PREPARATION AND CHARACTERIZATION OF SCHIFF BASE POLYMERS DERIVED FROM 4,4'-METHYLENEBIS(CINNAMALDEHYDE)

New Schiff base polymers poly[4,4＇-methylenebis（cinnamaldehyde）ethylenediimine] （PMBCen）, poly[4,4＇- methylenebis（cinnamaldehyde）1,2-propylenediimine] （PMBCPn）, poly[4,4＇-methylenebis（cinnamaldehyde）1,3-propylenediimine] （PMBCPR）, poly[4,4＇-methylenebis（cinnamaldehyde） 1,2-phenylenediimine] （PMBCPh）, poly[4,4＇-methylenebis（cinnamaldehyde）meso-stilbenediimine] （PMBCS）, poly[4,4＇-methylenebis（cinnamaldehyde）urea] （PMBCUR）, poly[4,4＇- methylenebis（cinnamaldehyde）semicarbazone] （PMBCSc）, poly[4,4＇-methylenebis（cinnamaldehyde）thiosemicarbazone] （PMBCTSc） and poly[4,4＇-methylenebis（cinnamaldehyde）hydrazone] （PMBCH） were formed by polycondensation of 4,4＇- methylenebis（cinnamaldehyde） with ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-phenylenediamine, meso-stilbenediamine, urea, semicarbazide, thiosemicarbazide and hydrazine, respectively. The dialdehyde and polymers have been characterized through elemental micro-analysis, IR, UV-Vis and ^1H-NMR spectroscopic techniques. Thermoanalytical studies and viscous flow of dilute solutions of dialdehyde and its polymers have been examined and compared.

Polymerization of isoprene catalyzed by neodymium heterocyclic Schiff base complex

Neodymium-based heterocyclic Schiff base complex was prepared and applied for the coordination polymerization of isoprene. This complex polymerized isoprene to afford products featuring high cis-1,4 stereospecificity （ca. 95%） and high molecular weight （ca, 10^5） in the presence of the triisobutyl aluminium （AliBu3） as cocatalyst, The microstructure of obtained polyisoprene was investigated by FTIR, 1^H NMR. Two different kinds of active centers in the catalyst system were examined by GPC method.

Lanthanum heterocyclic Schiff-base complex initiated ring-opening polymerization of ε-caprolactone

Lanthanum complex supported by the heterocyclic Schiff-base ligand of N-(2-pyridyl)-3,5-di-tert-butyl-salicylaldimine was prepared and employed for the ring-opening polymerization(ROP)ofε-caprolactone(ε-CL).The polymers obtained with this initiator showed a unimodal molecular weight distribution implied that only one active species was present.Mechanism study revealed that the polymerization proceeds via acyl-oxygen bond cleavage.

Synthesis,Crystal Structure and Characterization of a Nickel Complex Based on Phenoxyimine Ligand and Catalysis of the Vinyl Polymerization of Norbornene

The title complex N,O-bis{2-[[（2-benzhydryl-4,6-dimethylphenyl）imino]-methyl]-phenol}-nickel（II）（C56H48N2NiO2） has been synthesized by the reaction of 2-[[（2-benzhydryl-4,6-dimethylphenyl）mino]-methyl]-phenol with Ni（CH3COO）2·4 H2O, and characterized by elemental analysis and IR spectrum. The spatial structure of the complex has been confirmed by single-crystal X-ray diffraction analysis. The compound belongs to the monoclinic system, space group C2/c with a = 39.035（8）, b = 13.276（3）, c = 17.679（4） A°, β = 98.06（3）°, V = 9071（3） A°^3, C56H48N2NiO2, Mr = 839.67, Z = 8, Dc = 1.230 Mg/m^3, μ = 0.472 mm^-1, F（000） = 3536, T = 293（2） K, the final R = 0.0675 and w R = 0.1345（I 〉 2s（I））. The compound showed excellent catalytic activity up to 1.268 × 10^7 g of PNB（mol of Ni）^-1h^-1 for the addition polymerization of norbornene by using methylaluminoxane（MAO） as a cocatalyst.

Synthesis, Crystal Structure and Norbornene Polymerization of a Palladium(Ⅱ) Complex Based on Phenoxyimine Ligand

The title complex N,O-bis{2-[[(2,6-benzhydryl-4-methylphenyl)imino]-methyl]-phenol}-palladium(II)(C_(80)H_(64)N_2O_2 Pd) has been synthesized by the reaction of 2-[[(2,6-benzhydryl-4-methylphenyl)imino]-methyl]-phenol with Pd(CH_3COO)_2, and characterized by IR spectrum and elemental analysis. The spatial structure of the complex has been verified by single-crystal X-ray diffraction analysis. The compound belongs to the monoclinic system, space group P21/n with a = 13.492(3), b = 16.924(3), c = 14.135(3) ?, β = 97.84(3)°, V = 3197.4(11) ?~3, C_(80)H_(64)N_2O_2 Pd, Mr = 1191.73, Z = 2, Dc = 1.238 Mg/m^3, μ = 0.339 mm^(-1), F(000) = 1240, T = 293(2) K, the final R = 0.0593 and wR = 0.1192(I > 2s(I)). The compound showed excellent catalytic activity up to 1.130 × 10~7 g of PNB(mol of Pd)^(-1)h^(-1) for the addition polymerization of norbornene by using methylaluminoxane(MAO) as a cocatalyst.

Schiff碱二价钐配合物[2-OC_6H_4CH═N(2,6-~iPr_2C_6H_3)]_2Sm(THF)_2催化己内酯开环聚合

The divalent Sm complex supported by Schiff base ligand [2 OC 6H 4CH [ZJLX,Y] N(2,6 i Pr 2 C 6H 3)] 2Sm(THF) 2 has been prepared by the reaction of 2Sm(THF) 2 has been prepared by the reaction of [2 OC 6H 4CH [ZJLX,Y] N(2,6 i Pr 2C 6H 3)]Na Na with SmI 2 in THF. It exhibits a good catalytic activity for the polymerization of ε caprolactone, and the polymer obtained has a narrow molecular weight distribution.

侧链型Schiff碱液晶研究——单体的合成与聚合

对具有Ｎ－（对甲基丙烯酰氧基苄叉基）取代苯胺骨架的一系列侧链型Ｓｃｈｉｆ碱液晶单体合成进行了研究，苯胺环上的取代基为卤素、强吸电子基及大体积基团，考察了取代基对液晶性质的影响。当取代基为４－氯，４－溴时，单体呈狭窄之液晶区间，而２，４－二氯取代物则无液晶性。当苯胺环上带有４－苯基的单体时，都呈宽的液晶区间。同时还对相应单体的自由基聚合及聚合物的相行为进行了研究。

无助催化剂下钕Schiff碱配合物催化MMA聚合

为了优化甲基丙烯酸甲酯(MMA)聚合反应的条件,提出将合成的新型稀土钕精氨酸Schiff碱配合物作为催化剂,催化MMA的聚合.采用核磁共振1HNMR、黏度测量及凝胶渗透色谱(GPC)等方法对聚合物的立体规整度、黏均分子量和相对分子质量分布分别进行表征.实验表明,当该配合物用量与单体MMA物质的量比为0.05%时,无需助催化剂,在80℃反应20h,聚合反应的转化率高达93%,聚合物的黏均分子量达到8.3×105,说明该配合物具有优良的催化活性,优化了MMA聚合反应条件.

Schiff碱钛配合物催化n-辛基联烯聚合

采用简便的方法,合成了Schiff碱钛配合物Ti(Salen)2Cl2[Salen为N,N-(3,5-di-tert-butylsalicylidene)anilinato]并与Al(i-Bu)3组成二元催化体系用于n-辛基联烯的聚合.实验结果表明,在单体与催化剂摩尔比为100,n(Al)/n(Ti)=50,催化剂于80℃陈化时间1h后,于80℃本体聚合16h得到聚n-辛基联烯,转化率100%,分子量Mw=1.1×105,MWD=1.77,1,2聚合链节单元质量分数为50%.

Synthesis and Crystal Structure of a Novel Bis(chlorido)-bridged One-dimensional Chain-like Copper(Ⅱ) Polymer

A copper（Ⅱ） complex [LCu2Cl4]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-（4-fluorophenyl）iminomethyl-8-quinolinoxy]butane（L）. X-ray crystal structure shows that it is a binuclear complex, and the crystal belongs to the triclinic system, space group P1, with a = 9.387（2）, b = 9.968（2）, c = 10.291（2） ？, α = 87.532（3）, β = 63.762（2）, γ = 86.628（3）o, V = 862.1（3） ？^3, Z = 1, Dc = 1.640 Mg/m^3, F（000） = 428, R = 0.0416 and wR = 0.1141. Each Cu（Ⅱ） metal ion coordinates with a quinoline N atom, an imine N atom, an ether oxygen atom and three chlorides, forming a distorted six-coordinated octahedronal structure. Each copper（Ⅱ） complexation unit links with one of the adjacent ligand copper complexation units through the chlorido bridging groups, thus generating an infinite one-dimensional chain structure. Such 1D chains further construct a 2D network structure by π-π stacking interactions.

RING-OPENING POLYMERIZATION OFε-CAPROLACTONE USING LANTHANIDE TRIS(N-PHENYL-3,5-DI-T-BUTYLSALICYLALDIMINATO)S AS SINGLE COMPONENT CATALYST

Ring-opening polymerization of ε-caprolactone has been carried out by using rare earth Schiff base complexes： lanthanide tris（N-phenyl-3,5-di-t-butylsalicylaldiminato）s [Ln（OPBS）3] as single component catalyst for the first time. The influences of different rare earth elements, monomer and catalyst concentration as well as reaction time on the polymerization were investigated. Mechanism studies showed that monomer inserts into the active site with the acyl-oxygen bond scission rather than the break of alkyl-oxygen bond.

葡聚糖改性尿素对冬小麦产量和肥料氮去向的影响

【目的】糖类物质具有调控氮素转化和作物生长的作用,目前尚不明确不同聚合度糖类物质与尿素反应对尿素氮肥利用、作物生长的影响及机理。通过将不同聚合度葡萄糖(葡聚糖)与15N尿素熔融制备葡聚糖改性尿素,分析葡聚糖改性尿素的结构变化与小麦产量和氮素吸收利用的关系,以期为葡聚糖在提高尿素氮肥利用效率中的应用提供科学依据。【方法】采用15N示踪技术,供试作物为冬小麦(济麦22),将葡萄糖(单体)、麦芽糖(2聚)、低聚麦芽糖(≈5聚)和聚葡萄糖(≈20聚)按1%添加量加入到熔融15N尿素(丰度为10.19%)中,制得葡聚糖改性尿素(葡萄糖、麦芽糖、低聚麦芽糖、聚葡萄糖改性尿素分别由GU、MU、OU和PU表示),以不同聚合度葡萄糖改性尿素和普通尿素(U)为供试肥料,运用田间土柱栽培试验研究葡聚糖改性尿素对小麦生长及肥料氮去向的影响。利用傅里叶红外变换(FTIR)光谱和13C核磁共振(13C NMR)波谱特征探究葡萄糖聚合度及其改性尿素的结构变化,并揭示其与小麦产量、氮肥利用的关系。【结果】(1)与U相比,葡聚糖改性尿素的FTIR谱图在3 343和1 601 cm-1处的伯酰胺振动强度减弱,13C NMR波谱在158-171 ppm处检测到一个新的化学位移峰,是葡聚糖的醛基与尿素的胺基发生席夫碱反应,生成含C=N物质的标志。(2)与U相比,不同聚合度葡萄糖改性尿素(GU、MU、OU、PU)增加了小麦产量,分别较U提高了1.9%、9.2%、10.3%和12.3%,主要通过增加小麦穗数和穗粒数实现增产。(3)与U相比,不同聚合度葡萄糖改性尿素的小麦籽粒总氮吸收量和肥料氮吸收量分别提高了8.7%-20.0%和6.1%-13.9%;MU、OU和PU处理的氮素吸收量均高于GU。(4)与U相比,不同聚合度葡萄糖改性尿素的15N利用率提高了2.0-6.1个百分点,肥料氮残留率提高了1.3-4.9个百分点,肥料氮损失率显著降低6.9-7.4个百分点。(5)相关性分析结果表明,小麦产量与葡萄糖聚合度呈显著正相关关系,而与席夫碱含量呈显著负相关;利用一元二次方程可显著拟合席夫碱含量与小麦产量和15N利用率的关系,葡萄糖聚合度5-8时,小麦产量和肥料氮利用率最高。【结论】与普通尿素相比,不同聚合度葡萄糖改性尿素可以增加小麦产量,促进氮素的吸收利用,提高肥料氮残留量,减少尿素氮肥损失。一定范围内,随着葡聚糖聚合度的增加,小麦产量和肥料氮吸收量逐渐增加,土壤中肥料氮残留量逐渐降低。葡萄糖聚合度为5-8,其对尿素改性增效的效果最佳。

Room temperature polymerization of alkyl isocyanates catalyzed by rare earth Schiff base complexes

The polymerization of alkyl isocyanates catalyzed by rare earth chloride salen complexes/triisobutyl aluminum (Ln(H2salen)2Cl3·2C2H7OH/Al(i-Bu)3) at room temperature was investigated. The influences of ligand structure, catalyst composition, polymerization temperature, polymerization time, the concentration of catalyst and monomer, and the polymerization solvent on the polymerization of isocyanates were studied. It was found that under the polymerization conditions, examined La(H2salenA)2Cl3·2C2-H7OH/Al(i-Bu)3 (H2salenA= N,N′-disalicylideneethylene diamine) is a fairly high efficient catalyst for the polymerization of n-hexyl isocyanate (n-HexNCO) to prepare high molecular weight poly(n-hexyl isocyanate) (PHNCO) with narrower molecular weight distribution at room temperature. PHNCO could be prepared with yield of 74.0%, number-average molecular weight (M n) of 40.20×104 and MWD of 1.79 under the following optimum conditions: [Al]/[La] = 30 (molar ratio), [n-HexNCO]/[La] = 100 (molar ratio), [n-HexNCO] = 3.43 mol/L polymerization at 20°C for 12 h in toluene. In the same polymerization conditions, poly (n-octyl isocyanate) (PONCO) with yield of 67.3%, and poly(n-butyl isocyanate) (PBNCO) with yield of 45.5%, could be prepared respectively. The kinetics of the polymerization of n-HexNCO was also investigated and found to be first-order with respect to both monomer and catalyst concentrations.

n-BuLi/THF体系希夫碱末端化学改性SSBR的研究

采用 2种希夫碱化合物对以n -BuLi/THF引发体系合成的溶液聚合丁二烯 -苯乙烯共聚物(SSBR)进行末端化学改性。研究结果表明 :改性后的SSBR其物理机械性能及抗湿滑性能良好 ,滚动阻力有所降低 ,说明用希夫碱化合物改性SSBR可以制备低滚动阻力橡胶。

高分子希夫碱金属配合物的研究进展 (Ⅱ)聚希夫碱金属配合物的制备、表征及性能

综述了近年来标题化合物的研究进展，制备方法包括：通过配体侧基缩聚、配位聚合及自动组装聚合。讨论了热稳定性、溶解性和液晶行为。

希夫碱钛配合物催化D,L-丙交酯本体开环合成聚乳酸

合成了一种新型双核希夫碱钛配合物,并将此作为催化剂用于D,L型丙交酯本体开环聚合,采用FT-IR、NMR、GPC对合成产物进行表征,研究结果表明该配合物具有催化丙交酯开环较高的催化活性和分子量可控性(PDI=1.09～1.24)。同时进一步研究了该催化剂用量,聚合温度及聚合时间对聚合反应的影响,发现在单体与催化剂摩尔比为2600,聚合时间为16h,聚合温度为160℃时,可得到数均分子质量Mn=9.058×104,PDI=1.16的聚乳酸材料。

稀土席夫碱配合物催化苯乙烯聚合

采用简便的方法合成了稀土席夫碱配合物Nd(H2Salen)2Cl3.2C2H5OH(H2Salen是指N,N-′disalicyli-deneethylenediamine),用红外光谱、元素分析和络合滴定的方法确定了配合物的分子式.发现Nd(H2Salen)2Cl3.2C2H5OH与Al(i-Bu)3和CCl4组成的三元催化体系是苯乙烯(St)溶液聚合的良好催化剂.在St/Nd摩尔比为1 000的低催化剂用量下,50℃聚合20 h,可以制得50%转化率,粘均相对分子质量为17.5×104,全同结构为52.3%,间规结构为47.7%的聚苯乙烯.

对苯二胺缩对苯二甲醛席夫碱及其配合物的制备和电化学性能

以对苯二胺和对苯二甲醛为原料缩合制备出对苯二胺缩对苯二甲醛席夫碱聚合物(PT),研究了采用不同物质的量之比的单体所制备的聚合物的电化学性能。利用席夫碱聚合物中N原子上的孤对电子与不同金属离子配位形成席夫碱配位聚合物(PT-M),并对所形成聚合物的电化学性能进行了研究。采用X射线衍射(XRD)、红外(IR)、热重-差示扫描量热法(TG-DSC)、扫描电子显微镜(SEM)和能谱(EDS)对产物进行了表征,PT-M的XRD峰强度相比于PT明显降低,表明金属离子配位进入分子链骨架中引起的空间位阻减少了分子链排列的有序性。采用循环伏安、恒电流充放电和交流阻抗评价了所制备的配位聚合物材料的电化学性能。研究发现,聚席夫碱铝配合物(PT-Al)表现出较优的电化学性能,在0.5 A·g^-1的电流密度下其电容值为649.6 F·g^-1,并且具有较好的循环稳定性,在8 A·g^-1的电流密度下循环1000次后仍有80.9%的电容保持率。

以西弗碱为封端剂原位合成官能化苯乙烯-丁二烯-苯乙烯嵌段共聚物

合成了西弗碱(N,N-二甲氨基苯甲醛缩苯胺,DMABA),用负离子原位聚合法合成了末端官能化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS),用模型聚合物的方法研究了DMABA与聚苯乙烯(PS)活性种的定量反应关系,以及反应温度、PS数均相对分子质量(M-n)对官能度的影响,并对官能化聚合物进行了分析表征。结果表明,DMABA能和PS活性种等摩尔进行反应,反应温度以及PS活性种的M-n对聚合物的官能度影响不大;以DMABA为封端剂,n-BuLi或六亚甲基亚胺锂为引发剂,可以制得高官能度的ω-SBS或α,ω-双端官能化SBS,在提高SBS极性的同时,对SBS的相对分子质量分布及微观结构影响不大。