梯形聚硅氧烷液晶的研究进展

摘 要 梯形聚硅氧烷液晶具有独特的稳定性、透明性及成膜性等优点,是一种性能优异的新型功能材料。本文综述了梯形聚硅氧烷液晶近年来的发展现状;介绍了梯形聚硅氧烷液晶的结构特点,根据液晶基元接枝到梯形高分子主链上的方式,将梯形聚硅氧烷液晶分为鱼骨形和划艇形两种;总结了挂接不同侧基的梯形聚硅氧烷的合成路线,包括梯形聚苯基倍半硅氧烷、梯形聚甲基倍半硅氧烷、梯形聚氢基倍半硅氧烷、梯形聚乙烯基倍半硅氧烷等;介绍了几种液晶基元不同的梯形聚硅氧烷液晶的合成;最后提出了几个梯形聚硅氧烷液晶研究工作面临的问题,并对梯形聚硅氧烷液晶的发展前景做出了展望。     

SYNTHESIS AND-CHARACTERIZATION OF THE SOLUBLE, HIGH MOLECULAR WEIGHT AND LADDERLIKE POLYHYDROSILSESQUIOXANE AND ITS COPOLYMERS

The high molecular ladderlike polyhydrosilsesquioxane (LPHSQ) and its copolymer, ladderlike random copolymethylhydrosilsesquioxane (LR-PMHSQ) and ladderlike block copolymethylsilsesqui-oxane(LB-PMHSQ) have been synthesized by a preaminolysis reaction of the corresponding trichlorosilane with 1 ,4-phenylene diamine(PDA) then by hydrolysis and polycondensation reactions The thermographs of these polymers measured by DSC method indicate that these macromolecular backbones are very rigid as seen from the DSC curves which are almost horizontal from room temperature until 350 ~C without noticeable glass transition. The content of Si—H group in the polymers can be regulated by changing the composition of the two copolymerized monomers. So the ladderlike polymers including its copolymers can be the useful precursors for the functional polymers, especially such as fishbone-like liquid crystalline polymers.     

SYNTHESIS OF NEW HIGH MOLECULAR WEIGHT AND REACTIVE LADDERLIKE POLYSILSESQUIOXANES*

Ladderlike polychloropropylsilsesquioxane (CP-T) was first synthesized by "stepwise coupling polymerization".The molecular weight of CP-T is as high as 1.7×10~5. It is a tough, elastic reactive ladderlike polymer and has good heat-resistant and adhesive properties. CP-T can further react with many nucleophilic reagents to generate new ladderlike reactivepolysilsesquioxanes, which can be used as potential precursors in the synthesis of functional ladderlike polymers.     

EFFECT OF POLYMERIZATION CONDITIONS ON THE LADDERLIKE STRUCTURE OF POLYPHENYLSILSESQUIOXANE

The ladderlike structure of PPSQ synthesized by using four kinds of catalysts (MgF_2,LiF, KOH and DCC) at different polymerization conditions has been investigated by IRand NMR. In the system using MgF_2 as the main catalyst, the most important factorwhich affects the ladderlike structure of PPSQ is the composition of the dual catalysts,MgF_2 and DCC. PPSQ prepared by using KOH as the catalyst has the highest regularityof ladderlike structure among all samples. PPSQ with different degree of ladder regularitycan be obtained by choice of polymerization conditions.     

H-BONDING SELF-ASSEMBLED TEMPLATE-CONTROLLED SYNTHESIS OF A NOVEL SOLUBLE AND REACTIVE AMIDE-BRIDGED LADDERLIKE POLYHYDROSILOXANE

A novel soluble and reactive amide-bridged ladderlike polyhydrosiloxane （ALPHS） was first synthesized by an amido H-bonding self-assembled template. ALPHS with molecular weight M^-a = 18300 has very highly ordered ladderlike structure, which was confirmed by a sharp resonance absorption peak of [-Si（H）O2/2 ] moiety with the half peak width △1/2 〈 0.5 in^29Si-NMR spectrum. Presence of the reactive Si-H groups gives ALPHS an opportunity to further derive a variety of functional polymers by versatile Si-H reactions such as hydrosilylation, condensation, and so on.     

SYNTHESIS AND CHARACTERIZATION OF A SOLUBLE LADDERLIKE POLYSILSESQUIOXANE CONTAINING REACTIVE ESTER GROUPS*

A novel soluble ladderlike polysilsesquioxane containing reactive ester groups (Ester-T) was synthesized for thefirst time by stepwise coupling polymerization including preammonolysis, controlled hydrolysis and polycondensation. Themonomer, 3-trichlorosilylpropoxy 4-acetoxybenzoate (M), was synthesized by hydrosilylation of allyloxy 4-acetoxybenzoatewith trichlorosilane in the presence of dicyclopentadienylplatinum (II) chloride (Cp_2PtCl_2) catalyst. Combination of FTIR,~1H-NMr, ~(13)C-NMR, ~(29)Si-NMR, XRD, DSC, TGA and VPO methods was used to demonstrate that the polymer obtained hasan ordered ladderlike structure. The synthesized Ester-T may have promising applications as a precursor of advanced functional polymers.     

SYNTHESIS AND CHARACTERIZATION OF A NOVEL REACTIVE OLIGOMERIC LADDERLIKE COPOLYMETHYL-AMINOPROPYL SILSESQUIOXANE

A novel ordered reactive oligomeric ladderlike copolymethyl-aminopropylsilsesquioxane (Me-AP-T), was successfully synthesized by an efficient hydrosilylation graft reaction of 1,1,1-trimethyl-N-2-propenyl-silanamine with a reactive oligomeric |adderlike copolymethyl-hydrosilsesquioxane (Me-H-T), which was prepared by “supramolecular chemistry-dictated stepwise coupling polymerization” process. FT-IR, ^1H- and ^29Si-NMR spectra show that hydrosilylation reaction proceeds completely. Moreover, ^1H-NMR spectra also indicate that both the molar ratios of ≡SiMe group to Si-H and ≡SiMe group to ≡SiPrNH2 are approximately 1:1 respectively based on the ratio of integrated resonance areas of the different groups. XRD analysis and ^29Si-NMR spectra are used for investigating the ladderlike structure of the polymers. A high Tg (128.38℃) of Me-AP-T shown in DSC measurement implies that the ordered reactive Me-AP-T macromolecules have much stiff chains.     

SYNTHESES AND STRUCTURES OF POLYPHENYLSILSESQUIOXANES

Phenyltrichlorosilane was hydrolyzed both ifi. toluene and in ether from which two kinds of prepolymers were obtained with different structures, molecular weights, and molecular weight distributions. Polymers were prepared from the prepolymers in various polymerization conditions. The ladderlike, branched, and crosslinked structures formed under different polymerization conditions were characterized by means of FTIR, ~1H and ~(29)Si-NMR, and elemental analysis. Azeotropic distillation of solvents and H_2O formed during polymerization was found useful in removing H_2O from the system and high molecular weight products with perfect ladderlike structure were obtained.     

SYNTHESIS OF HIGH THERMOSTABLE SILICONE GELS CONSTRUCTED WITH LADDERLIKE POLYSILSESQUIOXANES*

Heat-resistant silicone gels were synthesized by replacing the single main chain polymethylhydrosiloxane withreactive ladderlike polyhydrosilsesquioxane copolymers. Because of the interaction between polydimethylsiloxane chainsand the ladderlike polysilsesquioxanes chains, the cyclization of the polydimethylsiloxane chains is hindered. The highthermal stability of the ladderlike polymers can improve the thermal stability of the silicone gels without sacrificing their good comprehensive properties.     

A novel aryl amide-bridged ladderlike polymethylsiloxane synthesized by an amido H-bonding self-assembled template

A novel soluble aryl amide-bridged ladderlike polymethylsiloxane (A-LPMS) was synthesized by stepwise coupling polymerization on the basis of amido H-bonding self-assembling template from monomer N,N'-bis(3-methyldiethoxylsilylpropyl)-[4,4'-oxybis(benzyl amide)]. The monomer was prepared in a high yield by the hydrosilylation reaction of template agent N,N'-diallyl-[4,4'-oxybis(benzyl amide)] with methyldiethoxysilane in the presence of dicyclopentadienylplatinum dichloride (Cp(2)PtCl(2)) as catalyst. A variety of techniques including (1)H NMR, (13)C NMR, (29)Si NMR, FTIR, XRD, DSC, and, especially, static and dynamic light scattering and viscosimetry were combined to confirm the presence of the ordered ladderlike structure of polymer A-LPMS.     

In situ poling and orientation stability of chromophore-bearing ladderlike polysiloxanes

A new, specially designed nonlinear optical (NLO) polymer is composed of ladderlike polysilsesquioxane as a backbone and “side-on or end-on” fixed stilbene chromophores. In-situ poling was carried out simultaneously during film formation via solvent evaporation and crosslinking which was caused by sequential hydrolysis and condensation of remained Si-H groups on macromolecules. The dipolar orientation after poling is described by an order parameter Φ which was measured using an original linear optical technique–UV dichroism. Orientation order and its decay are influenced by chromophore loading, crosslinking degree and poling condition. Compared with corresponding single chain polymers, a poled thin film of ladderlike NLO polymers demonstrates more stable poling-induced orientation.     

Synthesis and characterization of a novel reactive ladderlike 4,4′‐phenylene ether‐bridged polyvinylsiloxane

A novel soluble, reactive ladderlike 4,4′‐phenylene ether‐bridged polyvinylsiloxane (L) was synthesized successfully for the first time by a stepwise coupling polymerization (SCP) including hydrolysis and polycondensation. The monomer, 4,4′‐bis(vinyldimethoxysilyl)phenylene ether (M), was synthesized by Grignard reaction. The structures of the monomer and the polymer were characterized by infrared spectrometry (IR), nuclear magnetic resonance (¹H NMR, ¹³C NMR, ²⁹Si NMR), mass spectrometry (MS), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and gel permeation chromatography (GPC). It is proposed from the characterization data that the polymer possesses an ordered ladderlike structure. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2702–2710, 2000     

SYNTHESES OF THE SOLUBLE,HIGH MOLECULAR WEIGHT AND LADDERLIKE POLYPH ENYLSILSESQUIOXAN E AND COPOLYMETHYLPHENYLSILSESQUIOXANES BY PREAMMINOLYSIS METHOD

Soluble, high molecular weight (MW) and ladderlike polyphenylsilsesquioxane (LPPSQ) and its copolymers, ladderlike random and block copolymethyiphenylsilsesquioxanes(LR-PMPSQ and LB-PMPSQ)have been prepared by preamminolysis, hydrolysis and polycondensation reactions. The preparation method can be carried out easily at the temperature below 95℃with high yield of 95 %, instead of the conventional way by using high-boiling solvent and any reaction activator or by precipitation with methanol. Three kinds of ladderlike polymers have been characterized. The MW's of the polymers reached to 10~6 without noticeable gelling. The scheme for synthetic route has been proposed.     

Synthesis,characterization, and properties of novel ladderlike phosphorus‐containing polysilsesquioxanes

Novel ladderlike polysilsesquioxanes that contain phosphorus were successfully synthesized by the sol–gel method. The polysilsesquioxanes were characterized by Fourier transform infrared spectroscopy, ²⁹Si NMR, and X‐ray diffraction. The characterizations demonstrated that the polymer possesses a typical ladderlike structure. The thermogravimetric and differential scanning calorimetric data revealed that the polysilsesquioxanes possess excellent thermal stability. A kinetic analysis of thermal degradation showed that the activation energy of thermal degradation is 187 kJ/mol, according to Kissinger's method. The activation energy of thermal degradation normally increases with conversion (from 171 to 309 kJ/mol) according to Ozawa's method. The average activation energy, calculated by Ozawa's method, was 209 kJ/mol. The scanning electron microscopic photograph and Si and P mappings of ladderlike polysilsesquioxanes showed that the particles were uniformly dispersed at the molecular level and that the sizes of the polysilsesquioxane particles were less than 100 nm. The ultraviolet–visible spectra of the ladderlike polysilsesquioxanes revealed no absorbance in the range of 400–800 nm. Ladderlike polysilsesquioxanes possess excellent optical transparency and excellent flame retardance. This transmittance may be used as a criterion for identifying the formation of a homogeneous phase. These polymers have great potential in waveguide applications. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1371–1379, 2003     

反应性梯形聚氢基倍半硅氧烷合成方法的改进

对反应性梯形聚氢基倍半硅氧烷 (H T)的合成方法进行了改进 .首先利用硅羟基与硅氯基之间的脱氯化氢缩聚来代替以前采用的硅羟基间脱水缩聚反应 ,进一步提高了作为梯撑的对苯二胺之间氢键在聚合反应中的模板作用 .另外利用三甲基氯硅烷与对苯二胺梯撑的聚硅氧烷中间体的末端硅羟基进行封端反应 ,从而保证在脱除对苯二胺梯撑模板分子过程中避免进一步的无规缩合导致支化或交联 ,得到的反应性梯形聚氢基倍半硅氧烷 (H T)的规整性有所改善 .热分析结果表明与单链聚二甲基硅氧烷的Tg(- 12 3℃ )相比 ,其Tg 高达 117 0℃ ,证明这种梯形高分子具有刚性链结构 .尤其是2 9Si NMR谱中代表梯形主链上硅原子 (SiO3 2 )峰的基线宽度Δ =5 ,而采用硅羟基间脱水缩合方法得到聚合物的Δ =8～ 10 .表明该反应性梯形聚氢基倍半硅氧烷H T的规整性得到了明显的提高 .而且 ,该聚合物又是第一个可溶性、反应性、纯梯形主链无机高分子 ,它可以进一步通过硅 氢侧基接枝反应制备不同类型的梯形无机主链功能高分子 .     

Surface free energy of ladderlike polyepoxysiloxane–diamine reaction systems

We studied three kinds of ladderlike polyepoxysiloxanes, which have different side groups grafted on the ladderlike backbones. 1,3‐Bis(aminopropyl)tetramethyl disiloxane (diamine) was used as the curing agent. The reaction between ladderlike polyepoxysiloxanes and diamine was investigated by contact angle measurements and surface free energy study. Several factors such as diamine amount, reaction time, and temperature can affect the systems' surface tension (or surface free energy), which were determined by two‐liquid geometric and three‐liquid acid‐base methods. The experimental results showed that an increase in the diamine amount in the reaction systems results in an increase in the polar part of surface free energy because of electron donate characteristics of the diamine. However, because epoxy (electron acceptor) and diamine (electron donor) react fast at elevated temperatures, increasing reaction temperature decreases the polar part of the surface free energy, while increases the nonpolar part of the surface free energy. The evolution of surface free energy with time for various epoxy–diamine reaction systems at various temperatures has also been studied. It was found that it took a relatively long time (50–60 h) to reach the equilibrium state. The experimental results can be well interpreted by the epoxy–diamine reaction mechanism and van Oss–Good's Lewis acid‐base theory. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1449–1460, 2000     

Surface study of ladderlike polyepoxysiloxanes

By using the two‐liquid geometric method and the three‐liquid acid‐base method, we are the first to determine the surface tensions of ladderlike polyepoxysiloxanes by the measurement of contact angles on thin films. Three kinds of ladderlike polymers have been synthesized: A C (which has the alkyl group and the epoxy group graft to the ladderlike polysilsesquioxane chain), A C P (which has the alkyl group, phenyl group, and epoxy group graft to the ladderlike chain), and A P (which has the phenyl group and epoxy group in the ladderlike side chain). The results showed that when different liquids and different theories are chosen to determine the surface energies, there are some minor differences in the values but a similar trend is still exhibited. The surface energies of these three polymers are in the following order of γ_{SA C} < γ_{SA C P} < γ_{SA P}. Interestingly, the surface energy increases for these polymers are mainly from the nonpolar part of the polyepoxysiloxanes. XPS surface analysis indicated that the Si and O ratios of these polymers at the air‐polymer interface were in the order of A C > A C P > A P, suggesting Si atoms were more likely to migrate to the polymer surface and the bulky effect of the phenyl groups could also interfere with the migration of the Si atoms. As a result, Si and O ratio at the interface determines the order of apparent surface energy for these three polymers. Experimental data also reflect that there are differences between the ladderlike polyepoxysiloxanes and the commercially available linear polysiloxanes. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 138–147, 2000     

Self‐assembling directed synthesis of a novel terephthalamide‐bridged ladderlike polysiloxane

A novel, soluble terephthalamide‐bridged ladderlike polysiloxane ( L ) was synthesized successfully for the first time by stepwise coupling polymerization. The process involved the hydrogen‐bonding self‐assembly of amido groups, which resulted in the formation of a more highly ordered polymeric structure. A novel monomer, bis(3‐methyldimethoxysilylpropyl) terephthalamide ( M ), was prepared by a hydrosilylation reaction in the presence of dicyclopentadienyl platinum dichloride as a catalyst. The structures of the monomer ( M ) and the polymer ( L ) were characterized by Fourier transform infrared, ¹H NMR, ¹³C NMR, ²⁹Si NMR, mass spectrometry, X‐ray diffraction, differential scanning calorimetry, and vapor pressure osmometry. All the characterization data indicated that the synthesized polymer ( L ) possessed an ordered ladderlike structure. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3161–3170, 2002     

Design,synthesis and magnetic properties of a ladderlike complex constructed by secondary building units

A secondary building unit (SBU), [Ni(2,2′-bipy)(5-npa)(H₂O)] _n [where 2,2′-bipy = 2,2′-bipyridine, 5-npa = 5-nitroisophthalic dianion], was synthesized as starting material of a polystep reaction. A ladderlike complex (LLC) Ni(II) coordination polymer, {[Ni(2,2′-bipy)(5-npa)(4,4′bipy)_0.5]·(H₂O)} _n , was constructed by polystep reaction using this SBU. In LLC, two SBUs were cross-linked by 4,4′-bipy [where 4,4′-bipy = 4,4′-bipyridine] forming a 1-D ladderlike structure. The magnetic properties of the LLC and SBU are discussed.     

Photo-driven liquid crystal cell using azobenzene-grafted ladderlike polysiloxane as command layer

A novel photo-driven liquid crystal (LC) cell was fabricated by sandwiching nematic LC molecules between two quartz plates whose surface was modified with 4-hexyloxy-4′-undecanyloxyazobenzene (6Az11)-grafted ladderlike copoly(methylhydrosilsesquioxane) (PMHSQ). Reversible changes of the alignment between homeotropic and planar modes were achieved. The transmittance through the cell and crossed polarizers could be controlled by the irradiation intensity of 365 nm UV light. A high contrast ratio over 100:1 was obtained.