蒎烯衍生物与CO_x和SO_2共聚反应合成新型材料的研究
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摘要
研究了以双环萜烯烃——蒎烯为基础原料合成一系列蒎烯衍生物，并将其作为单体分别与SO_2、CO和CO_2进行共聚，制备得到新材料，并对这些材料的物理性能进行了表征，取得了很好的进展和重要的研究结果，为可再生资源制备新材料提供了理论基础，具有较为重要的理论意义和潜在的参考应用价值，主要研究结果如下：
（1）采用微波辐照法合成了冰片烯和冰片二烯，通过实验得到的最佳合成工艺条件为：0.1mol2-氯莰烷（2,6-二氯莰烷），0.3mol叔丁醇钾，N,N’-二甲基甲酰胺作溶剂，微波辐照温度120℃，微波功为400W，微波辐照时间为60min，原料可达到完全转化，产物选择性为100%，与传统油浴加热法相比，微波辐照法极大地提高了反应效率；同时探讨了合成氯莰烷和冰片烯与冰片二烯的反应机理，表明蒎烯在酸性条件下发生了瓦格聂尔-梅尔魏因重排反应得到氯莰烷，而氯莰烷生成烯烃的反应则是一个双分子消除反应（E2）历程。
（2）以双环萜烯烃——蒎烯、冰片烯和冰片二烯作为共聚单体，分别与SO_2、SO_2和马来酸酐以及SO_2和苯乙烯进行自由基共聚反应，采用FT-IR、GPC、SEM、能谱分析仪和元素分析对共聚产物进行了分析和表征，并探讨了共聚反应的机理，表明聚合反应是原料与三重态3SO_2以自由基链方式进行的自由基共聚。
（3）以冰片烯和冰片二烯作为共聚单体，采用乙酸钯/2,2’-联吡啶/硝基苯/三氟甲基磺酸铜/甲醇/甲苯组成的均相催化剂体系催化双环萜烯烃与CO的共聚反应，通过实验得到的适宜工艺条件为：10mmol冰片烯（冰片二烯），催化体系由0.1mmol乙酸钯、0.06mmol2,2-联吡啶、0.02mmol三氟甲基磺酸铜和0.07mmol硝基苯组成，15mL体积比为2:1的甲苯/甲醇混合溶剂，CO气体压力为3.5MPa，在60℃下反应2h；采用FT-IR、GPC、元素分析和热重分析对最佳工艺条件下所得的冰片烯/CO共聚物进行了分析和表征。结果表明，冰片烯与CO的共聚反应主要得到低分子量的低聚物，聚合物在185℃前都比较稳定；采用FT-IR、GPC、SEM、DSC、X-射线衍射、元素分析、核磁共振和热重分析对最佳工艺条件下所得的冰片二烯/CO共聚物进行了分析和表征。结果表明，冰片二烯与CO的共聚反应得到的共聚物为白色块状固体，而且具有一定的结晶性，不易溶于极性溶剂中，玻璃化转变温度为145℃，聚合物在290℃前都比较稳定；此外，对其共聚反应机理进行了探讨。
（4）双环萜烯烃进行环氧化反应合成环氧化双环萜烯烃。在相转移催化剂作用下，以自制的浓度约35%过氧乙酸作为环氧化试剂，制备得到了2,3-环氧蒎烷和2,10-环氧蒎烷，结果表明，加入相转移催化剂有利于提高环氧蒎烷的选择性，其中2,3-环氧蒎烷的选择性达92.20%，2,10-环氧蒎烷的选择性达85.90%；以间氯过氧苯甲酸（m-CPBA）作为环氧化试剂，制备得到环氧冰片烯和环氧冰片二烯，最佳宜工艺条件为：向三口烧瓶中加入1mmol冰片烯（冰片二烯）和10mL二氯甲烷后，机械搅拌作用下于20℃下加入3mmolm-CPBA，反应2h，冰片烯和冰片二烯均可完全转化，环氧冰片烯的选择性可达90.46%，环氧冰片二烯的选择性为90.27%；探讨了蒎烯环氧化得到环氧蒎烷的反应机理和冰片烯和冰片二烯在m-CPBA作用下的环氧化反应机理。
（5）以实验室自制的环氧双环萜烯烃为原料，与CO_2进行共聚反应，所使用的催化剂是由沉淀法合成的Zn_3[Co(CN)_6]_2基的DMC催化剂，分别采用FT-IR和TG分析对催化剂的结构和热稳定性能进行了表征。
Serials of pinene derivant were synthesized using bicyclic terpene pinene as raw materials,and copolymerization reaction of those pinene derivant with SO_2, CO or CO_2were studied,main results as follow:
(1) Bornylene and bornadiene were synthesized by using2-Chlorocamphane and2,6-Dichlorocamphane as raw materials under microwave irradiation heating, the optimumprocess condition was in a glass flask,0.1mol2-Chlorocamphane (2,6-Dichlorocamphane)and0.3mol potassium tert-butoxide were charged, then added N, N'-dimethylformamide assolvent, in the microwave oven, the reaction mixture was heated with120℃for around60minunder microwave power of400W, results showed that the conversion of raw materials and theselectivity of products both up to100%, Compare to traditional oil bath heating, microwaveirradiation heating shortened the reaction time greatly and improved the reaction efficiencyimmensely. Furthermore, mechanism of the isomerization and rearrangement reaction of pineneto obtain2-Chlorocamphane and2,6-Dichlorocamphane and the elimination reaction of2-Chlorocamphane and2,6-Dichlorocamphane to obtain bornylene and bornadiene werediscussed.
(2) Copolymerization of bicyclic terpene with SO_2, SO_2and maleic anhydride or SO_2andstyrene were also studied, copolymers were characterized by using FT-IR, GPC and SEManalysis. Moreover, mechanism of the copolymerization reaction was studied.
(3) Copolymerization of bornylene or bornadiene with CO were studied, a homogeneouscatalyst system made up of Pd(OAc)2/2,2'-bipyridine/nitrobenzene/Cu(OTf)2/methanol/toluene was used as the catalyst, results showed that the optimum process condition as follow:10mmol bornylene (bornadiene) was placed into the autoclave, a homogeneous catalystcontaining0.1mmol Pd(OAc)2,0.06mmol2,2'-bipyridine,0.07mmol nitrobenzene, and0.02mmol Cu(OTf)2was dissolved in15mL solvent mixture composed of methanol/toluene (v/v,2/1), the solution was charged, and the autoclave was subsequently pressurized to3.5MPa withCO. The mixture was reacted at60°C for2h under stirring. The bornylene/CO copolymer wascharacterized by FT-IR、GPC、EA and TG analysis, it was found that only oligomer which wasstable before185℃was obtained in the copolymerization of bornylene with CO. Thebornadiene/CO copolymer was by FT-IR, GPC, SEM,DSC, X-ray, EA,1H NMR,13C NMRand TG analysis, it demonstrated that the resultant copolymer was white solid and showed poor solubility in polar organic solvents, thermal analyses revealed that it is partially crystalline witha Tgof145°C, and it was stable before290°C. Furthermore, mechanism of thecopolymerization reaction was studied.
(4)2,3-Epoxy pinane and2,10-eposy pinane were synthesized by using peroxyacetic acidas epoxidizing agent and catalyzing with phase transfer catalyst, the optimum process conditionas follow:0.8mol anhydrous sodium carbonate,1.0mmol TEBA and30mL methylenedichloride were charged into a three-neck flask,3.0mol high concentration peroxyacetic acidwas added dropwise with stirring under20℃, thereafter, the reaction mixture continued at thistemperature for2h with continuous stirring, results showed that the selectivity of2,3-epoxypinane was92.20%and2,10-epoxy pinane was85.90%. Epoxy bornylene and epoxybornadiene were synthesized by using m-CPBA as epoxidizing agent, the optimum processcondition as follow:1mol bornylene (bornadiene) and10mL methylene dichloride werecharged into a three-neck flask,3mmol m-CPBA was added with stirring under20℃, thereafter,the reaction mixture continued at this temperature for2h with continuous stirring, resultsshowed that the conversion of bornylene and bornadiene both up to100%, the selectivity ofepoxy bornylene was90.46%and epoxy bornadiene was90.27%. Furthermore, mechanism ofthe epoxidation reaction of pinene to obtain epoxy pinane catalyzing with phase transfercatalyst and epoxidation reaction of bornylene and bornadiene by of pinene to obtain2-Chlorocamphane and2,6-Dichlorocamphane and the elimination reaction of2-Chlorocamphane and2,6-Dichlorocamphane to obtain bornylene and bornadiene by usingm-CPBA as epoxidizing agent to obtain epoxide were discussed.
(5) Copolymerization of epoxy bicyclic terpene with CO were studied, Zn_3[Co(CN)_6]_2based DMC catalyst which synthesized by using precipitation method was used as catalyst, thestructure and thermal stability of catalyst were characterized by FT-IR and TG analysis.
（1）采用微波辐照法合成了冰片烯和冰片二烯，通过实验得到的最佳合成工艺条件为：0.1mol2-氯莰烷（2,6-二氯莰烷），0.3mol叔丁醇钾，N,N’-二甲基甲酰胺作溶剂，微波辐照温度120℃，微波功为400W，微波辐照时间为60min，原料可达到完全转化，产物选择性为100%，与传统油浴加热法相比，微波辐照法极大地提高了反应效率；同时探讨了合成氯莰烷和冰片烯与冰片二烯的反应机理，表明蒎烯在酸性条件下发生了瓦格聂尔-梅尔魏因重排反应得到氯莰烷，而氯莰烷生成烯烃的反应则是一个双分子消除反应（E2）历程。
（2）以双环萜烯烃——蒎烯、冰片烯和冰片二烯作为共聚单体，分别与SO_2、SO_2和马来酸酐以及SO_2和苯乙烯进行自由基共聚反应，采用FT-IR、GPC、SEM、能谱分析仪和元素分析对共聚产物进行了分析和表征，并探讨了共聚反应的机理，表明聚合反应是原料与三重态3SO_2以自由基链方式进行的自由基共聚。
（3）以冰片烯和冰片二烯作为共聚单体，采用乙酸钯/2,2’-联吡啶/硝基苯/三氟甲基磺酸铜/甲醇/甲苯组成的均相催化剂体系催化双环萜烯烃与CO的共聚反应，通过实验得到的适宜工艺条件为：10mmol冰片烯（冰片二烯），催化体系由0.1mmol乙酸钯、0.06mmol2,2-联吡啶、0.02mmol三氟甲基磺酸铜和0.07mmol硝基苯组成，15mL体积比为2:1的甲苯/甲醇混合溶剂，CO气体压力为3.5MPa，在60℃下反应2h；采用FT-IR、GPC、元素分析和热重分析对最佳工艺条件下所得的冰片烯/CO共聚物进行了分析和表征。结果表明，冰片烯与CO的共聚反应主要得到低分子量的低聚物，聚合物在185℃前都比较稳定；采用FT-IR、GPC、SEM、DSC、X-射线衍射、元素分析、核磁共振和热重分析对最佳工艺条件下所得的冰片二烯/CO共聚物进行了分析和表征。结果表明，冰片二烯与CO的共聚反应得到的共聚物为白色块状固体，而且具有一定的结晶性，不易溶于极性溶剂中，玻璃化转变温度为145℃，聚合物在290℃前都比较稳定；此外，对其共聚反应机理进行了探讨。
（4）双环萜烯烃进行环氧化反应合成环氧化双环萜烯烃。在相转移催化剂作用下，以自制的浓度约35%过氧乙酸作为环氧化试剂，制备得到了2,3-环氧蒎烷和2,10-环氧蒎烷，结果表明，加入相转移催化剂有利于提高环氧蒎烷的选择性，其中2,3-环氧蒎烷的选择性达92.20%，2,10-环氧蒎烷的选择性达85.90%；以间氯过氧苯甲酸（m-CPBA）作为环氧化试剂，制备得到环氧冰片烯和环氧冰片二烯，最佳宜工艺条件为：向三口烧瓶中加入1mmol冰片烯（冰片二烯）和10mL二氯甲烷后，机械搅拌作用下于20℃下加入3mmolm-CPBA，反应2h，冰片烯和冰片二烯均可完全转化，环氧冰片烯的选择性可达90.46%，环氧冰片二烯的选择性为90.27%；探讨了蒎烯环氧化得到环氧蒎烷的反应机理和冰片烯和冰片二烯在m-CPBA作用下的环氧化反应机理。
（5）以实验室自制的环氧双环萜烯烃为原料，与CO_2进行共聚反应，所使用的催化剂是由沉淀法合成的Zn_3[Co(CN)_6]_2基的DMC催化剂，分别采用FT-IR和TG分析对催化剂的结构和热稳定性能进行了表征。
Serials of pinene derivant were synthesized using bicyclic terpene pinene as raw materials,and copolymerization reaction of those pinene derivant with SO_2, CO or CO_2were studied,main results as follow:
(1) Bornylene and bornadiene were synthesized by using2-Chlorocamphane and2,6-Dichlorocamphane as raw materials under microwave irradiation heating, the optimumprocess condition was in a glass flask,0.1mol2-Chlorocamphane (2,6-Dichlorocamphane)and0.3mol potassium tert-butoxide were charged, then added N, N'-dimethylformamide assolvent, in the microwave oven, the reaction mixture was heated with120℃for around60minunder microwave power of400W, results showed that the conversion of raw materials and theselectivity of products both up to100%, Compare to traditional oil bath heating, microwaveirradiation heating shortened the reaction time greatly and improved the reaction efficiencyimmensely. Furthermore, mechanism of the isomerization and rearrangement reaction of pineneto obtain2-Chlorocamphane and2,6-Dichlorocamphane and the elimination reaction of2-Chlorocamphane and2,6-Dichlorocamphane to obtain bornylene and bornadiene werediscussed.
(2) Copolymerization of bicyclic terpene with SO_2, SO_2and maleic anhydride or SO_2andstyrene were also studied, copolymers were characterized by using FT-IR, GPC and SEManalysis. Moreover, mechanism of the copolymerization reaction was studied.
(3) Copolymerization of bornylene or bornadiene with CO were studied, a homogeneouscatalyst system made up of Pd(OAc)2/2,2'-bipyridine/nitrobenzene/Cu(OTf)2/methanol/toluene was used as the catalyst, results showed that the optimum process condition as follow:10mmol bornylene (bornadiene) was placed into the autoclave, a homogeneous catalystcontaining0.1mmol Pd(OAc)2,0.06mmol2,2'-bipyridine,0.07mmol nitrobenzene, and0.02mmol Cu(OTf)2was dissolved in15mL solvent mixture composed of methanol/toluene (v/v,2/1), the solution was charged, and the autoclave was subsequently pressurized to3.5MPa withCO. The mixture was reacted at60°C for2h under stirring. The bornylene/CO copolymer wascharacterized by FT-IR、GPC、EA and TG analysis, it was found that only oligomer which wasstable before185℃was obtained in the copolymerization of bornylene with CO. Thebornadiene/CO copolymer was by FT-IR, GPC, SEM,DSC, X-ray, EA,1H NMR,13C NMRand TG analysis, it demonstrated that the resultant copolymer was white solid and showed poor solubility in polar organic solvents, thermal analyses revealed that it is partially crystalline witha Tgof145°C, and it was stable before290°C. Furthermore, mechanism of thecopolymerization reaction was studied.
(4)2,3-Epoxy pinane and2,10-eposy pinane were synthesized by using peroxyacetic acidas epoxidizing agent and catalyzing with phase transfer catalyst, the optimum process conditionas follow:0.8mol anhydrous sodium carbonate,1.0mmol TEBA and30mL methylenedichloride were charged into a three-neck flask,3.0mol high concentration peroxyacetic acidwas added dropwise with stirring under20℃, thereafter, the reaction mixture continued at thistemperature for2h with continuous stirring, results showed that the selectivity of2,3-epoxypinane was92.20%and2,10-epoxy pinane was85.90%. Epoxy bornylene and epoxybornadiene were synthesized by using m-CPBA as epoxidizing agent, the optimum processcondition as follow:1mol bornylene (bornadiene) and10mL methylene dichloride werecharged into a three-neck flask,3mmol m-CPBA was added with stirring under20℃, thereafter,the reaction mixture continued at this temperature for2h with continuous stirring, resultsshowed that the conversion of bornylene and bornadiene both up to100%, the selectivity ofepoxy bornylene was90.46%and epoxy bornadiene was90.27%. Furthermore, mechanism ofthe epoxidation reaction of pinene to obtain epoxy pinane catalyzing with phase transfercatalyst and epoxidation reaction of bornylene and bornadiene by of pinene to obtain2-Chlorocamphane and2,6-Dichlorocamphane and the elimination reaction of2-Chlorocamphane and2,6-Dichlorocamphane to obtain bornylene and bornadiene by usingm-CPBA as epoxidizing agent to obtain epoxide were discussed.
(5) Copolymerization of epoxy bicyclic terpene with CO were studied, Zn_3[Co(CN)_6]_2based DMC catalyst which synthesized by using precipitation method was used as catalyst, thestructure and thermal stability of catalyst were characterized by FT-IR and TG analysis.
引文
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