STUDY ON THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY POLYPROPYLENE-BASED VANADYL POLYIMIDODIACETATE——THIOUREA REDOX SYSTEM

The present paper deals with the kinetics of polymerization of acrylonitrile (AN) initialed by the redox system of polypropylene-based vanadyi polyimidodiacetate (PV)-thiourea (TU)in aqueous sulfuric acid in the temperature range from 25 to 40℃. The polymerization rate was measured by varying the concentrations of monomer, vanadyl polyimidodiacetate, thiourea and sulfuric acid. The overall rate of polymerization was summarized asRp=2.2×10~5e~(-6.560/RT) [AN]~(1.0)[PV]~(0.50)[TU]~(1.5)[H_2SO_4]~(2.0)The molecular weight of polyacrylonitrile based on the experimental data was:(?)=k 1/T [pv]~(0.50)[TU]~(1.5)[H_2SO_4]~(2.0)These results indicated that the chain radicals are terminated by combination and/or disproportionation rather than chain transfer. The cooperation effect of carboxylic groups and the macromolecular field effect of polymer supporter are the characters of vanadyl polyimidodiacetate such as the case reported in early paper.     

笼形聚肟偕亚氨二乙酸钒(Ⅳ)-硫脲体系引发丙烯腈聚合的研究

研究了笼形聚肟偕亚氨二乙酸钒(CPV)-硫脲(TU)体系在硝酸溶液中引发丙烯腈(AN)聚合反应.表观聚合速度(R_P)是 R_P=1.0×10~8e~(-10.500/RT)[AN]~(1.0)[CPV]~(1.0)[TU]~(1.5)[HNO_3]~(3.0) 聚合诱导期(τ)随反应温度和物料浓度发生变化,可表示为 1/τ=5.2×10~9e~(-12.800/RT)[AN]~1.0[CPV]~1.0[TU]~1.5[HNO_3]~3.0实验结果表明,聚合反应以单基终止为特征,可能是和高分子载体较大的空间位阻有关.     

DEPENDENCE OF ACRYLONITRILE POLYMERIZATION KINETICS ON THE COMPOSITION OF POLYAMIDOXIME-THIOUREA SYSTEM

The polymerization of acrylonitrile (AN) initiated by polypropylene based-polyamidoxime (PPAO)-thiourea (TU) system was investigated at [TU]/[PPAO]>0.5 molar ratio. It shows that the variation of the concentrations of PPAO, thiourea and nitric acid does not exert an observable influence on the reaction rate. The overall rate of polymerization (R_p) isR_p = 2.07e~(-7,800/RT)[ AN]~(2.0)The zero order dependence on PPAO and thiourea concentrations and the lowest value of the collision frequence factor were considered to be a feature of the primary radical termination.     

笼形聚肟偕亚氨二乙酸钒(Ⅳ)-硫脲体系引发丙烯腈聚合的研究

 研究了笼形聚肟偕亚氨二乙酸钒(CPV)-硫脲(TU)体系在硝酸溶液中引发丙烯腈(AN)聚合反应.表观聚合速度(R_P)是 R_P=1.0×10⁸e(-10.500/RT)[AN]^1.0[CPV]^1.0[TU]^1.5[HNO₃]^3.0 聚合诱导期(τ)随反应温度和物料浓度发生变化,可表示为 1/τ=5.2×10⁹e^-12.800/RT[AN]^1.0[CPV]^1.0[TU]^1.5[HNO₃]^3.0实验结果表明,聚合反应以单基终止为特征,可能是和高分子载体较大的空间位阻有关.     

POLYMERIZATION OF ACRYLONITRILE WITH ORGANOLANTHANIDES AS SINGLE-COMPONENT CATALYSTS

 Ind₂Y(μ-Et)₂AlEt₂ and Ind₂LnN(i-Pr)₂ (Ln = Y, Yb) were used as a single-component catalyst for the polymerization of acrylonitrile (AN) respectively. The regularity of polymerization of AN and stereoregularity of polyacrylonitrile (PAN) were also studied in both cases. Both catalysts can produce PAN with molecular weight from I0,000to 30,000. In addition, the catalytic activity and molecular weights were increased by the addition of PhONa.     

MECHANISM FOR THE INITIATION OF ACRYLONITRILE POLYMERIZATION BY POLYPROPYLENE-BASED POLYAMIDOXIME-THIOUREA COMBINATION

Polymerization of acrylonitrile (AN) in aqueous nitric acid initiated by polypropylene-based polyamidoxime (PPAO)-thiourea (TU) combination has been investigated. The overall rate of polymerization (R_p) under the conditions of [TU]/[PPAO]<0.5 molar ratio isThe molecular weights of the polymers were found to be inversely proportional to 3/2-power of nitric acid concentration and 1-power of thiourea concentration. In addition, it is independent with the concentrations of monomer and PPAO, and decreases with increasing temperature.On the basis of these experimental results, a coordination-proton transfer mechanism for the initiation was proposed and discussed.     

NONCONVENTIONAL EMULSION POLYMERIZATION OF ACRYLONITRILE CATALYZED BY in situ METAL COMPLEXw

 Nano-sized polyacrylonitrile (PAN) particles were prepared under the catalytic effect of in situ developed CoCl₂/EDTA complex with ammonium persulfate as the initiator in the absence of any added emulsifier. The emulsion polymerization was studied at varying concentrations of the initiator, monomer, complex and solvent over a temperature range of 30-70^oC. The overall activation energy (Ea, 49.79 kJ/mol), energy of dissociation of initiator (Ed, 82.68 kJ/mol), number of micelles (0.163 x 1018) and the viscosity average molecular weight of the polymer were computed. The distribution of particle sizes was determined by transmission electron microscopy (TEM). It was found that the oil-in-water polymerization was stabilized by the presence of the CoCl₂/EDTA in situ complex reducing the particle size into the nano order. The average diameters of PAN nano particles, obtained by TEM, were in the range of 50–150 nm at the maximum conversion. The experimental particle size was mainly dependent on the concentration of the complex and temperature.     

聚偕氨肟—硫脲络合物的组成对丙烯腈聚合的影响

在聚丙烯基聚偕氨肟(PPAO)—硫脲(TU)体系引发丙烯腈(AN)聚合过程中,将 c(TU)/c(PPAO)摩尔比调节在0.5以上,可以观察到 PPAO、硫脲和硝酸浓度的变化对聚合速度都不产生实质性的影响,但聚合诱导期则随 c(TU)/c(PPAO)摩尔比增大而延长。根据实验结果,得表观聚合速度R_p=2.07e~(-32.6KJ/RT)c~(2.0)(AN)碰撞频率因子极低和引发体系的零级反应是链自由基向初级自由基碰撞终止的特征。     

丙烯腈与衣康酸的溶液共聚合

为了获得性能优越的碳纤维,聚丙烯腈（ＰＡＮ）纤维已经成为应用最广泛的前驱体之一［１］．事实表明,碳纤维的性能在很大程度上依赖于前驱体纤维的性能［１］,利用丙烯腈与少量其它单体进行共聚,可使聚合物的力学性能（机械强度、弹性、塑性等）得到明显的改善．由已报道的文章可知,与丙烯腈共聚时所采用的其它单体主要有丙烯酸、甲基丙烯酸、丙烯酸酯、丙烯酰胺、衣康酸等［２～７］,所采用的溶剂主要为二甲基甲酰胺（ＤＭＦ）．对在二甲基亚砜（ＤＭＳＯ）为溶剂中的聚合条件,并未见详细报道．本文以ＤＭＳＯ为溶剂,用偶氮二异丁…     

过氧化氢的热分解及其引发丙烯腈聚合反应的研究

本文研究了过氧化氢在二甲基甲酰胺中的热分解反应,测定了不同温度下的分解速率常数和表现活化能。同时研究了过氧化氢引发丙烯腈的聚合反应,确定了聚合动力学方程。     

STUDIES ON THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY METAVANADATE-CONTAININ G ANION EXCHANGER-THIOUREA REDOX SYSTEM

The polymerization of acrylonitrile (AN) in aqueous nitric acid initiated by metavanadate-containing anion exchange resin (PV)-thiourea (TU) redox system at 20—40℃. has been investigated. The overall rate of polymerization (R_p) is given byR_p=1.92×10~4e~(-6.860/RT) [AN]~(1.2) [PV]~(0.44) [TU]~(1.0)[HNO_3]~(1.0)The kinetic parameters differed from those of V~(5+)-TU system indicated that the generation of the primary radicals is mainly a difffusion-controlled reaction. The effect of macromolecular field arisen from the polymer matrix exerts a great influence on the polymerization process.     

笼形聚偕胺肟树脂的研究HX／ACAO树脂吸附贵金属

氢卤酸、硝酸、硫酸、磷酸和硼酸处理的笼形聚偕胺肟树脂（ＨＸ／Ａ－ＣＡＯ）对Ａｇ＋和等贵金属离子的吸附能力按如下顺序：ＰｄＣｌ４２－：Ｈ３ＢＯ３／ＡＣＡＯ＞ＢＣＡＯ＞Ｈ３ＰＯ４／ＡＣＡＯ＞ＨＩ／ＡＣＡＯ＞Ｈ２ＳＯ４／ＡＣＡＯ＞ＨＣｌ／ＡＣＡＯ＞ＨＮＯ３／ＡＣＡＯ＞ＨＦ／ＡＣＡＯ．ＩｒＣｌ６２－：ＢＣＡＯ＞Ｈ３ＰＯ４／ＡＣＡＯ＞Ｈ３ＢＯ３／ＡＣＡＯ＞ＨＣｌ／ＡＣＡＯ＞ＨＦ／ＡＣＡＯ＞ＨＩ／ＡＣＡＯ＞Ｈ２ＳＯ４／ＡＣＡＯ≥ＨＮＯ３／ＡＣＡＯ．ＰｔＣｌ６２：ＢＣＡＯ＞Ｈ３ＢＯ３／ＡＣＡＯ＞Ｈ２ＳＯ４／ＡＣＡＯ＞ＨＮＯ３／ＡＣＡＯ＞ＨＣｌ／ＡＣＡＯ＞ＨＦ／ＡＣＡＯ＞Ｈ３ＰＯ４／ＡＣＡＯ＞ＨＩ／ＡＣＡＯ．Ａｇ＋：ＢＣＡＯ＞Ｈ３ＢＯ３／ＡＣＡＯ＞ＨＩ／ＡＣＡＯ＞Ｈ２ＳＯ４／ＡＣＡＯ＞ＨＦ／ＡＣＡＯ＞ＨＣｌ／ＡＣＡＯ＞Ｈ３ＰＯ４／ＡＣＡＯ＞ＨＮＯ３／ＡＣＡＯ．ＡｕＣｌ４－：ＢＣＡＯ＞Ｈ３ＢＯ３＞Ｈ３ＰＯ４／ＡＣＡＯ＞ＨＦ／ＡＣＡＯ＞ＨＣｌ／Ａ－ＣＡＯ＞Ｈ２ＳＯ４／ＡＣＡＯ＞ＨＩ／ＡＣＡＯ＞ＨＮＯ３／Ａ－ＣＡＯ．研究了Ｈ３ＢＯ３／ＡＣＡＯ树脂对Ａｇ＋和离子的吸附动力学，讨论了吸附机理．     

NONCONVENTIONAL EMULSION POLYMERIZATION OF ACRYLONITRILE CATALYZED BY in situ METAL COMPLEX

Nano-sized polyacrylonitrile (PAN) particles were prepared under the catalytic effect of in situ developed CoCl2/EDTA complex with ammonium persulfate as the initiator in the absence of any added emulsifier. The emulsion polymerization was studied at varying concentrations of the initiator, monomer, complex and solvent over a temperature range of 30-70℃. The overall activation energy (Ea, 49.79 kJ/mol), energy of dissociation of initiator (Ed,82.68 kJ/mol), number of micelles (0.163×1018) and the viscosity average molecular weight of the polymer were computed. The distribution of particle sizes was determined by transmission electron microscopy (TEM). It was found that the oil-in-water polymerization was stabilized by the presence of the CoCl2/EDTA in situ complex reducing the particle size into the nano order. The average diameters of PAN nano particles, obtained by TEM, were in the range of 50-150 nm at the maximum conversion. The experimental particle size was mainly dependent on the concentration of the complex and temperature.     

杨梅形聚肟偕亚氨二乙酸钒(Ⅳ)—硫脲体系引发丙烯腈聚合的研究

研究了杨梅形聚肟偕亚氨二乙酸树脂负载VO~(2+)(PV)与疏脲(TU)组合在硝酸溶液中引发丙烯腈(AN)的聚合反应。在实验条件下,表观聚全速度可表示为 R_p=1.91×10~5e~(-45.0/RT)c~(1.9)(AN)c~(1.0)(HNO_3)c~(0.60)(PV)c~(1.50)(TU) 聚合诱导期(τ)与反应物浓度和聚合温度关系是 1/τ=8.27×10~7e~(-38.3/RT)c~(1.9)(HNO_3)c~(0.60)(PV)C~(1.50)(TU)=K_τ;·R_i/R_p 在酸性介质中,氨羧基的协同作用促使键合的VO~(2+)氧化为VO_2~+,随后硫脲配位并通过氢桥缔合,后者分解生成初级自由基,引发丙烯腈的聚合反应。     

TERMINATION AND TRANSFER OF THE CHAIN RADICALS IN THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY VANADIUM(V)-THIOUREA REDOX SYSTEM

The dependence of the molecular weights on the concentration of reactants in the polymerization of acrylonitrile initiated by vanadium (V)-thiourea redox system has been investigated. It was found that the molecular weights of the polymer change nonlinearly with increasing concentrations of nitric acid and thiourea. Probably, the composition of the complexes exert a great influence on the chain initiation and termination. The reaction of "complextermination" gives rise to the decrease of the molecular weights markedly while the concentrations of thiourea and vanadium (V)in the range from one to three molar ratios.     

净化丙烯腈废气催化剂的研究

研究了贵金属Ｐｄ，Ｐｔ，非贵金属Ｃｕ－Ｍｎ氧化物沸石等催化剂对含－ＣＮ有机物丙烯腈的氧化活性，结果表明，以Ｃｕ－Ｍｎ作活性组分、ＺｒＯ２作助活性组分的催化剂对丙烯腈有较高的氧化活性，较强的控ＮＯｘ能力、较低的起燃温度、较宽的浓度处理范围和较魇空速处理能力，３００ｈ稳定性试验后催化剂活性仍在９９％以上。Ｏ２－ＴＰＤ及扫描电镜表征结果很好地支持了反应结果。     

羧化聚丙烯载体的链结构对丙烯腈聚合的影响

研究了羧化聚丙烯载体(不饱和羧酸接枝聚丙烯)接枝链的结构对丙烯腈聚合速度的影响。在引发活性方面对聚羧酸氧钒(聚合物负载催化剂)、异丁酸氧钒(小分子同系物)和硫酸氧钒(小分子非同系物)作了对比。实验结果表明:(1)(P-COO)_2VO两羧基之间存在着协同作用;(2)大分子链效应加强了羧基的协同作用;(3)聚羧酸链的d-、1-构型、羧基间距和载体的传质效应对聚合速度均有影响;(4)在本实验条件下,引发机理与高分子载体的链结构无关。     

聚丙烯基聚偕氨肟—硫脲络合物引发丙烯腈聚合动力学及机理

研究了硝酸溶液中聚丙烯基聚偕氨肟(PPAO)—硫脲(TU)络合物引发丙烯腈(AN)聚合动力学。在[TU]/[PPAO]<0.5摩尔比的条件下,表观聚合速度(R_p)是R_p=9.1×10~4e~(-45.2k J/RT)[AN]~(2.0)[HNO_3]~(1.5)[TU]~(1.0)聚合物分子量随聚合温度升高而下降,并与硝酸浓度的1.5次方和硫脲浓度的1.0次方成反比,与丙烯腈浓度和 PPAO 浓度无关。可表示为_m=K·1/T·(1/[HNO_3]~(1.5)[TU]~(1.0))=K_M·1/T·(R_p/R_t)根据实验结果,提出了“络合—质子转移”引发机理。     

芳氧基钇在DMF中引发丙烯腈聚合的动力学研究

用单组分三(2,6-二叔丁基4甲基苯氧基)钇配合物[Y(OAr)3]引发丙烯腈聚合,发现介质对聚合反应的影响很大,在介电常数较大的极性溶剂N,N-二甲基甲酰胺(DMF)中,AN聚合反应的活性较高,在50℃下聚合3h,丙烯腈聚合反应转化率达到94%,所得聚丙烯腈(PAN)含52%间规结构.在DMF中聚合反应速率与单体、引发剂的浓度分别呈一级关系,丙烯腈聚合反应的表观活化能为22.1kJ·mol-1.     

笼形聚偕胺肟树脂对羧酸的吸附作用

研究了碱处理笼形聚偕胺肟树脂（ＢＣＡＯ）对饱和一元脂肪酸、二元脂肪酸、不饱和脂肪酸、α－取 代乙酸和羟基羧酸的吸附作用。发现ＢＣＡＯ对羧酸强烈吸附。一元羧酸在ＢＣＡＯ上以多分子层吸附占优势,二元和三元羧酸则以单分子层吸附为主要特征;后者作为阴离子聚体吸着在ＢＣＡＯ表面,形成了对外来的羧酸阴离子起排斥作用的离子场。