一氯甲基—七甲基环四硅氧烷的性质及其应用研究
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摘要
碳官能基有机硅化合物(Carbon-Functional Organosilicon Compounds)是指在有机硅高分子中引入碳官能基，从而形成具有新的物理化学性质的有机硅材料，无论在理论研究上还是实际工业生产中都有极其重要的价值。本论文通过在八甲基环四硅氧烷(D_4)甲基上引入卤素氯，从而一步即合成了含碳官能基的有机硅化合物-一氯甲基-七甲基环四硅氧烷(以下以D_4Cl代指，下文同)；进而通过氯在相转移催化下，以相对温和的条件引入羧基、醚基等碳官能基团，改善有机硅氧烷的疏水性，制备两亲性化合物。对合成的D_4Cl的性质进行了广泛研究，进行了药物固载、微乳液聚合，并且将含氯甲基官能基团的有机硅氧烷作为引发剂进行了甲基丙烯酸甲酯(MM)的原子转移自由基聚合(ATRP)。通过ATRP将有机硅和MMA共聚，有望应用于有机硅橡胶的改性，提高力学性能。同时，有机硅的优异性质也被引入到碳聚合物中。全文包括：
首先，研究了D_4Cl在浓硫酸催化下的阳离子本体开环聚合动力学，考察了反应温度和催化剂浓度的影响，得到如下结论：(1)由反应机理推导其动力学速率方程，测得聚合活化能为40．37 kJ／mol；升高反应温度和催化剂浓度，能够加速聚合反应速率。但速率常数增加的趋势随着催化剂浓度的增加而减缓；(2)吸电子基团对硅氧烷的聚合速率影响明显，与八甲基环四硅氧烷相比，在相同条件下，D_4Cl的聚合速率降低，聚合活化能提高。
其次，考察了D_4Cl中C-Cl键的反应活性。在碱催化条件下，将5-氟尿嘧啶(Fluorouracil)药物固载到聚(一氯代甲基-七甲基环四硅氧烷)上；在相转移催化条件下，采用醋酸钾、对溴苯酚和对羟基苯甲醛与D_4Cl进行官能团取代反应，并在碱存在下得到了相应的聚合物。这就证明了D_4Cl中C-Cl键具有一定的反应活性。
再次，通过对D_4Cl／CTAB／乙二醇／水体系相行为的研究，绘制了该体系的拟三元相图，得到了微乳液区、液晶区、相分离区以及乳液区，在此基础上选取微乳液区进行了D_4Cl的微乳液聚合，得到了粒径约50nm含氯甲基的聚硅氧烷微球，将得到的微乳液进行消抑泡实验，实验结果令人非常满意。
最后，根据D_4Cl以及单体MMA的特点，以D_4Cl单体和聚合之后的D_4Cl分别为引发剂，CuCl／bpy为催化剂，进行了MMA的悬浮原子转移自由基聚合反应(ATRP)，制备了末端为有机硅氧烷环、MMA为链的聚合物和有机硅氧烷为主链、MMA为侧链的蜈蚣形聚合物。两种聚合物分子量均达80万左右，分散系数在1．3-1．4之间。
本课题有如下几方面的创新点：
(1)D_4Cl的拟三元相图绘制及微乳液聚合尚未见报道，并且得到了消抑泡性能优异的消泡剂。
(2)将D_4Cl作为引发剂应用于ATRP也属首创，并且得到了分子量达80万、分子量窄分布的聚合物。
Carbon-Functional Organosilicon Compounds are these ones that certain carbon-functional groups are introduced in organosilicon polymers. Organosilicon materials with carbon-functional groups which have new physical and chemical properties own extremely important value either in theory or in practical industrial production. In this paper, active groups were introduced in Octamethylcyclotetrasiloxane(D_4) by substitution of chlorine atom, monochlormethyl-heptamethycyclotetrasiloxane(D4Cl) was obtained and then carbon-functional groups such as carboxyl, ether group were introduced in organosilicon polymers with phase transfer catalyst by chlorine atom under mild conditions. By this way, the amphiphilic copolymer was obtained to improve the hydrophobicity of organosilicon. Furthermore properties of D_4Cl were studied extensively. Drug immobilization and microemusion polymerization about D_4Cl were investigated. Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was carried out, organosilicon compounds with chlormethyl groups as initiators. The copolymer of organosilicon and MMA may be used to improve mechanical properties of organic silicon rubber. Meanwhile the good properties of organosilicon were introduced to carbon polymers. The main work and conclusions as following.
First, the bulk polymerization kinetics of D_4Cl monomer with concentrated sulfuric acid as catalyst was investigated, and the effects of temperature and catalyst concentration on the polymerization rate were studied. The results show that the polymerization rate increases with increasing of temperature and catalyst concentration, and the activation energy is calculated out to be 40.37 kJ·mol~(-1) . But the increasing trend of polymerization rate constant becomes weaker with increasing of catalyst concentration. Compared with the cationic ring-opening polymerization of D_4, the activation energy of D_4Cl is higher, but its polymerization rate is lowered, which means electron withdrawing groups affect the polymerization rate obviously. Second, the reactivity of C-Cl bond in D_4Cl was investigated. Fluorouracil was added by chemical bond to poly(monochlormethyl-heptamethycyclotetrasiloxane) under a condition of base as catalyst. Functional groups substitution reactions were carried out successfully between potassium acetate and D_4Cl with phase transfer catalyst and a polymer with relevant carbon-fucntional group was obtained eventually by base catalyzed. So do p-bromophenol and p-hydroxybenzaldehyde and relevant polymers with certain functional groups were obtained. The results show that the reactivity of C-Cl bond can be stimulated under a proper condition.
Third, the phase behavior of D_4Cl /CTAB/glycol/water pseudo-ternary system was studied and the pseudo-ternary phase diagram under 80 88888 was obtained. The microemulsion polymerization was carried out according to some proper material ratios and polyorganosiloxane particles with diameter in 50 nm were obtained. The antifoam performance of the microemulsion was also investigated and the result was perfect.
Finally, atom transfer radical suspension polymerizations of MMA was carried out. D_4Cl and poly(monochlormethyl-heptamethycyclotetrasiloxane) as initiators respectively, CuCl/bpy as catalyst and poly(methyl methacrylate)(PMMA) with end of cyclic siloxane and a centipede-like polymer with polysiloxane as main chain and PMMA as branch chain were obtained, which polydispersities of the polymers were small(1 .3-1.4) and molecular weight was 800 thousand or so.
The innovations of this paper as follow.
(1) The pseudo-ternary phase diagram and microemusion polymerization of D_4Cl have never been reported and a kind of perfect defoamer with good antifoam performance was obtained.
(2) It is first reported to use D_4Cl monomer and polymer as initiators in ATRP and the molecular weight of polymer by this way can be huge to 800 thousand but the polydispersities of the polymers were small(1.3-1.4).
首先，研究了D_4Cl在浓硫酸催化下的阳离子本体开环聚合动力学，考察了反应温度和催化剂浓度的影响，得到如下结论：(1)由反应机理推导其动力学速率方程，测得聚合活化能为40．37 kJ／mol；升高反应温度和催化剂浓度，能够加速聚合反应速率。但速率常数增加的趋势随着催化剂浓度的增加而减缓；(2)吸电子基团对硅氧烷的聚合速率影响明显，与八甲基环四硅氧烷相比，在相同条件下，D_4Cl的聚合速率降低，聚合活化能提高。
其次，考察了D_4Cl中C-Cl键的反应活性。在碱催化条件下，将5-氟尿嘧啶(Fluorouracil)药物固载到聚(一氯代甲基-七甲基环四硅氧烷)上；在相转移催化条件下，采用醋酸钾、对溴苯酚和对羟基苯甲醛与D_4Cl进行官能团取代反应，并在碱存在下得到了相应的聚合物。这就证明了D_4Cl中C-Cl键具有一定的反应活性。
再次，通过对D_4Cl／CTAB／乙二醇／水体系相行为的研究，绘制了该体系的拟三元相图，得到了微乳液区、液晶区、相分离区以及乳液区，在此基础上选取微乳液区进行了D_4Cl的微乳液聚合，得到了粒径约50nm含氯甲基的聚硅氧烷微球，将得到的微乳液进行消抑泡实验，实验结果令人非常满意。
最后，根据D_4Cl以及单体MMA的特点，以D_4Cl单体和聚合之后的D_4Cl分别为引发剂，CuCl／bpy为催化剂，进行了MMA的悬浮原子转移自由基聚合反应(ATRP)，制备了末端为有机硅氧烷环、MMA为链的聚合物和有机硅氧烷为主链、MMA为侧链的蜈蚣形聚合物。两种聚合物分子量均达80万左右，分散系数在1．3-1．4之间。
本课题有如下几方面的创新点：
(1)D_4Cl的拟三元相图绘制及微乳液聚合尚未见报道，并且得到了消抑泡性能优异的消泡剂。
(2)将D_4Cl作为引发剂应用于ATRP也属首创，并且得到了分子量达80万、分子量窄分布的聚合物。
Carbon-Functional Organosilicon Compounds are these ones that certain carbon-functional groups are introduced in organosilicon polymers. Organosilicon materials with carbon-functional groups which have new physical and chemical properties own extremely important value either in theory or in practical industrial production. In this paper, active groups were introduced in Octamethylcyclotetrasiloxane(D_4) by substitution of chlorine atom, monochlormethyl-heptamethycyclotetrasiloxane(D4Cl) was obtained and then carbon-functional groups such as carboxyl, ether group were introduced in organosilicon polymers with phase transfer catalyst by chlorine atom under mild conditions. By this way, the amphiphilic copolymer was obtained to improve the hydrophobicity of organosilicon. Furthermore properties of D_4Cl were studied extensively. Drug immobilization and microemusion polymerization about D_4Cl were investigated. Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was carried out, organosilicon compounds with chlormethyl groups as initiators. The copolymer of organosilicon and MMA may be used to improve mechanical properties of organic silicon rubber. Meanwhile the good properties of organosilicon were introduced to carbon polymers. The main work and conclusions as following.
First, the bulk polymerization kinetics of D_4Cl monomer with concentrated sulfuric acid as catalyst was investigated, and the effects of temperature and catalyst concentration on the polymerization rate were studied. The results show that the polymerization rate increases with increasing of temperature and catalyst concentration, and the activation energy is calculated out to be 40.37 kJ·mol~(-1) . But the increasing trend of polymerization rate constant becomes weaker with increasing of catalyst concentration. Compared with the cationic ring-opening polymerization of D_4, the activation energy of D_4Cl is higher, but its polymerization rate is lowered, which means electron withdrawing groups affect the polymerization rate obviously. Second, the reactivity of C-Cl bond in D_4Cl was investigated. Fluorouracil was added by chemical bond to poly(monochlormethyl-heptamethycyclotetrasiloxane) under a condition of base as catalyst. Functional groups substitution reactions were carried out successfully between potassium acetate and D_4Cl with phase transfer catalyst and a polymer with relevant carbon-fucntional group was obtained eventually by base catalyzed. So do p-bromophenol and p-hydroxybenzaldehyde and relevant polymers with certain functional groups were obtained. The results show that the reactivity of C-Cl bond can be stimulated under a proper condition.
Third, the phase behavior of D_4Cl /CTAB/glycol/water pseudo-ternary system was studied and the pseudo-ternary phase diagram under 80 88888 was obtained. The microemulsion polymerization was carried out according to some proper material ratios and polyorganosiloxane particles with diameter in 50 nm were obtained. The antifoam performance of the microemulsion was also investigated and the result was perfect.
Finally, atom transfer radical suspension polymerizations of MMA was carried out. D_4Cl and poly(monochlormethyl-heptamethycyclotetrasiloxane) as initiators respectively, CuCl/bpy as catalyst and poly(methyl methacrylate)(PMMA) with end of cyclic siloxane and a centipede-like polymer with polysiloxane as main chain and PMMA as branch chain were obtained, which polydispersities of the polymers were small(1 .3-1.4) and molecular weight was 800 thousand or so.
The innovations of this paper as follow.
(1) The pseudo-ternary phase diagram and microemusion polymerization of D_4Cl have never been reported and a kind of perfect defoamer with good antifoam performance was obtained.
(2) It is first reported to use D_4Cl monomer and polymer as initiators in ATRP and the molecular weight of polymer by this way can be huge to 800 thousand but the polydispersities of the polymers were small(1.3-1.4).
引文
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