Metalpolymers on the Basis of Vinylacetate
Metalpolymers in the Basis of Vinylacetate: Synthesis, Properties and Application
Tech Area / Field
- CHE-POL/Polymer Chemistry/Chemistry
3 Approved without Funding
Yerevan Institute "Plastpolymer", Armenia, Yerevan
- National Research Council, Italy, Rome\nDepartment of Chemistry, USA, OH, Cincinnati\nCarnegie Mellon University / Department of Chemistry, USA, PA, Pittsburgh
Project summaryThe creation of polymeric materials, containing chemically connected metals in their content, has actively developed recently on the joint of metal-organical chemistry and chemistry of high molecular compounds. On the one hand, it is determined by practical value of metal-containing polymers, possessing a number of unique properties: high catalytic activity, unusual magnetic, electro-physical, biological activity, etc. On the other hand, metal-containing monomers are convenient model systems for studying mechanisms of the chain growth during radical polymerization, since they contain an atom of metal in their content, capable of coordination interaction both with macro radical and with monomer. It is of great interest and importance in terms of development of theoretical bases of controlling the stage growth of polymeric chain. Metal-containing polymers are obtained by MCM (co) polymerization (more often radical) or by polymer analogous transformations.
Currently, the subject of intensive researches are also colloid dispersions of nanosize particles (NSP) of metals, which are obtained by restoration the ions of metal in mixtures of polymers. Alongside with noble metals, in recent years, there have been conducted researches on obtaining by this method nano-composites of active metals, such as iron, nickel, copper. Presently, there are conducted some ways of obtaining nano-composites. MCM polymerization with the successive transformation into metals of NSP should be singled out.
In terms of obtaining metal-containing copolymers and metal-filled composites with NSP of metals, vinylacetate polymers are practically not studied.
There are many unsolved problems in chemistry of MCM. First, it concerns copolymerization of MCM of transitional metals with traditional monomers, especially in water medium. Thus, practically there are no systematic investigations of copolymerization of MCM with vinyl monomers, particularly with vinylacetate. Out of all vinyl monomers, vinylacetate is distinguished by the fact that a big part of it (about 70%) is used in the practice of world industry for obtaining water polymer dispersions. Polyvinylacetate (PVA) dispersions are widely used in many branches of industry. However, PVA has a decreased water-, atmospheric- and bio-resistance, insufficient adhesion strength, not high physical-mechanical characteristics. Therefore, the researches on the production of materials on the basis of PVA with improved technological and usage properties are of great importance. On the effective ways of solving this problem is PVA modification. The suggested project implies the search of purposeful modification of polyvinylacetate, also polyvinylacetate dispersion.
The suggested project assumes the search of ways of purposeful modification of PVA, including Polyvinylacetate dispersion.
The objective of the given work is implementation of polymers on the basis of vinylacetate with improved properties at the expense of modification with the help of metals. The improvement of properties assumes resistance to the influence of external factors- thermal and heat resistance, high mechanical and adhesion strength, resistance to biodamages (fungi resistance), fungicide activity. The achievement of the set objective is possible; 1) by copolymerization of vinylacetate with metal-containg monomers of ionic type; 2) by metals of nano-size particles.
In the project, the study of copolymerization of vinylacetate with (met)acrylate, maleinate, itaconate of transitional metals, such as Zn, Co, Ni, Fe, etc. are suggested. Also the study of their influence on copolymerization of vinylacetate with unsaturated carbonic acids is suggested. The use of comonomers such as(met)acrylate, maleinate, itaconate of transitional metals in the course of the stated investigations is determined by availability of the substances, relatively soft conditions of synthesis and their relative stability.
An important stage in the suggested work is the synthesis and investigation of colloid-chemical properties of Zn- and other metal-containing dispersions on the basis of vinylacetate, possessing biological activity, particularly fungicide activity. Fungicide tinorganical acrylate latexes are known,however from ecological point of view, researchers' attention recently has been drawn to Zn-containing latexes. A high fungi-resistance of Zn-acrylate latexes has been shown. It's known, that PVA-dispersions are subjected to the influence of moulds. Hence, the improvement of fungi resistance of PVA-dispersions is an important scientific-industrial task.
Since in nano-dispersion condition substances discover new unusual properties, it's assumed to investigate the possibility of obtaining metal- PVA of nano-composites. The obtained materials will differ by high adhesion strength and catalytic activity. Comparison of properties of PVA materials, containing metal in nano-dispersion condition and metal, chemically connected with polymeric chain, will be of scientific and practical interest.
The participants' main scientific interest is emulsion, suspension copolymerization in water medium. Some participants of the suggested project currently participate in the project A-183 ISTC, where they also study emulsion and suspension copolymerization of vinylacetate. Some participants of the project have experience of many years on the implementation of catalytic processes of industrial organical synthesis, study of fugicide activity, electron-microscopic investigations. A new prospective area of participant's interest are metalcontaining polymers. Works of the laboratory on polymeric nontoxical means of plant protection from pests in an exchange of traditional pesticides are of great scientific and practical interest. Researches, conducted up until now as well as in the frame of A-183 project, have been directed towards killing pests. In the suggested project, the main attention is paid to the struggle against plant diseases, which are initiated by fungi. It's assumed that metal-containing polymers must have a high fugicide activity. The suggested project is a new independent work, not associated with project A-183.
The work, suggested in this project, is related to «Applied Research» category. The necessity of investigations, suggested in the project, comes out of practical need for improving the properties of PVA. However, the obtained results on establishing the connection between the content,structure and properties of the obtained products can be not only of practical interest, but also scientific - theoretical interest. The expected results in accordance with the stages of the implementation are the following:
Scientific – the discovery of the common and inpidual mechanisms of copolymerization of vinylacetate with MCM depending on the nature of metal and peculiarities; of vinylacetate copolimerization with MCM in water mediumpeculiarities in water medium -will be of benefit for chemistry of metal-polymers. Comparison of colloid-chemical properties of two systems:1) dispersions, obtained during the copolymerization with MCM;2) metals of NSP, stabilized by PVA- will expand the knowledge of nano-technologies.
Industrial – the implementation of available methods of synthesis of stable MCP will be applied in industrial production of PVA- dispersion. New brands of glues, paints, adhesives will be created on the basis of metal-containg PVA-dispersions. High fungi resistance of MCP will provide the safety of protection from infection by moulds during PVA storage (multi-tonnage product).
Ecological – during application of the implemented MCP with biocide activity, lower ecological loading will be achieved at the expense of the application of less toxical metals. The synthesis of bio-resistant metal-containg PVA-disperions will increase resistance to biodamages of glues and paints on the basis of PVA and accordingly covers on their basis. The improvement of fungi-resistance will expand PVA application during restoration of historical and cultural monuments.
Economical – the conducted MCP of vinylacetate with fungicide activity will be applied as plant protection means from diseases. From diseases (it's possible simaltaneously both from pests and diseases). One of the most important factors of the increase of fruit and berry cultivation crop capacity is their protection from vermins and diseases. According to the specialist’s data, more than 30 thousand of various diseases permanently or periodically affect plants and more than 10 thousand species of insects and ticks greatly damage agriculture. The protection of crops and grapes, including grapes in Ararat hills of Armenia, will have an effect on agriculture.
The expected areas of application of the obtained MCP are chemical industry, agriculture. However, the use of products of copolymerization of vinylacetate with MCM is not limited by the given examples. A significant expansion of the areas of application can be expected,perhaps in the area of creation catalytic systems.
For achieving the set objective in the project, the solution of the following main objectives: 1) the study of VA copolymerization with metal-containing monomers; 2) the synthesis of metal-containing polymers and nano-composites on the basis of PVA; 3) the study of the properties of the obtained metalpolymers; 4) the search for the ways of possible application of the obtained products.
For implementing the project, the following content of work is expected:
– Comparative investigations of two methods of synthesis of MCP: 1. copolymerization of MCM on the basis of acrylate, metacrylate, maleinate, itaconate with vinylacetate; 2. obtaining MCP through polymer-analogous transformations of copolymers of vinylacetate with unsaturated carbonic acids. The synthesis of stable metal-containg PVA may be complicated because of the formation of sewed structures. Accordindly, the selection of synthesis conditions of stable dispersions is necessary. The search for optimal copolymer content, type and amount of emulsifier, the selection of initiating system are the tasks of synthesis. It would be interesting to find approaches to synthesis of MCP by the mechanism of controlled «living» radical polymerization.
– The study of physical-chemical, physical-mechanical and specific colloid-chemical properties. The comparison of two colloid systems will be conducted:1. metal-containg dispersions on the basis of vinylacetate; 2. NSP of metals, stabilized by PVA.
– The study of biological activity, also fungicide activity; creation of new highly-effective and safe preparations on the basis of MCP for plant protection from diseases. The solution of the suggested tasks in the project will extend good opportunities for creating polymer compositions on the basis of PVA dispersions.
The fulfilment of the work will allow to provide partial involvement of the scientists, earlier related to weapon knowledge and to use their potential in resolving world tasks and it will contribute to the integration of the project participants in the world scientific community.
The realization of the project will be conducted by researchers of the Institute « Plastpolymer» at the laboratories of the Institute. Methods of chemical analysis and contemporary physical-chemical methods (GLCh, UV-, IR-,HMR-spectroscopy, electron microscopy) will be used.
The role of foreign collaborators is:
– in the mutual discussion of the results and information exchange;
– in the course of the project implementation;
– presenting comments on technical summaries;
– conducting cooperative investigations.
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