| Polusulfone (PSF) as one kind of high performance material exhibits high mechanical properties, good electronic insulating and thermal resistance, as well as good dimensional stability and excellent water stability. PSF can be used in photo-sensitive material and proton conductivity material and any other places. This paper uses commercial product as the polymer main chain, first to synthesize the CMPSF by chloromethylation, then CMPSF react with three kinds of photo-sensitive groups to get the photo-sensitive polysulfone, at last the sulfonic groups are grafted into the polymer in two different methods. They are four parts in this paper.1. We used Blanc chloromethylation to make the rigidity polysulfone have active groups. The chloromethylation use the chlorine methyl ether as the chlorine methylation reagent and adopting ZnCl2 as catalysts to get the chloromethylated polysulfone (CMPSF). We can change the reaction condition to gain the best reaction conditions. We synthesize series kinds of CMPSF with different chloromethylation ratios for the next reaction with the functional monomers. The polymers were characterized by FT-IR, 1H NMR and differential scanning calorimetry (DSC).2. Three different kinds of photosensitive monomers 4-hydroxychalcone, cinnamic acid and 4-hydroxyethylchalcone reacted with the CMPSF which the chloromethylation ratios is 50%. We can get three kinds of photosensitive polymers CMPSF-HC, CMPSF-CMA and CMPSF-HEC with the photosensitive groups in the side-chain. The resulting polymers exhibited good dissolvability and high photosensitivity. CMPSF-HC shows the maximum extent of photoreaction for the polymer film, and the photoreaction was about 55.2%.3. A series of function polymer with the photosensitive groups and the sulfonic groups in the side-chain were synthesized by nucleophilic substitutions. Different chalcone ratio CMPSF-HC were first synthesized by controlling the reaction time, then we used NaOH as the catalyst and TBAB as the phase transfer catalyst, the sulfonic groups react with the chloromethyl groups in the side chain,CMPSF-HC-HSNa with different sulfonic groups were synthesized successfully. The polymers were characterized by UV-vis, FT-IR, 1H NMR and thermo gravimetric analysis (TGA). We also studied the IEC, water uptake and swelling ratio, the oxidative stability and hydrolytic stability of CMPSF-HC-HSNa membrane. The series of CMPSF-HC-HSNa exhibit high photosensitivity and oxidative stability, also the polymer own a considerable IEC,which give a feasibility to used as the proton conductivity membrane.4. With the target to improve the IEC, we use the CMPSF-HC which the chalcone ratios is 60% (40% chloromethyl groups was left ) as macroinitiator to prepare grafted copolymers PSSA through ATRP by initiating sodium 4-vinlbenzenesulfonate (SSA) successively in the present of copper chloride / bipyridine. The resulting copolymers CMPSF-HC- g-PSSA were investigated by 1H NMR spectroscopies. The amount of sulfonic groups was test by titration use NaOH as the benchmark. The results showed that IEC was effected by reaction time, reaction temperature and the amount of the monomer. The most approprite temperature for this ATRP reaction was 130℃. The polymer showed a IEC value 1.435 after reacted 36h. And IEC increased with the extended of the reaction time. This could provide a theoretic to get high IEC polymers which can be totally used in proton exchange membrane. |
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