丙烯酸酯和丙烯酰胺基热响应聚合物的水化和热响应行为研究

发布时间：2020-11-19 16:05

　　 This research focusses on the comparison of hydration and thermal response of acrylate and acrylamide based thermo-responsive polymers.Acrylate based thermo-responsive polymers are well known for their flexibility which makes them suitable for application in textile.However,their swelling capability and transition behaviour are not as pronounced as acrylamide based thermo-responsive polymers.To study their differences in hydration and thermal response,polyethyleneglycolmethyletheracrylate(POEGMA300),poly(2-(2(methoxyethoxy)ethyl 2-methyacrylate)(PMEO2MA)and poly(methoxy diethylene glycol acrylate)(PMDEGA)are selected as the acrylate based thermo-responsive polymers.While Poly(N-isopropylacrylamide)(PNIPAM)and poly(N-isopropyl meth acrylamide)(PNIPMAM)are chosen as the acrylamide based thermo-responsive polymers.During this research,a comparison between PMDEGA film and PNIPMAM films are first performed.In situ neutron reflectivity(NR)is used for this investigation.PNIPMAM film presented a much more pronounced swelling capability than the PMDEGA film in the same vapour atmosphere.In addition,the thermal response of hydrated PNIPMAM film under a thermal stimulus is much more abrupt than that of the PMDEGA film.After comparing the homopolymer films,the block copolymer PMEO2MA-b-POEGMA300 is synthesized.The transition behaviour of this block copolymer is studied in solution as well as in thin film.For the synthesis of this block copolymer the atom transfer radical polymerization(ATRP)method is used.First OEGMA300-Br is synthesised,followed by a similar procedure in which OEGMA300-Br is used as initiator and MEO2MA was added to synthesis PMEO2MA-b-POEGMA300.The obtained block copolymer is characterized by H-NMR and GPC to confirm its molecular weight and structure.Then the block copolymer is dissolved in water and the transition behaviour in aqueous solution is investigated.This is performed by UV-Vis spectroscopy and also dynamic light scattering.This shows that PMEO2MA-b-POEGMA300 has two LCST points.The block copolymer self-assembles into micellar structure when the temperature increases.After that,thin films are prepared by spin-coating the block copolymer on silicon wafers.Homogenous thin films with a smooth surface are obtained.The swelling and transition behaviour of the thin film by studied by white light interferometry.In a D2O vapour atmosphere at a constant temperature of 23~°C the film thickness first increases,which shows absorption of the D2O.When the temperature is increased,the film thickness decreases linearly.Once the acrylate based thermo-responsive block copolymer was investigated successfully,a combination of acrylate and acrylamide based block copolymer(PNIPMAM-b-POEGMA300 and PNIPMAM-b-POEGMA300)is attempt to synthesis.To the best of our knowledge,they are not synthesised by ATRP before.Because this block copolymer is a combination of acrylate and acrylamide based thermo-responsive polymers,it is not possible to use the same ATRP method as for PMEO2MA-b-POEGMA300.After a long process of trial,finally these block copolymers are successfully synthesized.Their molecular structures are characterized by H-NMR and GPC.Their behaviour in aqueous solution is studied by UV-Vis.This showed a sharp decrease of transmittance between 35°C and 45°C.This is not unexpected because PNIPAM and PNIPMAM are known for their sharp transition.Further investigations will be performed on their swelling and transition behaviours in thin films.
【学位单位】：浙江理工大学
【学位级别】：硕士
【学位年份】：2019
【中图分类】：TQ317
【文章目录】：
ABSTRACT
1.THEORETICAL BACKGROUND
    1.1 HOMOPOLYMERS,COPOLYMERS AND BLOCK COPOLYMERS
        1.1.1 Self-assembly of block copolymers in bulk
        1.1.2 Self-assembly of block copolymers in solution
        1.1.3 Self-assembly of block copolymer thin films
    1.2 THERMO-RESPONSIVE POLYMERS
        1.2.1 Behaviour change of temperature-sensitive polymers
    1.3 SYNTHESIS OF LINEAR BLOCK COPOLYMERS
        1.3.1 Atom transfer radial polymerization（ATRP）
        1.3.2 Reversible addition fragmentation chain transfer（RAFT）
        1.3.3 Nitroxide mediated free radical process（NMP）
    1.4 PREPARATION OF POLYMER THIN FILM
        1.4.1 Techniques for the preparation of polymer thin film
    1.5 CHARACTERIZATION AND MEASUREMENT METHODS
        1.5.1 Gel permeation chromatography
        1.5.2 H-NMR
        1.5.3 UV-Visible spectrophotometry
        1.5.4.Dynamic light scattering
        1.5.5 White light interferometry
        1.5.6 Neutron reflectometry（NR）
    1.6 APPLICATION OF THERMO-RESPONSIVE POLYMER FILMS
        1.6.1 Textiles
        1.6.2 Medical applications
2.COMPARISON BETWEEN THE SWELLING BEHAVIOUR OF ACRYLATE AND ACRYLAMIDE BASED THERMO-RESPONSIVE POLYMER FILMS
    2.1 INTRODUCTION
    2.2 THE PROCEDURE
    2.3 PERFORMANCE TESTING BY IN SITU NEUTRON REFLECTIVITY MEASUREMENTS
    2.4 RESULTS AND DISCUSSION
2MA-B-POEGMA₃₀₀'>3.SYNTHESIS AND CHARACTERIZATION OF PMEO₂MA-B-POEGMA300

    3.1 INTRODUCTION
    3.2 THE SYNTHESIS PROCEDURE
        3.2.1 Chemical compounds
        3.2.2 Equipment
        3.2.3 Experiment procedure
    3.3 PREPARATION OF THIN FILM
        3.3.1 Cleaning procedure of silicon wafer
        3.3.2 Preparation of film
    3.4 STRUCTURAL CHARACTERIZATION AND PERFORMANCE TESTING
        3.4.1 Gel permeation chromatography（GPC）
        3.4.2 Nuclear magnetic resonance spectroscopy（H-NMR）
        3.4.3 UV-Vis spectroscopy
        3.4.4 Dynamic light scattering（DLS）
        3.4.5 White light interference（WLI）
    3.5 RESULTS AND DISCUSSION
        3.5.1 Structural characterization
        3.5.2 Block copolymer PMEO2MA-b-POEGMA300 in solution
        3.5.3 Characterization of block copolymer PMEO2MA-b-POEGMA300 film
300 AND PNIPMAM-B-POEGMA₃₀₀'>4.SYNTHESIS AND CHARACTERIZATION OF PNIPAM-B-POEGMA₃₀₀ AND PNIPMAM-B-POEGMA₃₀₀

    4.1 INTRODUCTION
    4.2 THE PROCEDURE
        4.2.1 Chemical compounds
        4.2.2 Equipment
        4.2.3 Experiment procedure
    4.3 STRUCTURAL CHARACTERIZATION AND PERFORMANCE TESTING
    4.4 RESULTS AND DISCUSSION
        4.4.1 Structural characterization
5.CONCLUSIONS
REFERENCES
Published work
Acknowledgement

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