Research On Synthesis Of New Materials By Copolymerization Of Pinene Derivatives With CO_x/SO₂

Serials of pinene derivant were synthesized using bicyclic terpene pinene as raw materials,and copolymerization reaction of those pinene derivant with SO₂, CO or CO₂were 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 SO₂, SO₂and maleic anhydride or SO₂andstyrene 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, Zn₃[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.