由氧化苯乙烯制备聚单硫代碳酸苯乙烯酯【字数：10352】
1Abstract 2第一章 绪论 31.1 氧硫化碳 31.1.1氧硫化碳的性质 31.1.2氧硫化碳的研究及其应用 41.2 DMCC催化剂 51.2.1DMCC催化剂简介 51.2.2 Zn-Co (III) DMCC催化剂的制备 71.3课题的提出及意义 71.3.1课题的提出 71.3.2课题的意义 9第二章 实验部分 102.1引言 102.2 实验表征共聚效果的参数 112.3原料和试剂 112.4实验仪器及测试 122.4 Zn-Co（III）DMCC催化氧硫化碳/氧化苯乙烯共聚反应 12第三章 结果与讨论 133.1氧硫化碳/氧化苯乙烯共聚体系分析 133.2 共聚产物的表征 143.3反应温度对氧硫化碳/氧化苯乙烯共聚反应的影响 153.3.1反应温度对单体转化率、链节选择性和共聚物选择性的影响 163.3.2反应温度对聚合物链节比例的影响 173.3.3反应温度对数均分子量和分子量分布的影响 213.4小结 23参考文献 24致谢 25由氧化苯乙烯制备聚单硫代碳酸苯乙烯酯氧硫化碳（COS）是与二氧化碳（CO2）和二硫化碳（CS2）结构类似的一碳（C1）单体一直被视为一种催化剂毒害物和工业废气，主要用作土壤熏蒸剂。主流的研究方向都是围绕在如何处理COS，而对COS的应用研究十分有限。DMCC催化剂从结构上来看是一种典型的配位络合物，称作双金属氰化络合物（double metal cyanide complex），最早被用来催化环氧化物的开环聚合以制备聚醚多元醇的催化剂，可以有效催化环氧开环聚合。Zn-Co (III) DMCC锌-钴双金属氰化物络合物催化剂结构类似普鲁士蓝结构，晶胞为面心立方点阵结构，所具有很高的结晶性。本文研究了氧硫化碳（COS）与环氧化物——氧化苯乙烯（STO）的催化共聚反应。将COS作为一碳单体，在Zn-Co (III) DMCC催化剂作用下与氧化苯乙烯开环加聚，合成得到高转化率、高聚合物选择性、高聚合物链节选择性的单硫代碳酸苯乙烯酯，系统阐述了COS与氧化苯乙烯共聚的规律与机理。锌-钴双金属氰化络合物催化剂(Zn-Co(III) DMCC)可有效催化COS与氧化苯乙烯共聚。转化率大于99%，共聚物选择性大于95%。加入过量的COS，在80℃-110℃ 条件下催化活性及选择性更高，在其粗产物的核磁氢谱中未检测到环状副产物。 *好棒文|www.hbsrm.com +Q: *351916072*
同时也未检测到碳酸酯链节、二硫代碳酸脂链节或相应的环状产物，这表明氧硫交换反应得到完全抑制，但因有STO单体均聚有聚醚生成导致无法得到全交替结构共聚物。共聚物上单硫代碳酸酯链节比例最高为88%。
目录
Abstract
Carbonyl sulfide (COS) is a monocarbon (C1) monomer with similar structure to carbon dioxide (CO2) and carbon disulfide (CS2), which has been regarded as a catalyst poison and industrial waste gas and mainly used as a soil fumigant. The mainstream research direction is around how to deal with COS, and the application of COS research is very limited.
The DMCC catalyst is a typical coordination complex in terms of structure, called the double metal cyanide complex.It was first used to catalyze the ringopening polymerization of epoxides to prepare polyether polyols. It can effectively catalyze the ringopening polymerization of epoxides. The structure of ZnCo (III) DMCC is similar to Prussian blue structure, and the crystal cells are planecentered cubic lattice structure, with high crystallinity.
The catalytic copolymerization of Carbonyl sulfide (COS) with styrene oxid（STO）was studied. Taking COS as a single carbon monomer, it was polymerized with styrene oxide ring opening under the action of ZnCo (III) DMCC catalyst, and poly(thiocarbonate) with high conversion rate, high product selectivity and high polymer linkage selectivity was synthesized
DMCC can effectively catalyze COS copolymerization with styrene oxide. The conversion rate was greater than 99% and the product selectivity was greater than 95%. Add too much COS, under the condition of 80 ℃ to 110 ℃ higher catalytic activity and selectivity, in its crude product hydrogen nuclear magnetic ring byproducts was detected in the spectrum. At the same time,no carbonate linkage joints, dithiocarbonate linkage joints or corresponding ring products were detected, which indicated that the oxygensulfur exchange reaction was completely inhibited. However, due to the formation of polyether by STO homopolymerize,it was impossible to obtain fully alternating structure copolymers. The highest proportion of poly(thiocarbonate) linkage on the copolymer was 88%.
Key Words:Carbonyl sulfide;ZnCo(III)DMCC;product selectivity;linkage selectivity
第一章 绪论 1.1 氧硫化碳
1.1.1氧硫化碳的性质
[1]氧硫化碳（COS），又称羰基硫,英文名称 carbonyl sulfide。常温常压下纯净的氧硫化碳是无色无味气体，可是通常因为其含有少量硫化氢而带有鸡蛋发臭的气味。氧硫化碳微溶于水，溶于乙醇和甲苯。极易溶于二硫化碳和氢氧化钾溶液。氧硫化碳可燃并且有毒，并且对人们的喉咙、肺部、皮肤、眼睛、鼻子等器官都有不同程度的刺激和腐蚀。
从氧硫化碳的分子构成来看，可以视为是CS2分子中的一个硫原子被氧原子取代也可以看做CO2分子中的一个氧原子被硫原子取代，物理性质大多介于二氧化碳和二硫化碳间，然而结构上的不同则导致了三者化学性质的区别，相比于两者，氧硫化碳具有更高的反应活性，能够和众多化合物发生反应。氧硫化碳、二氧化碳、二硫化碳三者都是线性结构，然而二氧化碳和二硫化碳为对称结构，其偶极矩为零，但氧硫化碳因为硫原子和氧原子的不同而具有偶极矩，并且碳氧键的键能与键长与碳硫键也不尽相同。由于这种特殊的非对称结构，在发生化学键断裂时随着C=S键和C=O键的断裂会产生两种不同的结构，因此使氧硫化碳比起另外两者在参与化学反应时会发生更多的变化情况。
表1.1 COS，CO2，CS2部分物理化学性质
性能
同时也未检测到碳酸酯链节、二硫代碳酸脂链节或相应的环状产物，这表明氧硫交换反应得到完全抑制，但因有STO单体均聚有聚醚生成导致无法得到全交替结构共聚物。共聚物上单硫代碳酸酯链节比例最高为88%。
目录
Abstract
Carbonyl sulfide (COS) is a monocarbon (C1) monomer with similar structure to carbon dioxide (CO2) and carbon disulfide (CS2), which has been regarded as a catalyst poison and industrial waste gas and mainly used as a soil fumigant. The mainstream research direction is around how to deal with COS, and the application of COS research is very limited.
The DMCC catalyst is a typical coordination complex in terms of structure, called the double metal cyanide complex.It was first used to catalyze the ringopening polymerization of epoxides to prepare polyether polyols. It can effectively catalyze the ringopening polymerization of epoxides. The structure of ZnCo (III) DMCC is similar to Prussian blue structure, and the crystal cells are planecentered cubic lattice structure, with high crystallinity.
The catalytic copolymerization of Carbonyl sulfide (COS) with styrene oxid（STO）was studied. Taking COS as a single carbon monomer, it was polymerized with styrene oxide ring opening under the action of ZnCo (III) DMCC catalyst, and poly(thiocarbonate) with high conversion rate, high product selectivity and high polymer linkage selectivity was synthesized
DMCC can effectively catalyze COS copolymerization with styrene oxide. The conversion rate was greater than 99% and the product selectivity was greater than 95%. Add too much COS, under the condition of 80 ℃ to 110 ℃ higher catalytic activity and selectivity, in its crude product hydrogen nuclear magnetic ring byproducts was detected in the spectrum. At the same time,no carbonate linkage joints, dithiocarbonate linkage joints or corresponding ring products were detected, which indicated that the oxygensulfur exchange reaction was completely inhibited. However, due to the formation of polyether by STO homopolymerize,it was impossible to obtain fully alternating structure copolymers. The highest proportion of poly(thiocarbonate) linkage on the copolymer was 88%.
Key Words:Carbonyl sulfide;ZnCo(III)DMCC;product selectivity;linkage selectivity
第一章 绪论 1.1 氧硫化碳
1.1.1氧硫化碳的性质
[1]氧硫化碳（COS），又称羰基硫,英文名称 carbonyl sulfide。常温常压下纯净的氧硫化碳是无色无味气体，可是通常因为其含有少量硫化氢而带有鸡蛋发臭的气味。氧硫化碳微溶于水，溶于乙醇和甲苯。极易溶于二硫化碳和氢氧化钾溶液。氧硫化碳可燃并且有毒，并且对人们的喉咙、肺部、皮肤、眼睛、鼻子等器官都有不同程度的刺激和腐蚀。
从氧硫化碳的分子构成来看，可以视为是CS2分子中的一个硫原子被氧原子取代也可以看做CO2分子中的一个氧原子被硫原子取代，物理性质大多介于二氧化碳和二硫化碳间，然而结构上的不同则导致了三者化学性质的区别，相比于两者，氧硫化碳具有更高的反应活性，能够和众多化合物发生反应。氧硫化碳、二氧化碳、二硫化碳三者都是线性结构，然而二氧化碳和二硫化碳为对称结构，其偶极矩为零，但氧硫化碳因为硫原子和氧原子的不同而具有偶极矩，并且碳氧键的键能与键长与碳硫键也不尽相同。由于这种特殊的非对称结构，在发生化学键断裂时随着C=S键和C=O键的断裂会产生两种不同的结构，因此使氧硫化碳比起另外两者在参与化学反应时会发生更多的变化情况。
表1.1 COS，CO2，CS2部分物理化学性质
性能
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