聚丙烯酸酯与有机硅杂化及酞菁功能杂化研究
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摘要
本论文由两部分研究工作组成。第一部分是聚丙烯酸酯与有机硅杂化反应研究,第二部分是聚丙烯酸酯与酞菁及其衍生物的功能杂化研究。
第一部分,首先通过乳液聚合方法,采用壬基酚聚氧乙烯醚(OP-10)和十二烷基苯磺酸钠(SDBS)作为乳化剂,合成了苯乙烯(St)/丙烯酸丁酯(BA)/乙酸乙烯酯(VAc)/丙烯酸-2-乙基己酯(2-EHA)四元共聚物,然后利用聚乙烯醇(PVA)代替SDBS,与OP-10组成低皂乳化剂,再一次合成出四元共聚物。当PVA用量为5%,聚合转化率最大,稳定性最好。同时以硅溶胶和正硅酸乙酯(TEOS)与四元共聚物进行杂化反应,红外分析证明TEOS在体系中经水解缩合参与羟基基团反应而得到有机-无机杂化乳液。当固定二氧化硅(SiO2)含量时,TEOS和硅溶胶的用量比对胶膜抗张强度的影响较大,通过测试证明当用量比TEOS:硅溶胶=1:1时,抗张强度有最大值。
第二部分,将实验室合成出来的铜酞菁(CuPc)与氯磺酸(HSO3Cl)反应,在酞菁苯环引入取代基团-SO2Cl,使得金属酞菁活化,这样不仅增加了其反应性,而且溶解性实验表明取代基团-SO2Cl的引入改善了其溶解性,将得到的CuPc-SO2Cl与咔唑反应,生成含金属CuPc、咔唑双官能团的化合物,接着采用非激光评估法-溶剂化变色法测定了其二阶非线性光学系数与基态偶极矩复合量βCTμg值是3.71×10-29 esu.D,表明咔唑/CuPc是一类具有潜在二阶非线性光学性能的化合物,最后通过溶液聚合法,合成出St/BA/甲基丙烯酸甲酯(MMA)三元共聚物,同时将合成的CuPc,钛氧酞菁(TiOPc)和咔唑/CuPc与聚丙烯酸酯分别进行功能杂化,通过红外证明CuPc,TiOPc和咔唑/CuPc的结构未发生明显的变化,聚丙烯酸酯可以作为潜在的载体。
This thesis is divided into two parts. The first part focuses on polyacrylate hybridized with organosilicon. The second part is polyacrylate functionally hybridized with phthalocyanine and its derivatives.
In the first part, using polyoxyethylene(10) nonyl phenyl ether (OP-10), and sodium dodecylbenzene sulfonate (SDBS) as emulsifier, and synthesis of styrene (St) /butyl acrylate(BA)/vinyl acetate (VAc)/2-ethylhexylacrylate(2-EHA) tetrapolymer through the emulsion polymerization. Then SDBS was replaced by PVA, and OP-10 to be the low-soap emulsifier. Tetrapolymer was synthesized again, when 5% PVA, the largest polymerization conversion rate, the best stability. A new kind of hybrid emulsion was synthesized by silica sol, TEOS and the tetrapolymer. Infrared spectrum (IR) proved that hydrolytic condensation polymeric reaction happened among PVA, silica sol and TEOS in the organic-inorganic hybrid emulsion. When fixed the content of silica, the ratio between silica sol and TEOS had strong influence on the tensile strength of membrane, when tested by using TEOS: Silica sol was 1:1, the membrane had a maximum tensile strength.
In the second part, the copper phthalocyanine (CuPc) reacting with chlorosulfonic acid (HSO3Cl) resulted that -SO2Cl is in the benzene ring, which enhanced reactivity and dissolubility of CuPc. The experiments showed that -SO2Cl group improved its dissolubility. Carbazole/CuPc-SO2Cl was synthesized by reaction between CuPc-SO2Cl and carbazole. Then the values of the nonlinear optical second-order polarizabilities and the ground state permanent dipole moments(βCTμg) was calculated by a non-laser evaluation method-the solvatochromic method. The value ofβCTμg of CuPc/Carbazole compounds was 3.71×10-29μg esu.D, which showed that carbazole/CuPc was a latent second optical compound. Finally, synthesis of styrene (St) / butyl acrylate (BA) /methyl methacrylate (MMA) terpolymer through solution polymerization.and it was functionally hybridized with CuPc, oxotitanium phthalocyanine(TiOPc), and carbazole/CuPc independently. IR could prove that CuPc, TiOPc and carbazole/CuPc had no noticeable change in their structures and polyacrylate would be a potential carrier.
第一部分,首先通过乳液聚合方法,采用壬基酚聚氧乙烯醚(OP-10)和十二烷基苯磺酸钠(SDBS)作为乳化剂,合成了苯乙烯(St)/丙烯酸丁酯(BA)/乙酸乙烯酯(VAc)/丙烯酸-2-乙基己酯(2-EHA)四元共聚物,然后利用聚乙烯醇(PVA)代替SDBS,与OP-10组成低皂乳化剂,再一次合成出四元共聚物。当PVA用量为5%,聚合转化率最大,稳定性最好。同时以硅溶胶和正硅酸乙酯(TEOS)与四元共聚物进行杂化反应,红外分析证明TEOS在体系中经水解缩合参与羟基基团反应而得到有机-无机杂化乳液。当固定二氧化硅(SiO2)含量时,TEOS和硅溶胶的用量比对胶膜抗张强度的影响较大,通过测试证明当用量比TEOS:硅溶胶=1:1时,抗张强度有最大值。
第二部分,将实验室合成出来的铜酞菁(CuPc)与氯磺酸(HSO3Cl)反应,在酞菁苯环引入取代基团-SO2Cl,使得金属酞菁活化,这样不仅增加了其反应性,而且溶解性实验表明取代基团-SO2Cl的引入改善了其溶解性,将得到的CuPc-SO2Cl与咔唑反应,生成含金属CuPc、咔唑双官能团的化合物,接着采用非激光评估法-溶剂化变色法测定了其二阶非线性光学系数与基态偶极矩复合量βCTμg值是3.71×10-29 esu.D,表明咔唑/CuPc是一类具有潜在二阶非线性光学性能的化合物,最后通过溶液聚合法,合成出St/BA/甲基丙烯酸甲酯(MMA)三元共聚物,同时将合成的CuPc,钛氧酞菁(TiOPc)和咔唑/CuPc与聚丙烯酸酯分别进行功能杂化,通过红外证明CuPc,TiOPc和咔唑/CuPc的结构未发生明显的变化,聚丙烯酸酯可以作为潜在的载体。
This thesis is divided into two parts. The first part focuses on polyacrylate hybridized with organosilicon. The second part is polyacrylate functionally hybridized with phthalocyanine and its derivatives.
In the first part, using polyoxyethylene(10) nonyl phenyl ether (OP-10), and sodium dodecylbenzene sulfonate (SDBS) as emulsifier, and synthesis of styrene (St) /butyl acrylate(BA)/vinyl acetate (VAc)/2-ethylhexylacrylate(2-EHA) tetrapolymer through the emulsion polymerization. Then SDBS was replaced by PVA, and OP-10 to be the low-soap emulsifier. Tetrapolymer was synthesized again, when 5% PVA, the largest polymerization conversion rate, the best stability. A new kind of hybrid emulsion was synthesized by silica sol, TEOS and the tetrapolymer. Infrared spectrum (IR) proved that hydrolytic condensation polymeric reaction happened among PVA, silica sol and TEOS in the organic-inorganic hybrid emulsion. When fixed the content of silica, the ratio between silica sol and TEOS had strong influence on the tensile strength of membrane, when tested by using TEOS: Silica sol was 1:1, the membrane had a maximum tensile strength.
In the second part, the copper phthalocyanine (CuPc) reacting with chlorosulfonic acid (HSO3Cl) resulted that -SO2Cl is in the benzene ring, which enhanced reactivity and dissolubility of CuPc. The experiments showed that -SO2Cl group improved its dissolubility. Carbazole/CuPc-SO2Cl was synthesized by reaction between CuPc-SO2Cl and carbazole. Then the values of the nonlinear optical second-order polarizabilities and the ground state permanent dipole moments(βCTμg) was calculated by a non-laser evaluation method-the solvatochromic method. The value ofβCTμg of CuPc/Carbazole compounds was 3.71×10-29μg esu.D, which showed that carbazole/CuPc was a latent second optical compound. Finally, synthesis of styrene (St) / butyl acrylate (BA) /methyl methacrylate (MMA) terpolymer through solution polymerization.and it was functionally hybridized with CuPc, oxotitanium phthalocyanine(TiOPc), and carbazole/CuPc independently. IR could prove that CuPc, TiOPc and carbazole/CuPc had no noticeable change in their structures and polyacrylate would be a potential carrier.
引文
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