丙烯酸丁酯－苯乙烯－丙烯腈共聚物的结构与力学性能

丙烯酸丁酯－苯乙烯－丙烯腈共聚物的结构与力学性能张会轩，韩业，张会良，冯之榴（吉林工学院化工系长春１３００１２）（中国科学院长春应用化学研究所长春）关键词ＡＳＡ，乳液聚合，粒子，力学性能丙烯酸丁酯－苯乙烯－丙烯腈共聚物（ＡＳＡ）是两相结构，聚丙烯酸丁...     

乙烯系单体自由基聚合的阻聚效应──XIX．取代哌啶羟胺和二叔丁基羟胺及其稳定自由基对苯乙烯－丙烯腈共聚合的影响

研究了二叔丁基羟胺（ＤＴＢＨＡ），二叔丁基氮氧自由基（ＤＴＢＮＯ），２，２，６，６－四甲基－４－羟基哌啶羟胺（ＴＭＨＰＨＡ）和２，２，６，６－四甲基－４－羟基哌啶－１－氧自由基（ＴＭＨＰＯ）对过氧化苯甲酰（ＢＰＯ）６０℃引发的苯乙烯（Ｍ１）－丙烯腈（Ｍ２）共聚合的阻聚物行为。结果表明，这些阻聚剂对Ｓｔ－ＡＮ共聚均表现良好的阻聚行为，其中氮氧自由基优于相应羟胺。同时观察到Ｓｔ－ＡＮ竞聚率的改变，羟胺     

ASYMMETRIC MICHAEL－TYPE ALKYLATION OF CHIRAL IMINES DIASTEREOSELECTIVE SYNTHESIS OF（＋）－α－CYPERONE AND （－）－10－EPI－α－CYPERONE

ＡＳＹＭＭＥＴＲＩＣ　ＭＩＣＨＡＥＬ－ＴＹＰＥ　ＡＬＫＹＬＡＴＩＯＮ　ＯＦ　ＣＨＩＲＡＬ　ＩＭＩＮＥＳ　ＤＩＡＳＴＥＲＥＯＳＥＬＥＣＴＩＶＥ　ＳＹＮＴＨＥＳＩＳ　ＯＦ（＋）－α－ＣＹＰＥＲＯＮＥ　ＡＮＤ　（－）－１０－ＥＰＩ－α－ＣＹＰＥＲＯＮＥＡＳ...     

STUDIES ON THE TOTAL SYNTHESIS OF（－）－（2R，5S）－2－METHYL－5－HYDROXYMETHYL－δ－VALEROLACTONE

ＳＴＵＤＩＥＳ　ＯＮ　ＴＨＥ　ＴＯＴＡＬ　ＳＹＮＴＨＥＳＩＳ　ＯＦ（－）－（２Ｒ，５Ｓ）－２－ＭＥＴＨＹＬ－５－ＨＹＤＲＯＸＹＭＥＴＨＹＬ－δ－ＶＡＬＥＲＯＬＡＣＴＯＮＥＳＴＵＤＩＥＳＯＮＴＨＥＴＯＴＡＬＳＹＮＴＨＥＳＩＳＯＦ（－）－（２Ｒ，５Ｓ）－...     

1,3—戊二烯／苯乙烯阳离子共聚合反应

本文研究了以甲苯为溶剂,ＡｌＣｌ３和ＢＦ３·ＯＥｔ２为引发剂,１,３－戊二烯（ＰＤ）与苯乙烯（Ｓｔ）的阳离子共聚合反应,并用红外光谱测定聚合物的微观结构。由共聚单体ＰＤ和Ｓｔ加入顺序的不同可生成无规共聚物Ｐ（ＰＤ－ｃｏ－Ｓｔ）和接枝共聚物Ｐ（ＰＤ－ｇ－Ｓｔ）和Ｐ（Ｓｔ－ｇ－ＰＤ）。无论是由ＡｌＣｌ３引发聚合反应,还是由ＢＦ３·ＯＥｔ２引发聚合反应,Ｓｔ上的碳阳离子的活性都高于ＰＤ上碳阳离子的活性。由ＡｌＣｌ３首先引发ＰＤ进行聚合反应,结束后再引入Ｓｔ时,聚合体系不能引发Ｓｔ聚合反应;相反ＡｌＣｌ３首先引发Ｓｔ聚合后的体系能继续引发ＰＤ的聚合反应。ＢＦ３·ＯＥｔ２无论先引发Ｓｔ或是ＰＤ,都能在聚合反应完成后接着引发另一单体而生成接枝共聚物Ｐ（ＰＤ－ｇ－Ｓｔ）和Ｐ（Ｓｔ－ｇ－ＰＤ）。二苯醚与烯丙基氯的加入,提高了碳阳离子的稳定性,增加了聚合物的分子量,但降低了碳阳离子的活性,使得聚合反应的产率降低,同时对Ｓｔ和ＰＤ碳阳离子的活性次序无明显影响     

SYNTHESIS OF 4－S－（1＂－ARYL－TETRAZOLE－5＂－YL）－4－DEOXY－4＇－DEMETHYL－EPIPODOPHYLLOTOXIN ANALOGUES

ＳＹＮＴＨＥＳＩＳ ＯＦ ４－Ｓ－（１＂－ＡＲＹＬ－ＴＥＴＲＡＺＯＬＥ－５＂－ＹＬ）－４－ＤＥＯＸＹ－４＇－ＤＥＭＥＴＨＹＬ－ＥＰＩＰＯＤＯＰＨＹＬＬＯＴＯＸＩＮ ＡＮＡＬＯＧＵＥＳ￥ＫｕａｎＫｅＬＵ；ＦａｎｇＭｉｎＬＩＵａｎｄＹａｏＺｕＣＨＥＮ（Ｄ...     

STUDIES ON THE SYNTHESIS OF SINULARIOL－D， SINULARIOL－A AND SINULARIC ACID－A．－SYNTHESIS OF （5R）－7，7－DIMETHOXY－5－［1－（2－TERT－BUTYLDIPHENYLSILOXYMETHYL）VINYL］－2－HEPTANONE

ＳＴＵＤＩＥＳＯＮＴＨＥＳＹＮＴＨＥＳＩＳＯＦＳＩＮＵＬＡＲＩＯＬ－Ｄ，ＳＩＮＵＬＡＲＩＯＬ－ＡＡＮＤＳＩＮＵＬＡＲＩＣＡＣＩＤ－Ａ．－ＳＹＮＴＨＥＳＩＳＯＦ（５Ｒ）－７，７－ＤＩＭＥＴＨＯＸＹ－５－［１－（２－ＴＥＲＴ－ＢＵＴＹＬＤＩＰＨＥＮＹＬＳ...     

BASE－CATALYZED PROTODESILYLATION OF （2H）－PYRI－DAZINON－5－YL SILYLMETHYL SULFIDES

ＢＡＳＥ－ＣＡＴＡＬＹＺＥＤＰＲＯＴＯＤＥＳＩＬＹＬＡＴＩＯＮＯＦ（２Ｈ）－ＰＹＲＩ－ＤＡＺＩＮＯＮ－５－ＹＬＳＩＬＹＬＭＥＴＨＹＬＳＵＬＦＩＤＥＳ￥ＺｈｅｎｇＪｉｅＨＥ；ＺｈｅｎｇＭｉｎｇＬＩ（ＩｎｓｔｉｔｕｔｅｏｆＥｌｅｍｅｎｔｏ－Ｏｒｇａｎｉｃ...     

SYNTHESIS AND ANTI－HUMAN IMMUNODEFICIENCY VIRUS－1（HIV－1） ACTIVITY OF 9－（2－PHOSPHONYLMETHOXYETHYL）ADENINE （1）AND ITS REGIOISOMER 3－（2－PHOSPHONYLMETHOXYETHYL）ADENINE（2）

ＳＹＮＴＨＥＳＩＳＡＮＤＡＮＴＩ－ＨＵＭＡＮＩＭＭＵＮＯＤＥＦＩＣＩＥＮＣＹＶＩＲＵＳ－１（ＨＩＶ－１）ＡＣＴＩＶＩＴＹＯＦ９－（２－ＰＨＯＳＰＨＯＮＹＬＭＥＴＨＯＸＹＥＴＨＹＬ）ＡＤＥＮＩＮＥ（１）ＡＮＤＩＴＳＲＥＧＩＯＩＳＯＭＥＲ３－（２－ＰＨＯ...     

SYNTHESIS OF DI－（2＇－DEOXY－2＇－FLUORO）PYRIMIDINENUCLEOSIDE PHOSPHATES AND PHOSPHOROTIOATES

ＳＹＮＴＨＥＳＩＳＯＦＤＩ－（２＇－ＤＥＯＸＹ－２＇－ＦＬＵＯＲＯ）ＰＹＲＩＭＩＤＩＮＥＮＵＣＬＥＯＳＩＤＥＰＨＯＳＰＨＡＴＥＳＡＮＤＰＨＯＳＰＨＯＲＯＴＩＯＡＴＥＳＺｈｅｎｇＦｕＷＡＮＧ；ＹｉＢｉｎｇＺＨＡＮＧ；ＹａｏＱｕａｎＣＨＥＮ（Ｌａｂｏｒａ...     

碳酸乙烯酯溶剂中丙烯腈的聚合行为

以碳酸乙烯酯为溶剂,偶氮二异丁腈（AIBN）为引发剂,采用溶液自由基聚合的方法对丙烯腈(AN)均聚合、丙烯腈/衣康酸(AN/IA)二元共聚及丙烯腈/衣康酸/丙烯酸甲酯(AN/IA/MA)三元共聚合进行了研究。 考察了反应温度对丙烯腈均聚合,以及聚合单体浓度对丙烯腈共聚合的影响,在60 ℃合成了相对分子质量高于4.5×105、单体转化率高于85%的丙烯腈均聚物及共聚物。 采用正十二烷基硫醇（DDT）和甲酰基哌啶（FP）作为链转移剂,对AN均聚物、AN/IA及AN/IA/MA共聚物的相对分子质量进行调控,考察了链转移剂浓度对聚合物相对分子质量和单体转化率的影响。 结果表明,w(DDT)为0.25%时（以单体质量计）,聚合物相对分子质量可有效调节到1×105,而单体转化率保持在80%以上。     

丙烯腈与衣康酸在DMSO/H_2O中的聚合及聚合物性能表征

采用丙烯腈 (AN)与衣康酸 (IA)为共聚单体 ,以偶氮二异丁腈为引发剂在混合介质二甲基亚砜 水(DMSO H2 O)中自由基沉淀共聚合 ,合成了高分子量的聚丙烯腈 .通过正交设计方法研究了聚合反应条件 ,如反应温度、单体浓度、混合介质DMSO H2 O配比等对聚合反应的转化率的影响 ,还重点探讨了混合介质DMSO H2 O配比对转化率和粘均分子量的影响 .采用DSC ,TG ,IR等手段研究了PAN均聚物及 (PAN co IA)的结构与性能 .研究结果表明 ,增加反应温度 ,降低单体浓度 ,降低喂料AN IA配比中IA的含量 ,均有利于提高聚合反应的转化率 .AN与IA共聚反应的转化率随着反应介质中DMSO含量的增加而降低 ,同时聚合物的粘均分子量也降低 .对于喂料AN IA配比中IA含量相同的P(AN co IA)共聚物 ,高分子量P(AN co IA)共聚物比常规低分子量的放热峰起始温度低 ,放热峰宽     

较高等规度丙烯腈成纤聚合物的合成

以无水氯化镁为添加剂,考察了不同条件下的丙烯腈聚合反应,研究了溶剂种类、聚合温度和氯化镁与丙烯腈的摩尔配比对聚合反应及聚合物等规度的影响,并确定了最佳反应条件,正己烷为溶剂,偶氮二异丁腈(AIBN)为引发剂,聚合温度为60℃,氯化镁与丙烯腈的摩尔比为2∶1.在此条件下,研究了单体浓度和引发剂浓度对丙烯腈(AN)均聚合、丙烯腈/衣康酸(AN/IA)二元共聚合和丙烯腈/衣康酸/丙烯酸甲酯(AN/IA/MA)三元共聚合反应的影响,并获得了较高等规度(三单元组全同分数30.2%～55.9%)的丙烯腈均聚物和共聚物.不同等规度的丙烯腈聚合物的热分析(DSC及TGA)表明,随着聚合物等规度的提高,聚合物的环化放热峰值温度向高温区移动,而且随着聚合物等规度的提高,环化放热峰变宽.随着聚合物等规度的提高,聚合物的热稳定性变差,热失重增加,碳收率降低.     

三种不同碳桥联双核茂钛配合物的合成及催化乙烯聚合研究

合成了3种不同结构的CnH₂n桥联双核茂钛配合物(CH₃)₂C[(C₅H₄)TiCl₂(C₅H₅)]₂(3),(CH₂)_n[(C₅H₄)TiCl₂(C₅H₅)]₂(6,n=3;7,n=4),并用1HNMR进行了表征.发现以甲苯为溶剂时,不仅提高了产率,而且有效地避免了副产物Cp₂TiCl₂的生成.研究了化合物7/MAO(甲基铝氧烷)催化乙烯聚合的反应,考察了反应条件对催化体系的影响.结果表明,催化活性随着n(Al)/n(Cat.)比的增大而提高,聚乙烯的分子量在n(Al)/n(Cat.)=500和50℃时达到最高值9.0102×10⁴;随着聚合时间的延长,催化活性下降,而产物分子量不断升高;随着温度的上升,50℃时催化活性和聚乙烯的分子量最高,分别为2.4074×10⁵gPE/(molTi·h)和6.8679×10⁴.随着桥联双核茂钛配合物碳桥的增长,催化活性增加,所得聚乙烯的分子量降低.     

“Living” free radical ring-opening copolymerization of 4,7-dimethyl-2-methylene-1,3-dioxepane and conventional vinyl monomers

It is the first report on the atom transfer radical ring-opening copolymerizations of unsaturated cyclic acetal: 4,7-dimethyl-2-methylene-1,3-dioxepane (DMMDO) with conventional vinyl monomers, styrene (St), acrylonitrile (AN) and methyl acrylate (MA) in the presence of ethyl α-bromobutyrate as initiator and CuBr/2,2^′-bipyridyl as catalyst/ligand at 110 °C. ¹H, ¹³C NMR and IR data show that the copolymerizations of DMMDO with St (or AN or MA) yield the copolymers, poly(DMMDO-co-St) [or poly(DMMDO-co-AN) or poly(DMMDO-co-MA)] with narrow molecular weight distribution, and low content of DMMDO in the copolymers for electron-donor St, higher contents of DMMDO for electron-acceptor AN or MA are observed.     

吡啶甲磺酸盐离子液体的固载化及其在聚甲醛二甲醚合成中的催化作用

采用键合法将吡啶甲磺酸盐离子液体负载在HZSM-5分子筛上,得到分子筛负载型离子液体催化剂,并将其用于聚甲醛二甲醚(PODEn)的合成。X射线衍射、红外光谱和N2吸附-脱附表征结果显示,吡啶甲磺酸盐离子液体较好地固载于分子筛上。用于催化合成PODEn时较适宜的反应条件为:离子液体负载量0.25 g、甲醇与三聚甲醛的物质的量比(即醇醛比)1.5、110℃、反应时间3 h,催化剂用量为总反应物质量的2.2%。缩合产物中柴油添加组分PODE3~8收率可达67.35%;与单纯离子液体或分子筛催化效果相比,PODE3~8收率得到提高。固载化离子液体易回收,可重复利用;当重复使用3次后,PODE3~8收率仍能达到45.62%。     

Synthesis of block copolymers by heterogeneously initiated emulsion polymerization

The contribution refers to the possibility of using emulsion polymerization of styrene, initiated by a heterogeneous initiator Chydroperoxide of isotactic powdered polypropylene) in the presence of a complex type activator, for the synthesis of block copolymers. Vinylmonomers with various water-solutibility, i.e. methyl methacrylate (MMA), acrylonitrile (AN) and maleic anhydride (MA), were utilized as comonomers of styrene. It was found that at the used conditions, the composition of block copolymers PS-b-P(S/AN) and PS-b-PCS/MA) can be varied by the time of polymerization of the first or second comonomer. The block copolymers were characterized by their molecular weight, and their thermal stability was also investigated.     

Radiation preparation and swelling behavior of sodium carboxymethyl cellulose hydrogels

Sodium carboxymethyl cellulose (CMC) is a kind of degraded polymer under γ-irradiation. However, in this work, it has been found that CMC crosslinks partially to form hydrogel by radiation technique at more than 20% CMC aqueous solution. The gel fraction increases with the dose. The crosslinking reaction of CMC is promoted in the presence of N₂ or N₂O due to the increase of free radicals on CMC backbone, but gel fraction of CMC hydrogel is not high (<40%). Some important values related to this kind of new CMC hydrogel synthesized under different conditions, such as radiation yield of crosslinking G(x), gelation dose R_g, number average molecular weight of network M_c were calculated according to the Charlesby–Pinner equation. The results indicated that although crosslinked CMC hydrogel could be prepared by radiation method, the rate of radiation degradation of CMC was faster than that of radiation crosslinking due to the character of CMC itself. Swelling dynamics of CMC hydrogel and its swelling behavior at different conditions, such as acidic, basic, inorganic salt as well as temperature were also investigated. Strong acidity, strong basicity, small amount of inorganic salts and lower temperature can reduce swelling ratio.     

丙烯腈共聚物动态热产物的在位和在线傅里叶红外光谱研究

用在位和在线傅里叶变换红外光谱法研究了丙烯腈(AN)/二丙酮丙烯酰胺(DAA)/丙烯酸甲酯(MA)三元共聚物在氮气中热解时固态和气态产物的动态变化过程。实验结果表明,以300℃下共聚物主要发生先环化后脱氢的反应。在300℃—950℃间,形成的六元环结构继续发生脱氢、脱氮、脱氧以及缩合交联和稠环化,析出HCN、NH₃、CH₄、CO和CO₂等气态产物和形成无定形碳素组元结构的固态残留物。     

Potentiometric study of Cu(II) and Ni(II) complexation with two high molecular weight poly(acrylic acids)

The copper (II) or nickel (II) complex formation with two poly(acrylic acids) of high molecular weight (Mw=2.5×10⁵ and 3×10⁶) was investigated in aqueous dilute solution (NaNO₃ 0.1 mol l⁻¹; 25°C). Potentiometric titrations were carried out, first to precise the acid-base properties of the two polymers, and secondly to determine the stability constants of the MA and MA₂ complex species formed. The Bjerrum's method, modified by Gregor et al. (J. Phys. Chem., 59 (1955) 34–39), for the study of polymeric acids was used. The results obtained showed that both polymers present very similar properties. As expected, copper (II) is more readily bound to poly(acrylic acids). CuA₂ was the predominant observed species; the global stability constant log β₁₀₂ was found to be close to 6.6. With nickel (II), none of the complex species MA or MA₂ becomes predominant (log β₁₀₂=5.5). Finally, the PAA complexes present a greater stability compared with that of monomeric analogs.