胆甾液晶／聚合物多组分体系的结构与性能研究（Ⅲ）──ChN／poly（MMA－CO－BMA）混合体系的形态结构

应用Ｘ射线衍射、偏光显微镜及电子显微镜研究了胆甾液晶与甲基丙烯酸甲酯（ＭＭＡ）─甲基丙烯酸丁酯（ＢＭＡ）无规共聚物共混体系的形态结构。研究了体系的结晶态及液晶态的行为和共聚物含量及组成对光学织构的影响。     

马来酸酐─环氧丙烷共聚物的合成及结构表征

本文将稀土络合物Ｎｄ（Ｐ２０４）３、Ｎｄ（Ｐ５０７）３、Ｎｄ（ｎａＰｈ）３、Ｎｄ（ａｃａｃ）３．３Ｈ２Ｏ与烷基铝组成的二元体系催化剂用于共聚马来酸酐（ＭＡｎ）与环氧丙烷（ＰＯ）获得成功．并采用１Ｈ—ＮＭＲ研究了共聚物三元组序列分布．结果表明，稀土络合催化剂为ＭＡｎ与ＰＯ共聚的优良催化刑，可得到高转化率、高交替度共聚物．共聚物数均分子量Ｍｎ和分子量分布分别为２０００—３０００、１．３—１．７，共聚物中ＭＡｎ的摩尔含量４０％以上．共聚物组成及序列分布与投料比、催化剂种类、溶剂性质等有关．理论计算表明，序列分布符合三级马尔可夫（Ｍａｒｋｏｆｆｉａｎ）过程．     

用含偶氮基的聚苯乙烯大分子引发剂合成两亲性嵌段共聚物

采用含偶氮基的聚苯乙烯预聚物（ＰＳ ＡＣＰＣ）作为引发剂，合成了苯乙烯（Ｓｔ）分别与甲基丙烯酸（ＭＡＡ）、甲基丙烯酸（β 羟丙酯）（ＨＰＭＡ）的嵌段共聚物，考察了ＰＳ ＡＣＰＣ引发第二单体的聚合反应行为，以及影响第二单体转化率和均聚物含量、共聚物组成的因素．用溶解性、凝胶渗透色谱（ＧＰＣ）、红外光谱（ＩＲ）、核磁共振（ＮＭＲ）、动态接触角（ＤＣＡ）等表征了嵌段共聚物．     

马来酸酐─环氧丙烷共聚物的合成及结构表征

本文将稀土络合物Ｎｄ（Ｐ２０４）３，Ｎｄ（Ｐ５０７），Ｎｄ（ｎａｐｈ）３，Ｎｄ（ａｃａｃ）３．３Ｈ２Ｏ与烷基铝组成的二元体系催化剂用于共聚马来酸酐（ＭＡｎ）与环氧丙烷（ＰＯ）获得成功，并采用１Ｈ－ＮＭＲ研究了共聚的优良催化剂，可得到高转化率，高交替度共聚物，共聚物数均分子量Ｍｎ和分子量分布分别为２０００－３０００，１．３－１．７，共聚物中ＭＡｎ的摩尔含量４０％以上。共聚物组成及序列分布与投料比，催     

共混水凝胶：3．苯乙烯─丙烯酰胺共聚物／聚（甲基丙烯酸β─羟乙酯）共混相容性的研究

用自由基溶液聚合的方法制备了聚（甲基丙烯酸β─羟乙酯）（ＰＨＥＭＡ）和一系列不同组成的苯乙烯－丙烯酰胺共聚物（ＰＳＡｍ）．利用ＤＳＣ，ＩＲ方法研究了ＰＳＡｍ／ＰＨＥＭＡ共混体系的相容性．观察到不同组成的ＰＳＡｍ与ＰＨＥＭＡ等重量比混合时，只有Ａｍ含量在４７～５７ｍｏｌ％范围内的ＰＳＡｍ与ＰＨＥＭＡ的共混物相容，即共混体系表现出一个“ｍｉｓｃｉｂｉｌｉｔｙｗｉｎｄｏｗ”．应用平均场理论计算了上述共混体系的相互作用参数，结果表明共聚物内不同链段间的拒斥力（ｒｅｐｕｌｓｉｏｎ）是使ＰＳＡｍ／ＰＨＥＭＡ共混体系产生“ｍｉｓｃｉｂｉｌｉｔｙｗｉｎｄｏｗ”的主要原因．     

聚（甲基丙烯酸甲酯—二甲基二烯丙基氯化铵）的合成及表征

以水和乙醇作混合溶剂，用逐步滴加甲基丙烯酸甲酯的方法，通过自由基聚合，由溶解性和共聚活性差异较大的两种单体ＭＭＡ和二甲基二烯丙基氯化铵合成了新型含阳离子共聚物聚，并用ＩＲ和＾１Ｈ－ＮＭＲ进行了分析表征。该共聚物溶于丙酮和水组成的二元溶剂，并与Ｐ（ＭＭＡ－ＭＡＡ）有较强的分子复合能力。     

新型五甲基茂基三苄氧基钛/甲基铝氧烷催化剂合成苯乙烯-乙烯共聚物及其表征

以五甲基茂基三苄氧基钛［Ｃｐ＊ Ｔｉ（ＯＢｚ）３］ 和甲基铝氧烷（ ＭＡＯ） 组成的催化体用本体法合成出苯乙烯 乙烯共聚物Ｐｏｌｙ（Ｓ ｃｏ Ｅ） ．考察了共聚温度,共聚时间,Ａｌ／Ｔｉ 摩尔比,主催化剂浓度［Ｔｉ］ 等条件对共聚反应的影响．共聚产物经沸丁酮,沸四氢呋喃（ＴＨＦ） 连续抽提分离,发现共聚物主要存在于ＴＨＦ 可溶级分中．可溶级分经ＤＳＣ,１３Ｃ ＮＭＲ,ＷＡＸＤ,ＤＭＡ 等手段分析,证明苯乙烯 乙烯共聚物为具有单一玻璃化转变温度（ Ｔｇ） 无熔融温度的无规共聚物,显示弹性体的粘弹性行为．     

甲基丙烯酸甲酯 - 甲基丙烯酸共聚物/梯形聚苯基硅倍半氧烷原位共混体系的性能研究

甲基丙烯酸甲酯 甲基丙烯酸共聚物（Ｐ（ＭＭＡ ＭＡＡ））与低分子量或高分子量梯形聚苯基硅倍半氧烷（ＰＰＳＱ）的共混物经原位聚合法制成．用光学透明法、荧光光谱、ＤＳＣ等技术研究了该共混体系的相容性及组分间的相互作用及结构转变．结果表明，当ＰＰＳＱ含量较小时，由于ＰＰＳＱ与Ｐ（ＭＭＡ ＭＡＡ）间存在着较强的氢键作用，该共混体系在一定配比下相容，且低分子量ＰＰＳＱ与Ｐ（ＭＭＡ ＭＡＡ）间的相容性较好．当ＰＰＳＱ的含量≤１％时，ＰＰＳＱ的加入对该共混物的Ｔｇ影响不大，但其Ｔｆ随ＰＰＳＱ含量增加而增大．此外，还测试了Ｐ（ＭＭＡ ＭＡＡ）／ＰＰＳＱ原位共混物的硬度及冲击强度．     

氯化聚乙烯对甲基丙烯酸甲酯／苯乙烯共聚动力学的影响

将甲基丙烯酸甲酯（ＭＭＡ）／苯乙烯（Ｓ）在氯化聚乙烯（ＣＰＥ）存在下进行悬浮溶胀接枝共聚，考察了ＣＰＥ对ＭＭＡ／Ｓ共聚动力学行为的影响．ＣＰＥ提高了聚合体系的粘度，使自动加速提前，扩散因素增加，对共聚有阻滞作用．ＣＰＥ是链转移剂，使ＭＭＡ／Ｓ共聚物分子量降低．ＣＰＥ对ＭＭＡ的吸附渗透优于对Ｓ的吸附，造成接技部分与非接技部分组成的差异．ＣＰＥ含量、溶胀时间、转化率、硫酸用量对共聚组成均有影响。     

甲基丙烯酸丁酯和苯乙烯的原子转移自由基共聚

研究了甲基丙烯酸丁酯（ＢＭＡ）和苯乙烯（Ｓ）这两种不同极性单体的原子转移自由基嵌段共聚和无规共聚,得到了实测分子量与理论分子量相近,分子量分布较窄的嵌段共聚物和无规共聚物．聚合过程中分子量和单体转化率成比例增加,多分散性指数变化不大．用１Ｈ ＮＭＲ法测定共聚组成,Ｋｅｌｅｎ Ｔｕｄｏｓ法计算竞聚率．得到ｒＳｔ＝０９１,ｒＢＭＡ＝０３２．     

COPOLYMERIZATION PROCESS OF TRIPHENYLMETHYL METHACRYLATE AND MMA WITH CHIRAL ANIONIC COMPLEX INITIATOR

The copolymerization process of triphenylmethyl methacrylate (TrMA) and methylmethacrylate (MMA) using chiral anionic complex initiator (-) SP-FlLi (Scheme 1) has beenstudied in toluene and THF, respectively. The copolymer obtained in toluene possessed muchhigher specific rotation than that in THF. These copolymers have shown a tendency to a random and a like alternating structure, respectively.     

Preparation and photochemical study of soluble optically active block copolymethacrylates and azo-containing random copolymethacrylates

A series of soluble optically active block copolymers of trityl methacrylate (TrMA) and cyclohexyldiphenylmethyl methacrylate (CHDPMA) with methyl methacrylate (MMA) and n-butyl methacrylate (n-BuMA) were synthesized using the complex of 9-fluorenyllithium and (S,S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane as an initiator in toluene at −78°C. Soluble optically active random copolymers derived from TrMA and azo methacrylates, 6-(4-phenylazophenoxy)hexyl methacrylate (PAHM) and 2-(4-phenylazophenoxy)ethyl methacrylate (PAEM), were obtained under similar anionic polymerization conditions. Optical activities of the copolymers largely depended on the weight percentage of TrMA or CHDPMA component in the polymer chains. Solubility and film formability were significantly improved for the copolymers. Irradiation of optically active TrMA–MMA and CHDPMA–MMA block copolymer films containing photoacid, diphenyl-p-tolylsulfonium triflate, causes the partial hydrolysis of bulky esters and results in the conformational randomization of helical chains, which in turn leads to a significant change in optical rotation of the films. Photoisomerization studies of azo-containing random copolymers indicate that the trans to cis isomerization induces the helical conformation racemization in solution. © 1997 John Wiley & Sons, Inc.     

丁烯二酸三乙基锡酯的共聚

合成了顺-及反-丁烯二酸三乙基锡酯,并研究了它们和苯乙烯及甲基丙烯酸甲酯的共聚合反应。两种锡酯都能与苯乙烯共聚,与甲基丙烯酸甲酯未能得到共聚物。     

旋光性聚甲基丙烯酸三苯甲酯的合成

<正> 旋光性聚甲基丙烯酸三苯甲酯(PTrMA,A)是一种新型旋光聚合物,其旋光性不是来自结构单元中的手性原子或基因,而是刚性的分子链呈长程单向螺旋构象,使分子链获得手征性的结果.自70年代末问世以来,在改进其合成方法和作为色谱固定相直接拆分手性化合物的应用方面受到人们注意,由于独特的结构,可以设想,如果将它带上特殊     

HELIX SENSE-SELECTIVE COPOLYMERIZATION OF TRIPHENYLMETHYL METHACRYLATE WITH CHIRAL ANIONIC INITIATORS

Optically active copolymers of pairs of three monomers, triphenyl (methyl methacrylate)and one or two pyridyl substituted methyl methacrylate homologues, were obtained by helix-sense-selective copolymerization using complexes of organolithium with chiral ligand as anionicinitiators in toluene at low temperature. The copolymers obtained with (-)-sparteine (Sp) and(S,S)-(+)-and (R, R)-(-)-2, 3-dimethoxy-1, 4-bis (dimethylamino) butanes((+)-and (-)-DDB) complexes of organolithium showed low optical activity, but PMP complex with N, N-diphenylethyleneamine monolithium amide (PMP-DPEDA-Li) was effective in synthesizingcopolymers of high optical rotation ([α]_D~(25) about+320～1370°)which were comparable to thoseof relative homopolymers with one-handed helical structure.     

PHOTOPOLYMERS: SYNTHESIS AND CHARACTERIZATION OF POLY(4-CINNA-MOYLPHENYL METHACRYLATE) WITH GLYCIDYL METHACRYLATE

Copolymers of 4-cinnmoylphenyl methacrylate (CPMA) with glycidyl methacrylate were synthesized in methyl ethyl ketone solution using benzoyl peroxide as initiator at 70 ± 1°C. They were characterized by UV, IR, ¹H-NMR, and ¹³C-NMR spectra. Their compositions were determined by ¹H-NMR technique. The monomer reactivity ratios were determined by the Fineman-Ross and Kelen-Tüdös methods. The molecular weights ([Mbar]_w and [Mbar]_n) of the polymers were determined by GPC technique. Thermogravimetric analysis of the copolymers were carried out in air. The T_g of the polymers were determined by differential scanning calorimetry. The photocrosslinking properties of the homo and copolymers were also discussed.     

Helix-sense-selective polymerization of phenyl[bis(2-pyridyl)]methyl methacrylate and chiral recognition ability of the polymer

A novel monomer, phenyl[bis(2-pyridyl)]methyl methacrylate (PB2PyMA), was synthesized. The solvolysis rate of PB2PyMA measured in CDCl₃–CD₃ OD [1/1 (v/v)] by ¹H-NMR spectroscopy at 35°C was much smaller than those of triphenylmethyl methacrylate (TrMA) and diphenyl-2-pyridylmethyl methacrylate (D2PyMA). PB2PyMA was anionically polymerized with the complexes of organolithiums with (?)-sparteine (Sp), (S,S)-(+)-and (R,R)?(-)-2,3-dimethoxy-1,4-bis(dimethylamino)butanes[(+)-and (?) -DDB], and (S)-(+)-1-(2-pyrrolidinylmethyl) pyrrolidine (PMP) in toluene at low temperature. The polymers obtained with Sp and DDB complexes showed low optical activity. PMP complexes, particularly that with N,N′-diphenylethylenediamine monolithium amide, were effective in synthesizing a polymer of high optical rotation ([α]²⁵₃₆₅ ～ +1350°) which was comparable to those of poly(TrMA) and poly(D2PyMA) with one-handed helical structure. The optical rotation of poly(PB2PyMA) in a mixture of CHCl₃ and 2,2,2-trifluoroethanol (9/1, v/v) slowly decreased with time. Optically active poly(PB2PyMA) coated on macroporous silica gel was able to resolve racemic compounds as a chiral stationary phase for high-performance liquid chromatography. © 1993 John Wiley & Sons, Inc.     

Synthesis and asymmetric polymerization of a series of methyl‐substituted triphenylmethyl methacrylate

Five novel ortho‐, meta‐, and para‐methyl‐substituted triphenylmethyl methacrylate monomers, such as o‐tolyldiphenylmethyl methacrylate (o‐MeTrMA), di‐o‐tolylphenylmethyl methacrylate (o‐Me₂TrMA), tris‐o‐tolylmethyl methacrylate (o‐Me₃TrMA), tris‐m‐tolylmethyl methacrylate (m‐Me₃TrMA), and tris‐p‐tolylmethyl methacrylate (p‐Me₃TrMA) have been synthesized. The methanolysis rates of these monomers were measured in CDCl₃‐CD₃OD (1:1, v/v) by ¹H NMR spectroscopy at 30 °C. It was found that the order of the methanolysis rates would be TrMA<o‐MeTrMA<o‐Me₂TrMA<o‐Me₃TrMA<m‐Me₃TrMA except p‐Me₃TrMA, which exhibited very good stability to methanolysis. The asymmetric polymerization of these monomers was investigated by chiral anionic complexes as initiators. The results showed that the ability to form a helical chain was effected not only by the types of chiral complex initiators, but also by the position and number of methyl‐substituted groups at the benzene rings of TrMA. The order of the ability of polymerization was o‐MeTrMA >o‐Me₂TrMA>o‐Me₃TrMA and m‐Me₃TrMA> p‐Me₃TrMA>o‐Me₃TrMA. These differences would be attributed to the different sizes and “propeller” steric structures of the bulky side groups. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 430–436, 2001     

Asymmetric polymerization of triphenylmethyl methacrylate by C2-chiral catalysts

Asymmetric polymerization of triphenylmethyl methacrylate (TrMA) was investigated with optically active anionic catalysts in toluene at ?78°C. The catalysts were prepared in various combinations of organolithium compounds with C²-chiral tertiary diamines ( 1 – 6 ). Tetramethyl-ethylenediamine derivative bearing an axially dissymmetric biphenyl moiety ( 1 ) and the binaphthyl analogue ( 4 ) were found to provide efficient catalysts for the preparation of highly isotactic poly(TrMA)s of very large optical rotations whose signs depended on the configurations of the diamines. Especially, the catalysts consisting of 1 gave nearly pure one-handed helical polymers soluble in tetrahydrofuran (THF) in excellent yields, regardless of the kind of the lithium compounds used. The BuLi- 1 catalyst caused the metallation of toluene used as the solvent, and hence the resulting polymer had a benzyl moiety as an initiator fragment. The polymerization was also discussed with respect to the mole ratio of 1 to BuLi. Circular dichroism (CD) spectra of the (?)- and (+)-polymers, which were obtained with the BuLi-(R)- 1 and -(S)- 1 catalysts, respectively, were virtually complete mirror images of each other. High performance liquid chromatography (HPLC) using the THF–soluble, optically active poly(TrMA) as chiral adsorbent realized the complete resolution of racemic compounds.     

Anionic copolymerization of optically active α-methylbenzyl methacrylate and trityl methacrylate. I. Reactivity of monomers

The monomer reactivity ratios were determined in the anionic copolymerization of (S)- or (RS)-α-methylbenzyl methacrylate (MBMA) and trityl methacrylate (TrMA) with butyllithium at ?78°C, and the stereoregularity of the yielded copolymer was investigated. In the copolymerization of (S)-MBMA (M₁) and TrMA (M₂) in toluene the monomer reactivity ratios were r₁ = 8.55 and r₂ = 0.005. On the other hand, those in the copolymerization of (RS)-MBMA with TrMA were r₁ = 4.30 and r₂ = 0.03. The copolymer of (S)-MBMA and TrMA prepared in toluene was a mixture of two types of copolymer: one consisted mainly of the (S)-MBMA unit and was highly isotactic and the other contained both monomers copiously. The same monomer reactivity ratios, r₁ = 0.39 and r₂ = 0.33, were obtained in the copolymerizations of the (S)-MBMA–TrMA and (RS)-MBMA–TrMA systems in tetrahydrofuran (THF). The microstructures of poly[(S)-MBMA-co-TrMA] and poly-[(RS)-MBMA-co-TrMA] produced in THF were similar where the isotacticity increased with an increase in the content of the TrMA unit.