氧化叔胺树脂的合成及其对苯酚的吸附性能研究

将D301树脂的叔胺基氧化，合成了大孔交联氧化叔胺树脂．比较D301树脂与氧化叔胺树脂对正己烷溶液中和水溶液苯酚的吸附性能，发现氧化叔胺树脂对苯酚的吸附量比D301树脂的有明显的增加．为弄清吸附量增加的原因，根据氧化叔胺树脂对正己烷溶液中苯酚的吸附等温线，利用热力学函数关系计算了等量吸附焓、吸附Gibbs自由能和吸附熵，发现叔胺树脂氧化后，与苯酚的相互作用和吸附的自发倾向增强，但吸附过程仍为氢键吸附．     

非水体系中大孔交联酰胺基树脂的吸附热力学

合成了大孔交联聚（N-甲基-N-对乙烯基苄基乙酰胺）树脂,测定了树脂对环己烷溶液中苯酚的吸附等温线,根据热力学函数关系计算了等量吸附焓、吉布斯吸附自由能和吸附熵,推测吸附过程为氢键吸附.同时,通过比较树脂对环己烷溶液中苯酚和邻硝基苯酚的吸附性能的差别,进一步论证了大孔交联聚（N-甲基-N-对乙烯基苄基乙酰胺）树脂对非水体系中酚类物质的吸附是基于氢键作用的机理.     

聚(N-对乙烯基苄基二甲胺)树脂对苯酚的吸附性能

采用二甲胺为功能化试剂,化学修饰氯甲基化苯乙烯-二乙烯基苯共聚物合成了大孔交联聚(N-对乙烯基苄基二甲胺)树脂,测得树脂的氯含量由4.2mmol/g降低到0.24mmol/g,树脂的弱碱交换量为4.0mmol/g,说明氯甲基化苯乙烯-二乙烯基苯共聚物发生胺化反应完全。在水溶液中,测定了大孔交联聚(N-对乙烯基苄基二甲胺)树脂对苯酚的吸附等温线,发现吸附平衡数据符合Freundlich等温吸附方程,相关系数大于0.99。计算得到在吸附量为15、20和25mg/g时,等量吸附焓在-20.81~-30.74kJ/mol范围内,吸附自由能和吸附熵均小于0,说明吸附过程中存在氢键作用,吸附是自发、混乱度变小的过程。比较树脂对水溶液中苯酚、对硝基苯酚和对硝基甲苯的吸附性能以及树脂对水、环己烷、乙醇和乙酸乙酯溶液中苯酚的吸附性能,进一步说明大孔交联聚(N-对乙烯基苄基二甲胺)树脂对水溶液中苯酚的吸附是基于疏水作用和氢键作用协同的机理。     

聚（对乙烯基苄基己内酰胺）树脂对非水体系中苯酚的吸附热力学

测定了聚（对乙烯基苄基己内酰胺）吸附树脂对正庚烷溶液中苯酚的吸附等温线,发现吸附等温线符合Freundlich等温吸附方程,相关系数大于0．99．根据热力学函数关系计算了等量吸附焓、Gibbs吸附自由能和吸附熵,等量吸附焓在30～40kJ／mol之间,推测吸附过程为氢键吸附．通过比较树脂对正庚烷中苯酚和邻硝基苯酚的吸附性能的差别,进一步论证了树脂对非水体系中酚类物质的吸附是基于氢键作用的机理．同时,聚（对乙烯基苄基己内酰胺）树脂对正庚烷溶液中苯酚的吸附相对水溶液中苯酚的吸附有更低的吸附焓变、吸附自由能变和吸附熵变．     

超高交联聚苯乙烯对非水体系中苯酚的吸附热力学研究

采用“一锅法”以氯化锌为催化剂合成了超高交联聚苯乙烯。测定了超高交联聚苯乙烯对环己烷中苯酚的吸附等温曲线，利用热力学函数关系计算出了吸附焓、吸附自由能和吸附熵，比较了超高交联聚苯乙烯对苯酚和苯甲醚吸附性能的差别，推测吸附过程的主要作用为氢键作用。以小分子化合物为模型，通过分子间相互作用能的计算，论证了树脂是通过其羰基氧原子与苯酚的羟基氢原子之间的氢键作用而吸附苯酚的。     

聚(N-甲基-N-对乙烯基苄基乙酰胺)对水中苯酚的吸附

由大孔交联氯甲基化聚苯乙烯进行甲胺化和乙酰化反应,合成了聚(N-甲基-N-对乙烯基苄基乙酰胺)树脂,树脂的氯含量由原来的3.95mmol/g降至0.63mmol/g.测定了树脂对水中苯酚的吸附等温线,结果表明,吸附平衡数据符合Freundlich等温方程.利用热力学函数关系计算了吸附焓、吸附自由能和吸附熵,结果表明,吸附量在10～40mg/g时,吸附焓为-71.20～-24.65kJ/mol,吸附自由能为-4.64～-6.07kJ/mol,吸附熵为-62.35～-218.56J/(mol·K).讨论了吸附过程中树脂对水中苯酚吸附的氢键与疏水作用的吸附机理.     

大孔交联聚(对乙烯基苄基苯基醚)树脂对苯酚的吸附机理

由氯甲基化聚苯乙烯合成了大孔交联聚(对乙烯基苄基苯基醚)树脂(简称为苯基醚树脂), 测定了其对正己烷和水中苯酚的吸附等温线, 计算了吸附焓. 同时, 比较了聚(对乙烯基苄甲醚)、苯基醚树脂、聚(对乙烯基苄基对硝基苯基醚)和聚(对乙烯基苄基对甲基苯基醚)对正己烷中苯酚的吸附性能以及氯甲基化聚苯乙烯和苯基醚树脂对水中苯酚、2,3,5-三甲基苯酚和对硝基甲苯的吸附性能. 结果表明, 苯基醚树脂是通过氢键吸附正己烷溶液中苯酚的, 而其对水中苯酚的吸附是基于氢键和疏水作用的协同.     

大孔交联聚(对乙烯基苄基苯胺)树脂对苯酚的吸附

由氯甲基化聚苯乙烯合成了大孔交联聚(对乙烯基苄基苯胺)树脂, 测定了其对正己烷和水中苯酚的吸附等温线, 计算了吸附焓. 结果表明, 苯胺基树脂主要是通过氢键吸附正己烷中苯酚的, 树脂负载的功能基氮原子和苯环都作为氢键受体与苯酚的羟基氢原子形成氢键, 而其对水中苯酚的吸附是基于氢键和疏水作用.     

D301大孔树脂吸附钒(V)的性能研究

研究了D301大孔树脂对钒的吸附性能.结果表明,pH值对D301树脂吸附钒的影响很大,与钒在溶液中的赋存状态有关,且在pH=2时吸附效果最好:测得吸附热力学参数分别为:△H=8.97kJ/mol,△G_(313)=-5.69kJ/mol,△G_(303)=-5.2kJ/mol,△G_(293)=-4.9kJ/mol,△S=46.84J/mol·K.等温吸附服从Freundlich经验式;考察了溶液浓度、搅拌速率对交换过程的影响,并对实验数据运用相关理论模型进行拟合,结果显示钒(V)在D301树脂上吸附交换过程控制步骤为颗粒扩散控制,反应级数n为0.2391.     

新型胺基修饰的超高交联聚合吸附剂吸附水中酚类化合物的研究

合成了新的胺基修饰的超高交联AH系列吸附树脂．以弱碱树脂D301和超高交联吸附树脂ND100为参照，测定了AH系列吸附树脂吸附水中苯酚、对氯苯酚、对甲苯酚、对硝基苯酚的吸附性能。结果表明：修饰的超高交联吸附树脂对苯酚．对甲苯酚、对氟苯酚的吸附量比ND100和D301更大，而D301树脂对对硝基苯酚有最大的吸附量．提出了AH系列树脂对4种酚类化合物吸附行为的作用机理．     

ADSORPTION OF PHENOL IN NON—AQUEOUS SYSTEM BASED ON HYDROGEN—BONDING

Two hydrogen-bonding adsorbents-macroporous crosslinked poly(P-nitrostyrene)and poly(p-vinylbenzyl amide)-were synthesized,and the adsorption property of phenol from cyclohexane solution onto the adsorbents was studied,The differential adsorption heasts for varied adsorption capacities calculated from the adsorption isotherms according to the Claperyron-Clausius equation lay in the range of hydrogen bond energy (8-50kJ/mol),The adsorption capaccity of o-nitrophenol in cyclohexane was moch less than that of phenol under the same condition.The adsorption capacity of phenol from cyclohexane onto polyacrylonitrile was much less than that onto poly(p-nitrostyrene)or poly(p-vinylbenzyl amide),All these results revealed that adsorption of phenol from cyclohexane by poly(p-nitrostyrene) or poly(p-vinylbenzyl amide)is based on hydrogen-bonding.     

ADSORPTION OF PHENOL IN NON-AQUEOUS SYSTEM BASED ON HYDROGEN-BONDING

1 INTRODUCTIONHydrogen-bonding adsorbents are functional polymers for adsorption and separation via theformation of hydrogen bond between the adsorbentS and adsorbates. Because hydrogen bond is astrong intermolecular (or intramolecular) force, hydrogen-bonding adsorbents have strong potentto adsorbing adsorbates with which can form hydrogen bond. In our previous work, three seriesof hydrogen-bonding adsorbents have been studied, which were adsorbents with hydrogendonator, adsorbentS with …     

SORPTION OF PHENOL ONTO GEL—TYPE CROSSLINKED POLYSTYRENEISOCYANURIC ACID RESIN

Spherical crosslinked polystyrene-isocyanuric acid resin was synthesized by reaction of chloromethylated polystryene with isocyanuric acid.The sorption isotherms of phenol from aqueous solution and cyclohexane solution onto the resin were measured.It is of interest to notice that the resin sorbed phenol efficiently though its specific surface area was 0 and did not swell in water,and the sorption capactity from aqueous solution was close to that of phenol onto XAD-4 at the same equilibrium concentration.Sorption enthalpies calculated from the isotherms according to the Clausius-Clapeyron equation were -21-25kJ/mol and -39-41kJ/mol respectively.These values impled that the sorption processes were based on hydrogen bonding.In addition.the details of the hydrogen bonding between the active sites of the resin and phenol were suggested.     

SORPTION OF PHENOL ONTO GEL-TYPE CROSSLINKED POLYSTYRENEISOCYANURIC ACID RESIN

I INTRODUCTIONIn our previous work, three series of macroporous hydrogen-bonding adsorbents have beenstudied, which were adsorbents with hydrogen donator, adsorbents with hydrogen acceptor, andadsorbents with both hydrogen donator and acceptor if-31. If a gel-type resin with hydrogendonator and/or acceptor contacts with a compound with hydrogen acceptor and/Or donatof, canthe gel-type resin sorb the compound based on of hydrogen bonding? Here we report the sorptionof phenol onto gel-type …     

ADSORPTION OF CAFFEINE BY HYDROGEN DONATING ADSORBENTS BASED ON HYDROGEN BONDING

The adsorption isotherms of caffeine from aqueous solution onto three hydrogen donating adsorbents-hydroxypolystyrene,polystryene-azo-pyrogallol,and D72 resin-were measured.The adsorption enthalpies calculated from the isotherms according to the Clausisu-Clapeyron equation were -24-36kJ/mol,-32-37kJ/mol,and -19-24kJ/mol respectively.These values implied that the adsorption processes were based on hydrogen bonding.Furthermore.the mechanism of the adsorption of caffeine onto D72 resin was studied by IR spectra and the small molecular model experiments,and the results showed that the adsorption of caffeine onto hydrogen donating adsorbents was based on hydrogen bonding.