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The 10th "Challenge Cup" National College Students' Extracurricular Academic and Scientific Works Competition
Statement of works
Study on Living Controlled Polymerization in Supercritical CO2 Medium
Full name of the school: East China University of Science and Technology
name of applicant
(collectively): Zhao Zhen, Pan Yong, Nursida? Pilates, He Hongbo
Category:
■ Academic papers in the field of natural science
Social investigation reports and academic papers on philosophy and social sciences.
□ Class A scientific and technological inventions and achievements
□ Scientific and Technological Invention and Production Class B
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□ Submit provincial works.
■ Works are delivered directly by colleges and universities.
A2。 Applicant information (collective project)
Note: 1. Must be filled in by the applicant himself as required;
2. The representative of the applicant must be the author with the highest academic qualifications, and the rest of the authors are arranged according to their academic qualifications;
3. The signature of the school registration management department in this form is regarded as confirmation of the applicant's situation.
Name of the applicant's representative Zhao Zhen Sex Male Date of Birth 1985 10 month.
School East China University of Science and Technology, major, grade, department of science and engineering, department of polymer materials, grade 04.
Academic System 4 Bachelor's Degree Admission Time September 2004
Study on Living Controlled Polymerization in Supercritical CO2 Medium
Title of graduation thesis
Postal code 200237 is omitted from the mailing address.
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Last name, first name, gender, age and educational unit of other authors.
Pan Yong, male, 22 years old, undergraduate, Department of Science and Technology Excellence, East China University of Science and Technology.
Nursida? Pilates Female 2 1 Undergraduate Department of Science and Technology Excellent Students of East China University of Science and Technology
He Hongbo, female, 2 1, undergraduate, School of Materials Science and Engineering, East China University of Science and Technology.
Whether the above authors are China junior college students, undergraduates, master students and doctoral students of full-time non-adult education full-time colleges and universities officially registered before July/KLOC-0, 2007.
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B 1。 Application of works (natural science academic papers)
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3. Please fill in the work classification according to the academic direction of the work or the main disciplines involved;
4. Does not include the works of master students and doctoral students.
Study on living controlled polymerization in supercritical CO2 medium.
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A machinery and control (including machinery, instruments, automation control, engineering, transportation, construction, etc.). )
B. information technology (including computers, telecommunications, communications, electronics, etc. )
C. Mathematics (including mathematics, physics, earth and space science, etc. )
D life sciences (including biology, agronomy, pharmacy, medicine, health, hygiene, food, etc. )
E energy and chemical industry (including energy, materials, petroleum, chemistry, chemical industry, ecology, environmental protection, etc. )
The purpose and basic idea of the writing work The purpose of this study is to realize the controlled polymerization of fluoroalkyl acrylate in supercritical CO2, to prepare a new fluorine-containing block polymer with controllable molecular weight and structure and excellent surface properties, and to explore the application of this kind of fluorine-containing block polymer.
Basic idea:
1. Because the environmentally friendly supercritical CO2 has good solubility in fluoropolymers, this study used it as a "green" reaction medium to replace the traditional chlorofluorocarbon solvents that seriously damaged the atmospheric ozone layer, and prepared high-quality fluoropolymer materials.
2. According to the latest development of living controllable radical polymerization technology and the performance requirements of materials, new fluorine-containing block copolymers with controllable molecular weight and chemical structure can be designed and synthesized.
3. According to the structural characteristics of block * * * polymers, develop their uses. Specifically including:
A * * block polymer is used as dispersion stabilizer to polymerize other fluorine-free monomers in supercritical CO2, which promotes the development of supercritical polymerization technology of fluorine-free monomers.
B, selecting a suitable solvent, using the solubility difference of the two polymer segments to form some micro-nano composite rough structures in the film-forming process, and enriching the fluorine-containing segments on the surface of the polymer film through solvent control, so as to finally obtain a new material with excellent surface properties.
Works science
Gender and progress
Unique, scientific and advanced:
In this study, the controllable polymerization of fluorinated alkyl acrylate monomer in supercritical CO2, a "green" medium, was realized for the first time, and several novel fluorinated alkyl acrylate triblock copolymers with controllable molecular weight and structure were prepared, and the structure and properties of the materials were systematically studied. This research is an interdisciplinary subject involving polymer chemistry and chemical engineering, which has good basic theoretical research significance and practical application value. Its characteristics are as follows:
1. This study combines two important research hotspots in the field of polymers, namely supercritical fluid technology and living polymerization technology. Fluoroalkyl acrylate homopolymer and block polymer with controllable molecular weight and structure were successfully prepared by free radical polymerization with controllable RAFT activity in supercritical CO2 green medium. This research has good theoretical significance and practical application value.
2. In this study, the RAFT polymerization of fluorine-containing monomers was realized in green medium supercritical CO2, and a novel fluorine-containing triblock polymer was prepared for the first time. Therefore, this study is another important supplement and development of living radical polymerization technology, which is very innovative.
3. The molecular structure and molecular weight of block * * * polymer have been successfully controlled in this study, which is of great significance for developing new fluorine-containing materials with high quality, high performance and no pollution.
4. Based on the structural characteristics of the prepared fluorine-containing block copolymer, its application as dispersion stabilizer of supercritical polymerization and preparation of superhydrophobic surface was developed, and its method and results were innovative and advanced.
5. The molecular weight, chemical structure and material properties of the prepared block copolymer were systematically studied by various characterization methods, and the relationship between material structure and properties was revealed, which was very theoretical and scientific.
The practical application value and practical significance of the work. The research content of this topic involves two fields: polymer chemistry and chemical engineering. This achievement has good theoretical research significance and practical application value, and its significance lies in:
1. The polymerization of fluoroalkyl acrylate with supercritical CO2 as dispersion medium replaces the traditional organic solvent, which reduces the use and recovery of organic matter, especially greatly reduces the environmental pollution caused by the volatilization of chlorofluorocarbons. At the same time, raw material CO2 comes from the by-product of petrochemical industry, which is easy to recover and reduces the emission of greenhouse gases. Today, with the increasingly serious environmental pollution and global warming, this is very necessary and meaningful.
2. The critical temperature and pressure of 2.CO2 are low (3 1℃, 7.4 MPa), and it is easy to realize supercritical state. The polymerization method is simple, the product is easy to purify, and there is no solvent residue, so it has a good industrial application prospect.
3. RAFT living polymerization of fluoroalkyl acrylate was realized in supercritical CO2 for the first time. This living polymerization technology has a wide range of monomers, simple implementation and good industrial prospects.
4. A novel fluorine-containing block copolymer with controllable structure was prepared by RAFT polymerization in supercritical CO2, and two new uses of the block copolymer were developed, which is of great significance for the development and application of new materials.
5. The prepared fluorine-containing block copolymer was used as dispersion stabilizer in supercritical polymerization of other fluorine-free monomers, which effectively improved the conversion rate of supercritical polymerization of other monomers, successfully prepared polymer products with high molecular weight and regular shape, and promoted the research and industrial application of dispersion polymerization of fluorine-free monomers in supercritical CO2.
6. Using the solubility difference of the prepared fluorine-containing block * * * polymer in two stages, the non-fluorine-containing segments in the * * * polymer are agglomerated and nucleated in a suitable solvent, while the fluorine-containing segments are enriched on the surface, thus forming a rough surface structure with low surface energy, obtaining a good hydrophobic and oleophobic effect, and further improving the surface properties of the material.
7. When fluoropolymers are used as anti-corrosion and anti-pollution materials, block polymers containing a small amount of fluorine monomers can be used instead of high fluoropolymer materials, which can greatly reduce the material cost without reducing the use performance.
In this study, a novel fluoropolymer material with controllable structure and properties was prepared by RAFT polymerization of fluoroalkyl acrylate in supercritical CO2, which is of great significance to environmental protection and the development of fluorine-containing materials.
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Supercritical CO2 is an environmentally friendly green solvent, which is of great significance to the preparation and application of fluoropolymer. In this paper, the RAFT living polymerization of fluoroalkyl acrylate was carried out in supercritical CO2 medium, and a series of homopolymer and block copolymer of fluoroalkyl acrylate with controllable molecular weight and structure were designed and synthesized. Infrared absorption spectrum, gel permeation chromatography, nuclear magnetic resonance spectrum and fluorine analysis show that the synthesized polymer has the expected structure. This paper also explores the application of the synthesized fluoroalkyl acrylate block * * * polymer. It is found that this block * * * polymer can be used as dispersion stabilizer for supercritical polymerization of ordinary monomers, which can obviously improve the polymerization conversion rate and product molecular weight, and the product has regular shape and uniform particle size. This result can promote the development of supercritical polymerization technology. In this paper, based on the solubility difference of block * * * polymers, a rough surface with fluorine-rich micro-nano composite structure was prepared, which has good hydrophobic and oleophobic effect.
When, where and what kind of organization held a meeting or reported it and won an award? 1., Willy, Li Xinxin,,, Han, "Study on emulsion polymerization of fluoroalkyl acrylate", organic fluorine industry, March 3, 2006.
2. Wool, Han,,, Zhao Ling,,,, "Preparation method of fluorine-containing block polymer", national invention patent, application number: 2007 1004085 1.9.
3. Willy, Zhao Zhen, Su Xiaoli, Zhao Ling, Nursida? Han, "RAFT Polymerization of Fluoroalkyl Acrylate in Supercritical CO2", 2007 National Symposium on Polymers, (Chengdu, 10, 2007), accepted.
4. AARON Li,, Yu Fan,,, Wu, Han, "Preparation of Novel FMA/MMA/FMA Triblock Copolymer by RAFT Polymerization in Supercritical CO2", submitted to Polymer Express.
5. In April 2007, this work won the first prize in the seventh "Endeavour Cup" extracurricular academic and scientific works competition of East China University of Science and Technology.
The evaluation result is none.
Please provide the retrieval catalogue of the existing technologies and technical documents that are valuable for understanding, reviewing and evaluating the declared works [1] J.L. Kendall, D.A. Canelas, J.M. Desimone, Polymerization in Supercritical Carbon Dioxide. Chemical review.1999,99 (.
[2] Desmond, Guan, Elsborn, Synthesis of fluoropolymer in supercritical carbon dioxide. Science,1992,257 (5072): 945-947
[3] J.M. Descimon, E.E. Murray. Dispersion polymerization in supercritical carbon dioxide. Science,1994,265 (5170): 356-359
[4] A. Goto, K. Sato, Y. Tsujii, et al. Mechanism and Kinetics of RAFT-based Living Radical Polymerization of Styrene and Methyl Methacrylate. Macromolecules. 200 1, 34(3): 402-408
[5] J. Chiefari, Y. K. Chong, F. Erole, et al. Living radical polymerization by reversible addition-fragmentation chain transfer: RAFT process, macromolecules,1998,31,5559-5562;
Pan Jingyun, He Junpo, Jiang, et al. Control MMA free radical polymerization and synthesis of block * * * polymers based on RAFT process. Journal of Chemistry of China University, 25th, 2004, 1759~ 1764.
[7] Wang, New Technology of Polymer Synthesis, Chemical Industry Press, 2004
Bai Ruiguang, You Yuzhen, Pan Chunyan, "Living" Radical Polymerization Initiated by 60Co γ Radiation in the Presence of Dibenzyl Thiocyanate, Rapid Polymer Communication, 2006,5438+0,22,315-319.
[9] Zhang, Ying Shengkang, A New Trend of Living Free Radical Polymerization-Reversible Addition-Chain Break Transfer Free Radical Polymerization, Synthetic Rubber Industry,1999.22 (3):135-139;
[10] Feng L. et al., superhydrophobicity from amphiphilic polymers, Angew. Chemistry. Edited by …, 2003,42(7):800
List of application materials (one application document, name and quantity of relevant materials)
1. Submit papers 1.
"Study on Living Controlled Polymerization in Supercritical CO2 Media", research paper.
2. Patent 1
"Preparation method of fluorine-containing block polymer", national invention patent.
3. 1 publish a paper.
"emulsion polymerization of fluoroalkyl acrylate", journal paper
management of scientific research
Department signature
The situation is true and I agree to recommend it.
June 2007 12
C. Overview of research status of similar topics at home and abroad
Note: 1. Applicants can fill in according to the type and situation of work;
2. Filling in this column is helpful for evaluation.
With the continuous progress of science and technology, people pay more and more attention to environmental problems, and chemical industry and chemical enterprises as big polluters urgently need to study and develop green chemistry to reduce and eliminate pollution. Supercritical CO2 is an ideal substitute for traditional organic solvents in polymerization. Supercritical CO2 is especially suitable for preparing fluoropolymers. Generally, chlorofluorocarbons (CFCs) are used as solvents for synthesizing fluoropolymers. However, CFC is forbidden to be discharged because it destroys the ozone layer in the atmosphere, and fluoropolymer has excellent solubility in supercritical CO2. Therefore, it is of great significance to use supercritical CO2 as an environmentally friendly green solvent to synthesize fluoropolymers.
At present, free radical polymerization in traditional solvents is still the main polymerization method of fluoroalkyl acrylate in industry, and recently developed living polymerization is the most effective means to synthesize polymers with specific structures and properties, which is convenient for accurate molecular design of polymers, control of polymer chemical structure, and preparation of monodisperse polymers with expected molecular structure, molecular weight and molecular weight distribution. Among them, reversible addition-chain fragmentation transfer (RAFT) free radical polymerization has become the most promising living/controlled free radical polymerization because of its wide range of suitable monomers and low polymerization temperature, and many methods such as bulk, solution, emulsion and suspension can be used. However, there are few reports on the polymerization of fluorine-containing monomer RAFT at present, which may be related to the poor solubility of fluorine-containing monomer and polymerization products in common organic solvents.
Fluorine-containing monomers and polymers have good solubility in supercritical CO2. 1992, Professor Desimone of the University of North Carolina and others used azodiisobutyronitrile (AIBN) as initiator to synthesize poly (1, 1- octyl dihydroperfluoropropionate) with higher molecular weight in supercritical CO2 for the first time, and then used supercritical CO2 as green reaction medium to carry out various polymerization reactions, which became chemistry. At present, the research in this field mainly focuses on two aspects: one is the homogeneous solution polymerization of fluorine-containing monomers in supercritical CO2, and the other is to add some fluorine-containing or silicon-containing block polymers as dispersion stabilizers to realize the polymerization of fluorine-free monomers in supercritical CO2. However, fluorine-containing block polymers as dispersion stabilizers are mostly prepared by ATRP method in solution.
At present, there are few reports about living polymerization in supercritical fluid, one of which is the preparation of fluorine-containing block polymers by ATRP method. However, this method needs to synthesize special fluorine-containing complexing agents and introduce copper salts, which will adversely affect the color and quality of products. However, there is no literature report on the RAFT polymerization in supercritical CO2. This method shows that the product quality and color are good by using thiocarbonate as RAFT reagent without adding other additives, so its research has good theoretical research significance and practical application value.
In addition, this study also takes advantage of the different solubility of each segment of the block * * * polymer to form some rough surface structures with micron and nano-composite when forming films in solution, thus making the materials have more excellent surface properties. In recent years, the preparation and characterization of this micro-nano surface has been a research hotspot at home and abroad.
D. Referee information and work description
Description: 1. To be filled in by the recommender himself;
2. The recommender must have a senior professional title and be the same as or related to the declared work.
Experts, scholars or professional technicians in the field (collectively recommended by the teaching and research group is also acceptable);
3. When the recommender fills in this part, it will be deemed that he agrees to recommend;
4. The signature of the recommender's unit is only regarded as confirmation of the recommender's identity.
Name of speaker: Han, gender, male, professor, 67 titles.
Work unit East China University of Science and Technology
Mailing address: No.0/30, Meilong Road, Xuhui District, Shanghai.
East China University of Science and Technology School of Materials Science and Engineering Postal Code 200237
Save the phone number at work and the phone number at home.
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Please state the authenticity of the applicant's statement. The applicant's statement is true. This work was completed by four students from the Department of Science and Technology Excellence and the College of Materials. The research was directed by associate professor Villi. The data in the research paper is reliable and the conclusion is correct.
Please give your opinions on the significance, technical level, application scope and promotion prospect of this work. The work is about the synthesis of fluorine-containing block * * * polymers. Using supercritical CO2 as the reaction medium, the problem of insolubility of fluorine-containing materials was solved. The polymer structure was successfully established by RAFT living polymerization, and the chemical construction and physical assembly of fluorine-containing materials were successfully realized, thus preparing high-quality materials. The research results are innovative and advanced, which is of great significance to the preparation of high-performance and pollution-free fluorine-containing materials.
Signature:
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The speaker's surname is Anna Zheng, gender, male age, professor, with 59 titles.
Work unit East China University of Science and Technology
Mailing address: No.0/30, Meilong Road, Xuhui District, Shanghai.
East China University of Science and Technology School of Materials Science and Engineering Postal Code 200237
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Signature date year month day.
Please state the authenticity of the applicant's statement. The applicant's situation is true. Since April 2006, four students have been engaged in related research work under the guidance of teachers in their spare time. At present, great progress has been made and relevant papers have been published or submitted.
Please give your opinions on the significance, technical level, application scope and promotion prospect of this work. In this study, two hot topics, supercritical fluid technology and RAFT living polymerization technology, were combined, and new fluorine-containing materials with controllable structure were prepared in supercritical CO2, and the application research of materials was actively carried out, and good results were achieved. Its technology has basically reached the advanced level in the world. The development of supercritical polymerization technology is of great significance to solve the pollution of chemical enterprises, especially those producing fluorine-containing materials. Developing high-end fluorine-containing products with independent intellectual property rights is also the development trend of enterprises in China. At present, this research has also been funded by Shanghai Sanaifu New Materials Co., Ltd., the largest organic fluorine producer in China.
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June 2007 12
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