-containing oligoester(meth)acrylates PhOEM-1, PhOEM-2, and PhOEM-3 were synthesized with significant differences in viscosity characteristics in the series PhOEM-1 << PhOEM-2 << PhOEM-3. The polymer based on PhOEM-1 exhibits inferior physicomechanical properties despite having lower viscosity. Hence, the aim of the study was to investigate the viscosity characteristics of mixtures of methacrylate binders of the same nature but different structures and functionalities. This was done by studying the rheological properties of the original oligoester(meth)acrylates and their mixtures taken in various ratios. The method used was to optimize compositions via a simplex lattice (Scheffe’s plan), in order to obtain PCM using the VaRTM technology.
Methods. The study of rheological properties of phosphorus-containing oligoester(meth)acrylates and their mixtures was conducted using the method of rotational viscometry on a Brookfield LVDV-II + Pro viscometer with a spindle 27 at different shear rates ranging from 0 to 70 s⁻¹ and temperatures from 30 to 70°C. Rheological studies were also conducted on a Lamy Rheology GT300 PLUS (GEL TIMER) viscometer in the same range of shear rates and temperatures.
Results. It was established that the objects under investigation can be characterized by viscosity values ranging from 96 to 2137 mPa∙s depending on the temperature. The nature of the viscous flow of phosphorus-containing oligoester(meth)acrylates and their mixtures is similar to that of Newtonian liquids only at certain shear rates. The effective activation energies of the viscous flow of binders and their mixtures were calculated, and the influence of temperature on the viscosity of binders was determined.
Conclusions. The study identified the features and nature of the flow curves of phosphorus-containing oligoester(meth)acrylate binders of the same nature but different structures and functionalities, as well as of their mixtures. The optimal composition ranges of threecomponent mixtures of phosphorus-containing oligoester(meth)acrylates for use in the VaRTM technological process in producing polymer composite materials within the temperature range of 30 to 70°C were defined. The optimal compositions and temperature conditions for obtaining polymer composite materials using the VaRTM technology were also identified. This enables the production of polymer products with complex geometric shapes and varying sizes.

1. Tkachuk A.I., Donetskii K.I., Terekhov I.V., Karavaev R.Yu. The use of thermosetting matrices for the manufacture of polymer composite materials by the non-autoclave molding methods. Aviatsionnye materialy i tekhnologii = Aviation Materials and Technologies. 2021;1(62):22–33 (in Russ.). https://doi.org/10.18577/2713-0193-2021-0-1-22-33

2. Kablov E.N. Innovative developments of FSUE “VIAM” SSC RF on realization of “Strategic directions for the development of materials and technologies for their processing for the period until 2030.” Aviatsionnye materialy i tekhnologii = Aviation Materials and Technologies. 2015;1(34):3–33 (in Russ.). http://doi.org/10.18577/2071-9140-2015-0-1-3-33

3. Kogan D.I., Chursova L.V., Panina N.N., et al. Advanced polymer materials with energy-efficient molding mode for structural composite products. Plasticheskie Massy. 2020;3–4: 52–54 (in Russ.). https://doi.org/10.35164/0554-2901-2020-3-4-52-54

4. Postnova M.V., Postnov V.I. Development experience outof-autoclave methods of formation PCM. Trudy VIAM = Proceedings of VIAM. 2014;4:6 (in Russ.). https://doi.org/10.18577/2307-6046-2014-0-4-6-6

5. Michels J., Widmann R., Czaderski C., Allahvirdizadeh R., Motavalli M. Glass transition evaluation of commercially available epoxy resins used for civil engineering applications. Compos. Part B: Eng. 2015;77:484–493. https://doi.org/10.1016/j.compositesb.2015.03.053

6. Merkulova Yu.I., Mukhametov R.R. Development of a lowviscosity epoxy binder for processing by vacuum infusion. Aviatsionnye materialy i tekhnologii = Aviation Materials and Technologies. 2014;1(30):39–41 (in Russ.). https://doi.org/10.18577/2071-9140-2014-0-1-39-41

7. Sakoshev Z.G., Blaznov A.N., Sakoshev E.G., Zadvornykh G.S. Investigation of rheological properties of binders based on epoxy resin and hardeners HT-152B, IMTHFA, and Etal-450. In: Technologies and Equipment of the Chemical, Biotechnological, and Food Industries: Materials of the 15th All-Russian Scientific and Practical Conference of Students, Graduate Students, and Young Scientists with International Participation. Biisk: Altai State Technical University; 2022. P. 234–237 (in Russ).

8. Mukhametov R.R., Akhmadieva K.R., Chursova L.V., Kogan D.I. New polymer binders for promising methods for the production of structural fibrous PCM. Aviatsionnye materialy i tekhnologii = Aviation Materials and Technologies. 2011;2(19):38–42 (in Russ.).

9. Sayapin S.N. New Approach to the Manufacturing Technology of Long Hollow Products Made of Fibrous Polymer Composite Materials. Izvestiya vysshikh uchebnykh zavedenii. Mashinostroenie = BMSTU Journal of Mechanical Engineering. 2022;11(752):38–46 (in Russ.). https://doi.org/10.18698/0536-1044-2022-11-38-46

10. Donetskiy K.I., Usacheva M.N., Khrulkov A.V. Infusion methods for the manufacture of polymer composite materials (Review). Part 1. Trudy VIAM = Proceedings of VIAM. 2022;6(112):58–67 (in Russ.). https://doi.org/10.18577/2307-6046-2022-0-6-58-67

11. Khrulkov A.V., Donetskiy K.I., Usacheva M.N., Goryansky A.N. Infusion methods for the manufacture of polymer composite materials (Review). Part 2. Trudy VIAM = Proceedings of VIAM. 2022;7(113):50–62 (in Russ.). https:// doi.org/10.18577/2307-2022-0-7-50-62

12. Novakov I.A, Bakhtina G.D., Kochnov A.B., Kostryukova Yu.V. Method of Producing Phosphorus-and-Chlorine-Containing Methacrylates: RF Pat. 2447079 C1. Publ. 10.04.2012 (in Russ.).

13. Tuzhikov O.I., Tuzhikov O.O., Buravov B.A., et al. Use of Oligoether Acrylate of ((((4-((1-(2-((bis((1-Chloro-3-(Methacryloyloxy)propan-2-yl)oxy)phosphine)-oxy)-3-Chlorophenoxy)-3-Chloropropan-2-yl)oxy)-1-Chlorobutan-2-yl)oxy)phosphindiyl)bis(oxy))bis(3-chloropropan-2,1-diyl)-bis(2-methacrylate) as a Monomer for Producing Thermoand Heat-Resistant Polymers with Low Inflammability: RF Pat. 2712107. Publ. 24.01.2020 (in Russ.).

14. Tuzhikov O.I., Tuzhikov O.O., Buravov B.A., et al. Use of Oligoether Acrylate of ((((((((((2-hydroxypropane-1, 3-diyl)bis(oxy))bis(4,1-phenylene))bis(propan-2,2-diyl))-bis(4.1-phenylene))bis(hydroxy))-bis(1- chloropropane-3,2-diyl))bis(oxy))-bis(phosphintriyl)) tetrakis(oxy))-tetrakis(3-chloropropane-2,1-diyl)tetrakis(2-methyl acrylate) as a Monomer for Obtaining Thermo- and Heat-Resistant Polymers with Low Inflammability: RF Pat. 2712116. Publ. 24.01.2020.

15. Buravov B.A., Al-Khamzawi A., Bochkarev E.S., Grichishkina N.Kh., Borisov S.V., Sidorenko N.V., Tuzhikov O.I., Tuzhikov O.O. Synthesis of new photo-cured phosphorus-containing oligoestermethacrylates with a spacer in the structure. Tonk. Khim. Tekhnol. = Fine Chem. Technol. 2022;17(5):410–426. https://doi.org/10.32362/2410-6593-2022-17-5-410-426

16. Kochetygov A.A. Analiz dannykh s ispol’zovaniem sistemy STATISTICA (Data Analysis using the STATISTICA System): a textbook. Tula: TulGU; 2023. 324 p. (in Russ.). ISBN 975-5-7679-5255-7

17. Polezhaeva N.I. Development of organic binder for solder pastes with strictly specified rheological characteristics. Reshetnevskie chteniya. 2018;1:619–620 (in Russ.).

18. Korotkova E.I. Optimizatsiya mnogofaktornogo eksperimenta v khimii ( Optimization of a Multifactorial Experiment in Chemistry): a textbook. Tomsk: TPU; 2021. 85 p. (in Russ.). ISBN 978-5-4387-1055-4

19. Vershinin V.I., Pertsev V.I. Planirovanie i matematicheskaya obrabotka rezul’tatov khimicheskogo eksperimenta (Planning and Mathematical Processing of the Results of a Chemical Experiment). St. Petersburg: Lan; 2022. 236 p. (in Russ.). ISBN 978-5-8114-9167-4

20. Chetverikova D.K., Brezhnev A.M. Features of planning a multifactorial experiment. In: Theory and Practice of Innovative Research in the Field of Natural Sciences: Materials of the All-Russian Scientific and Practical Conference with International Participation. Orenburg: Orenburg State University; 2022. P. 221–225 (in Russ.).

21. Chepurnenko A.S., Kondrat’eva T.N. Prediction of Rheological Parameters of Polymers by Machine Learning Methods. Advanced Engineering Research ( Rostov-on-Don). 2024;24(1):36–47 (in Russ.). https://doi.org/10.23947/2687-1653-2024-24-1-36-47