New Methacrylate Macromonomers
New Family of (Met) Acrylic Macromonomers, New Polymers and Related Materials
Tech Area / Field
- CHE-POL/Polymer Chemistry/Chemistry
- MAT-ELE/Organic and Electronics Materials/Materials
8 Project completed
Senior Project Manager
Institute of Problems of Chemical Physics, Russia, Moscow reg., Chernogolovka
- Dupont de Nemours, Germany, Bad Homburg\nLaboratoire des Materiaux Macromoleculaires INSA , France, Lyon\nCNRS/Université de Claude Bernard-Lyon 1 / Laboratoire de Physico-Chimie des Materiaux Luminescents, France, Lyon\nGeorgia Institute of Technology / School of Polymer, Textile & Fiber Engineering, USA, GA, Atlanta
Project summaryPolymers based on the esters of acrylic and methacrylic acids are widely used in industry and remain the object of continual interest for scientific research. In IPCP RAS, a great experience has been accumulated in studying of cross-linked polymers based on esters of (meth)acrylic** hereinafter this term means derivatives of both acrylic and methacrylic acids. acids and other cross-linked polymers. The results obtained in the Institute have been summarized in four books and numerous original papers and reviews.
The project is aimed at the further development of the methods for synthesis of polymers with controlled fracture toughness, which were developed in the frame of #358 ISTC Project. The main emphasis in the project is put on the development of a novel, simple, one-step method for synthesis of (meth)acrylate* macromonomers with heterochain, instead of carbon-chain, structure of the main chain. This polymer is characterized, in addition to its heterochain structure, by the presence of (meth)acrylate group as one of terminal groups and end-capped by functional group as other terminal group. This invention gives powerful impulse for further development of chemistry and technology of polymers based on acrylic and methacrylic acids. Based on this invention, similar macromonomers with different functional groups as the second terminal group (hydroxyl, urethane, isocyanate, allophonate, carboxyl, maleinate, carbamide, amino, hydrazide, trialkoxysilane, acrylate, methacrylate and others) will be synthesized and characterized. Products of their radical polymerization and co-polymerization with other vinyl monomers (styrene, methylmethacrylate, and others) will be synthesized and characterized. New cross-linked polymers will be synthesized by radical polymerization of polyesterdiol di(meth)acrylates and their co-polycondensation with diamines via Michael reaction.
Synthesized reactive polymers, as well as theoretical concepts on the formation of heterophase polymers with controlled morphology and fracture toughness developed in terms of ISTC Project #358, will become the background for development of new polymeric materials of various applications, and technologies of their production. The formation of such class of new reactive
polymers will help in solving of many scientific and applied problems, some of them being formulated as the objective of this Project.
The team of highly qualified scientists and experts of the Institute that participated in implementation of the previous ISTC Project # 358 will solve these tasks. In the framework of that Project, different problems of synthesis and modification of network polymers and related materials have been studied, including development of new methods of modifiers synthesis and studying of their thermodynamic characteristics, development of the theory of cure reaction-induced microphase separation, etc. 34 researchers will participate in the Project implementation, among them 4 Doctors of Sciences and 20 Candidates of Sciences (Ph.D.).
As a result, macromonomers with polyester main chains based on (meth)acrylates with different functional terminal groups will be synthesized and characterized, kinetics and mechanism of macromonomers formation will be studied. Based on the data obtained, synthesis of macromonomers synthesis will be optimized. Based on macromonomers with terminal hydroxyl group, new polyesterdiol di(meth)acrylates will be synthesized and characterized.
Condensation products of macromonomers and polyesterdiol di(meth)acrylates with di- and polyamines will be synthesized and characterized. All generated macromonomers will be tested and characterized as surfactants, sizings and compatibilizers. Based on synthesized macromonomers and polyesterdiol di(meth)acrylates, new graft- and cross-linked polymers will be produced by radical polymerization via chemical and/or photoinitiation, and will be characterized. In addition, linear copolymers of macromonomers with vinyl monomers, and cross-linked polymers upon copolymerization of vinyl monomers with polyesterdiol di(meth)acrylates will be synthesized and characterized.
Macromonomers and polyesterdiol di(meth)acrylates will be used to modify the properties of highly filled materials of “Corian” type (artificial marble) produced by DuPont.
Synthesized (meth)acrylate macromonomers, di- and poly(meth)acrylate oligomers will be used as new finishing and repairing automotive and furniture coatings, printing plates and photoresist materials produced by DuPont.
Generated products will be used as modifying additives for increasing fracture toughness and ductility of polymeric matrices based on cross-linked polymers, in particular, polyepoxides and polybismaleimides. Influence of these additives on kinetics of cure and cure reaction-induced microphase separation, morphology and mechanical properties of forming heterophase polyepoxide and polybismaleimide matrices will be studied.
As far as feasibility of the suggested approach has been demonstrated, we are sure that all synthetic tasks of the Project will be fulfilled because they are based on common for polymeric chemistry approaches. There are no doubts in feasibility of other parts of the Project.
The project under consideration is consistent with the main objective of ISTC because it provides former weapon scientists and other specialists with possibilities to participate in civil research. It ensures further development of basic and applied research started in the previous ISTC Project # 358. The results of the latter one are presented in 112 publications in International (23) and Russian (89) journals (edited both in Russian and English), and in the book “Heterophase Network Polymers: Synthesis, Characterization and Properties”, B.A.Rozenberg, G.M.Sigalov, Eds., Gordon & Breach, which includes the reports of the Project participants and foreign collaborators at annual workshops. In addition, one RF patent and one positive decision on the application have been obtained; 5 RF patent applications are pending. The Project participants have delivered 20 plenary and invited lectures and 34 poster reports on the results of the Project at International and Russian scientific conferences. In fact, the previous ISTC project enabled a real integration of Russian scientists into international scientific community. The most of these scientists will be participants of the submitted Project. During implementation of the previous project none of its participants was involved in weapon research. New equipment has been acquired. The device for gel-permeation chromatography with refractometric and UV-spectroscopic detectors purchased in terms of the previous Project will be one of the main devices for estimation of molecular-mass characteristics of synthesized polymers. It is obvious that all positive changes corresponding to ISTC objectives will be further developed in the framework of the submitted project.
In addition, much closer cooperation with foreign collaborators, in particular, with DuPont has been planned. As it can be seen, many objectives of this Project are consistent with the interests of this Company.
It is supposed to perform joint testing and cross-checks of results obtained in the course of project implementation for particular industrial applications in DuPont technologies.
Besides, it is supposed continual information exchange in the course of project implementation, provide comments to the technical reports (quarterly, annual final, etc.), submitted by IPCP RAS to the ISTC, conduction of joint workshops, assistance and material support for project participants to join international meetings Cooperation with DuPont will provide the evaluation of commercialization possibilities for new polymer materials and related articles, including those in Russian market. The stage of commercial realization of the Project on the basis of final results is envisaged.
A great experience in studying polymeric matrices for solid propellants and rocket cases accumulated in IPCP RAS will be used in experimental investigations on synthesis of macromonomers and related polymers, kinetics and mechanism of the processes under study, structural arrangement and physical-mechanical properties of synthesized polymers. Methods of isothermal and differential scanning calorimetry, dilatometry, IR- and UV-spectroscopy, polynuclear high resolution NMR spectroscopy, chemical analysis, gel-permeation, absorption and liquid chromatography, mass-spectroscopy, thermo-mechanical analysis, electron and scanning microscopy available in IPCP RAS will be used.
Phase diagrams of starting systems will be obtained using interference method and method of optical microscopy, and for reacting systems the method of light scattering will be used.
Rheokinetic investigations will be performed using rotational viscometer.
Mechanical properties of synthesized polymers will be measured using universal testing machine. Thermal properties of polymers will be characterized by differential scanning calorimeter, thermomechanical analysis and thermal gravitometric analysis.
For theoretical studies, experience accumulated in the Institute will be used, as well as soft- and hardware, including supercomputer, available in IPCP RAS.
* hereinafter this term means derivatives of both acrylic and methacrylic acids.