Solid and thermal properties of ABA‐type triblock copolymers designed using difunctional fluorine‐containing polyimide macroinitiators with methyl methacrylate

BACKGROUND: ABA‐type poly(methyl methacrylate) (PMMA) and fluorine‐containing polyimide triblock copolymers are potentially beneficial for electric materials. In the work reported here, triblock copolymers with various block lengths were prepared from fluorine‐containing difunctional polyimide macroinitiators and methyl methacrylate monomer through atom‐transfer radical polymerization. The effects of structure on their solid and thermal properties were studied. RESULTS: The weight ratios of the triblock copolymers derived using thermogravimetric analysis were shown to be almost identical to the ratios determined using ¹H NMR. The solid properties (film density and maximum d‐spacing value) and thermal properties (glass transition and thermal expansion) were shown to be strongly dependent on the weight ratios of both PMMA and polyimide components. Furthermore, a porous film, which showed a lower dielectric constant of 2.48 at 1 MHz, could be prepared by heating a triblock copolymer film to induce the thermal degradation of the PMMA component. CONCLUSION: The use of the polyimide macroinitiator was useful in the preparation of ABA‐type triblock copolymers to control each block length that influences the solid and thermal properties. Additionally, the triblock copolymers have great potential in preparing porous polyimides in the application of electric materials as interlayer insulation membranes of large‐scale integration. Copyright © 2009 Society of Chemical Industry     

Structure and properties of polyimide‐g‐nylon 6 and nylon 6‐b‐polyimide‐b‐nylon 6 copolymers

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ε‐caprolactam. Nylon 6‐b‐polyimide‐b‐nylon 6 copolymers were prepared by the use of phenyl 4‐aminobenzoate as an end‐capping agent in the preparation of a series of imide oligomers. The oligomers were then used to activate the anionic polymerization of ε‐caprolactam. In both the graft and copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. All the block copolymers had higher moduli and tensile strengths than those of nylon 6. However, their elongations at break were much lower. The graft copolymers based on 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and 2,2′‐bis[4‐(4‐aminophenoxy)phenyl]propane displayed elongations comparable to that of nylon 6 and the highest moduli and tensile strengths of all the copolymers. The thermal stability, moisture resistance, and impact strength were dramatically increased by the incorporation of only 5 wt % polyimide into both the graft and block copolymers. The graft and block copolymers also exhibited improved melt processability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 300–308, 2006     

Synthesis and properties of poly(imide siloxane) block copolymers with different block lengths

Several poly(imide siloxane) block copolymers with the same bis(γ‐aminopropyl)polydimethylsiloxane (APPS) content were prepared. The polyimide hard block was composed of 4,4′‐oxydianiline and 3,3′,4,4′‐diphenylthioether dianhydride (TDPA), and the polysiloxane soft block was composed of APPS and TDPA. The length of polysiloxane soft block increased simultaneously with increasing the length of polyimide hard block. For better understanding the structure–property relations, the corresponding randomly segmented poly(imide siloxane) copolymer was also prepared. These copolymers were characterized by FT‐IR, ¹H‐NMR, dynamic mechanical thermal analysis, thermogravimetric analysis, polarized optical microscope, rheology and tensile test. Two glass transition temperatures (T_g) were found in the randomly segmented copolymer, while three T_gs were found in the block copolymers. In addition, the T_gs, storage modulus, tensile modulus, solubility, elastic recovery, surface morphology and complex viscosity of the copolymers varied regularly with increasing the lengths of both blocks. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Porous polyimide films obtained by using lithium chloride as pore‐forming agent

Porous polymer films have been obtained from polyimide based on benzophenonetetracarboxylic dianhydride and 4,4'‐diamino‐3,3'‐dimethyl‐diphenylmethane by incorporating lithium chloride (LiCl) in the poly(amidic acid) precursor and subsequently leaching out the maximum possible LiCl by water Soxhlet extraction for 6 h. The resulting porous polyimide films were characterized with regard to their pore size, thermal stability and dielectric properties. The morphology of the porous polyimide films showed a uniform distribution and various pore sizes depending on the initial quantity of added pore‐forming agent. © 2013 Society of Chemical Industry     

Preparation of polyimide/nylon 6 graft copolymers from polyimides containing ester moieties: Synthesis and characterization

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ?‐caprolactam. In the graft copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. The thermal stability and chemical resistance were dramatically increased by the incorporation of only 5 wt % polyimide in the graft copolymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 309–318, 2006     

Synthesis of poly(propylene glycol)‐grafted polyimide precursors and preparation of nanoporous polyimides

A novel approach to prepare a polyimide nanofoam was explored by using a polyimide precursor grafted with a labile poly(propylene glycol) (PPG) oligomer. The PPG‐grafted polyimide precursor, poly((amic acid)‐co‐(amic ester)), was synthesized via partial esterification of poly(amic acid) derived from pyromellitic dianhydride (PMDA) and 4,4′‐oxydianiline (ODA) with bromo‐terminated poly(propylene glycol) in the presence of K₂CO₃ in hexamethylphosphoramide and N‐methylpyrrolidone. The precursor polymer film was spin‐coated onto a glass substrate, then imidized at 200 °C under nitrogen, and subsequently the PPG graft was decomposed by heating the film at 300 °C for 9 h in air, resulting in the PMDA/ODA polyimide nanofoam. The precursor polymers, polyimides and foamed polyimides were characterized by a variety of techniques including ¹H‐NMR spectroscopy, Fourier‐transform infrared (FT‐IR) spectroscopy, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The homogeneously distributed nano‐sized pores of 20–40 nm were observed by transmission electron microscopy (TEM) of the foamed polyimide. Copyright © 2004 Society of Chemical Industry     

基于偏氯乙烯嵌段共聚物的多级多孔炭的制备

采用可逆加成-断裂链转移（RAFT）活性自由基聚合制备了聚苯乙烯-b-聚偏氯乙烯-b-聚苯乙烯嵌段共聚物（PS-b-PVDC-b-PS）,以此嵌段共聚物为碳前驱体,直接碳化制备微孔-中孔复合多级多孔炭。采用凝胶渗透色谱仪和核磁共振仪表征了嵌段共聚物结构,表明通过RAFT聚合可制得分子量较高（M_n^GPC >6000 g·mol^-1）和分子量分布较窄（PDI<1.5）的PS-b-PVDC-b-PS。采用热重分析表征嵌段共聚物热解特性,采用扫描电镜、N₂吸脱附表征多孔炭形貌和孔隙结构。结果表明嵌段共聚物同时具有PVDC和PS链段的热失重峰,PS链段可完全热解而具有形成中孔的模板作用,PVDC链段热降解形成含微孔的炭骨架,最终形成兼有微孔和中孔的多级多孔炭;随着PS嵌段含量的增加,嵌段共聚物的成炭率逐渐降低,孔隙尺寸逐渐增大;当PS/PVDC聚合度比为4.3时,多孔炭的比表面积、中孔率和平均孔径达到最大,分别为839 m²·g^-1、54%和2.02 nm。     

Synthesis and characterization of novel biodegradable triblock copolymers from L-Lactide,glycolide, and PPG

Copolymers with a PPG center block and two arms of random glycolide/lactide copolymers have been synthesized and characterized. Compared to random glycolide/lactide copolymers, these new polymers have high toughness and low elastic modulus.¹ H-NMR spectral lines of glycolide CH₂ protons of the copolymers are essentially identical. These materials show no crystallization transition in DSC thermograms and their melting points with respect to PLLA appeared at lower temperatures, indicating the pivotal role of the PPG center block in the copolymer. Degradation in aqueous media (pH = 6.9, 70°C) with stirring, subjected the two end blocks to hydrolytic degradation. The glycolyl ester bond cleavage was faster than for the lactyl ester bond. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 633–637, 1999     

Synthesis and characterization of poly(propylene glycol) polytrioxamide and poly(urea oxamide) segmented copolymers

This report describes the synthesis and characterization of unprecedented poly(propylene glycol) (PPG) polytrioxamide and poly(urea oxamide) (UOx) segmented copolymers containing monodisperse hard segments. Synthesis of the segmented copolymers relied on an efficient two‐step end‐capping sequence, which resulted in novel difunctional oxamic hydrazide‐terminated polyether oligomers. Polymerization with oxalyl chloride or 4,4′‐methylenebis(cyclohexyl isocyanate) provided the desired segmented copolymers displaying thermoplastic elastomeric behavior. Variable‐temperature Fourier transform infrared and ¹H NMR spectroscopies confirmed the presence of hard segment structures and revealed ordered hydrogen bonding interactions with thermal dissociation profiles similar to those of polyurea and polyoxamide copolymer analogs. Dynamic mechanical analysis of PPG‐UOx exhibited a longer, rubbery plateau with increased moduli compared to PPG polyurea, and tensile analysis revealed a dramatic increase in copolymer toughness due to enhanced hydrogen bonding. A new step‐growth polymerization strategy is described that is capable of producing tunable hydrogen bonding segmented copolymer architectures. © 2013 Society of Chemical Industry     

PSA performances and viscoelastic properties of SIS‐based PSA blends with H‐DCPD tackifiers

Hotmelt pressure sensitive adhesives (PSAs) usually contain styrenic block copolymers like styrene–isoprene–styrene (SIS), SBS, SEBS, tackifier, oil, and additives. These block copolymers individually reveal no tack. Therefore, a tackifier is a low molecular weight material with high glass transition temperature (T_g), and imparts the tacky property to PSA. The SIS block copolymer with different diblocks was blended with hydrogenated dicyclopentadiene (H‐DCPD tackifier), which has three kinds of T_g. PSA performance was evaluated by probe tack, peel strength, and shear adhesion failure temperature. PSA is a viscoelastic material, so that its performance is significantly related to the viscoelastic properties of PSAs. We tested the viscoelastic properties by dynamic mechanical analysis and the thermal properties by differential scanning calorimeter to investigate the relation between viscoelastic properties and PSA performance. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2839–2846, 2006     

Flame retardancy of a polycarbonate–polydimethylsiloxane block copolymer: The effect of the dimethylsiloxane block size

This report describes the flame retardancy of a polycarbonate (PC)–polydimethylsiloxane (PDMS) block copolymer with a dimethylsiloxane (DMS) block size of 15–350 units, and the effects of the block size and amount of DMS on the flame retardancy are studied. PC–PDMS block copolymers with DMS units of 40–130 had high limiting oxygen index values with 1.0 wt % PDMS. The PDMS block size influenced the PDMS dispersibility in PC, and a moderate PDMS dispersion (ca. 50 nm) caused high flame retardancy for PC. These PC–PDMS block copolymers could form a lot of fine bubbles in the role of good thermal insulators through the reaction of PC and PDMS in combustion. Furthermore, the silica particles from PDMS remained mostly on the surface of the char, so the amount of char with high oxidation resistance increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 565–575, 2006     

Poly(n-butyl methacrylate) end-capped polyrotaxanes via ATRP initiated with α-cyclodextrin and Pluronic 17R4 based inclusion complexes

A series of polyrotaxane (PR)-based triblock copolymers comprising a PR middle block and poly(n-butyl methacrylate) (PBMA) flanked blocks were prepared via bulk ATRP of n-butyl methacrylate initiated with polypseudorotaxanes self-assembled from α-cyclodextrins (α-CDs) with 2-bromoisobutyryl terminated Pluronic 17R4 at 35 °C. Their structure was verified by ¹H NMR, FTIR, GPC, WXRD and TGA analyses. The dethreading of entrapped α-CDs during the polymerization process was effectively impeded through an elaborated choice of Pluronic 17R4, a PPG–PEG–PPG triblock copolymer, in which α-CDs site-selectively include with the middle PEG block and are inhibited by the flanked PPG blocks. The degree of polymerization of attached PBMA blocks appeared to be tunable to some extent. The polydispersity index of the resulting PR-based triblock copolymers is in a low range of 1.28–1.50. As an attempt toward the materialization of these unique supramolecular polymers, a selected sample was dissolved in methylene dichloride and electrospun into micro-sized particles. Nevertheless, they can be not only casted into tough films but also melt extruded into sticks.     

Syntheses and characterization of poly(phenylene sulfide)–poly(ether sulfone) block copolymers

Poly(phenylene sulfide)-poly(ether sulfone) (PPS–PES) block copolymers were synthesized by polycondensation of chloro-terminated PPS oligomers and hydroxylic-terminated PES oligomers at atmospheric pressure. The structure and compositions of PPS–PES block copolymers were analyzed quantitatively by FTIR spectroscopy. It was found that the contents of PES in copolymers increase with the amount of PES in the added materials; however, the quantities of PES contents in copolymers are lower than its quantities in the added materials. The solubility, crystallization behavior, and thermal properties of PPS-PES block copolymers were studied through a solubility test, X-ray diffraction, DSC, and TGA. It was primarily proved that the copolymers have better solubility, lower crystallinity, and higher glass transition (T_g) than those of PPS. The nonisothermal crystallization kinetics and thermal decomposition kinetics of block copolymers were also studied; furthermore, the crystallization kinetic parameters and the activation energy of thermal decomposition were calculated. © 1996 John Wiley & Sons, Inc.     

Porous pyridine based polyimide–silica nanocomposites with low dielectric constant

Highly porous polymer–silica hybrid materials were prepared based on the organo-soluble polyimides of four various dianhydride and 2,5-diaminopyridine. 3-Aminopropyltriethoxysilane (APS) was used to increase the intrachain chemical bonding and interchain hydrogen bonding between the polyimide and silica moieties, respectively. The chemical interaction would significantly affect the morphologies and properties of the prepared films. The produced polyimide–silica composites were investigated by X-ray diffraction analysis, scanning electron microscope and thermal analysis tecniques. The effect of silica modified with functional group of 3-aminopropyltriethoxy silane on the porous structure and dielectric properties as well as the thermal stability of films were investigated. Capacitances were determined with a HP4294A at a frequency between 1 kHz and 1 MHz. The dielectric constant was significantly reduced with increasing silica modified with APS. The result indicates that the composite materials are potentially useful in low dielectric materials.     

Crystallization Behavior of Nanocomposites Synthesized from the Poly (L-lactide)-poly (Propylene Glycol) and Organoclay

This study explored the thermal behavior of PLLA–PPG nanocomposite with added organoclay. The modified clay was evenly dispersed into the matrix of LPG1000 to synthesize the nanoscale polymer. Thermogravimetric analysis and differential scanning calorimetry were used to measure the thermal properties of the PLLA–PPG copolymers. Wide-angle X-ray diffraction was used to identify the crystal structure of PLLA–PPG copolymer. The crystal growth of PLLA–PPG copolymer with various proportions of added clay was observed by using polarized optical microscopy and transmission electron microscopy. The results show that adding clay could enhance the thermal stability of LPG1000 and significantly change its crystal property.     

Synthesis and Characteristics of Novel Poly(Imide Siloxane) Segmented Copolymers

New poly(imide siloxane) copolymers for possible use as tough environmentally stable structural matrix resins and structure adhesives have been prepared. Thus, 3,3'-4,4'-benzophenone tertracarboxylic dianhydride was reacted with various Mn aminopropyl-terminated polydimethylsiloxane oligomers and a meta-substituted diamine “chain-extender” such as 3,3'-diaminodiphenyl sulfone or 3,3'-diaminobenzophenone to produce the siloxane-modified poly(amic acid). Thin films were cast from the reaction mixtures and subsequent thermal dehydration produced the poly(imide siloxane) block or segmented copolymers. Upper “cure” temperatures of 300°C were used to insure complete imidization. By varying the amount and molecular weight of the siloxane oligomer, a variety of novel copolymers of controlled composition have been synthesized. Tough, transparent, flexible soluble films were produced by this method. The thermal and bulk properties of films having low to moderate siloxane content closely resemble those of the unmodified polyimide controls. However, toughness and surface behavior can be enhanced.     

Polyimide–polydimethylsiloxane copolymers for low‐dielectric‐constant and moisture‐resistance applications

Novel, randomly coupled, soluble, segmented polyimide–polydimethylsiloxane (PI–PDMS) copolymers were prepared from aminoalkyl‐terminated polydimethylsiloxane (At–PDMS), 4,4′‐oxydianiline diamine, pyromellitic dianhydride, and 4,4′‐diphenylmethane diisocyanate (MDI). When At–PDMS was introduced into the polyimide chain, the polyimide copolymers exhibited lower dielectric constants and better moisture resistance and mechanical properties. The reductions in the dielectric constant of the PI–PDMS copolymers could be attributed to the incorporation of polydimethylsiloxane (PDMS) into the polyimide chain and the nanopores in the film generated by carbon dioxide evolvement during the reaction. The lowest dielectric constant was 2.58 with 25 wt % PDMS and 5 wt % MDI. In addition, the water contact angles of the resultant copolymers increased from 51 to 109° when the contents of PDMS increased from 0 to 25 wt %. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The role of the ratio (PEG:PPG) of a triblock copolymer (PPG‐b‐PEG‐b‐PPG) in the cure kinetics,miscibility and thermal and mechanical properties in an epoxy matrix

The aim of this study was to evaluate the role of different poly(ethylene glycol):poly(propylene glycol) (PEG:PPG) molar ratios in a triblock copolymer in the cure kinetics, miscibility and thermal and mechanical properties in an epoxy matrix. The poly(propylene glycol)‐block‐poly(ethylene glycol)‐block‐poly(propylene glycol) (PPG‐b‐PEG‐b‐PPG) triblock copolymers used had two different molecular masses: 3300 and 2000 g mol^?1. The mass concentration of PEG in the copolymer structure played a key role in the miscibility and cure kinetics of the blend as well as in the thermal–mechanical properties. Phase separation was observed only for blends formed with the 3300 g mol^?1 triblock copolymer at 20 wt%. Concerning thermal properties, the miscibility of the copolymer in the epoxy matrix reduced the T_g value by 13 °C, although a 62% increase in fracture toughness (K_IC) was observed. After the addition of PPG‐b‐PEG‐b‐PPG with 3300 g mol^?1 there was a reduction in the modulus of elasticity by 8% compared to the neat matrix; no significant changes were observed in T_g values for the immiscible system. The use of PPG‐b‐PEG‐b‐PPG with 2000 g mol^?1 reduced the modulus of elasticity by approximately 47% and increased toughness (K_IC) up to 43%. Finally, for the curing kinetics of all materials, the incorporation of the triblock copolymer PPG‐b‐PEG‐b‐PPG delayed the cure reaction of the DGEBA/DDM (DGEBA, diglycidyl ether of bisphenol A; DDM, Q3‐4,4′‐Diaminodiphenylmethane) system when there is miscibility and accelerated the cure reaction when it is immiscible. All experimental curing reactions could be fitted to the Kamal autocatalytic model presenting an excellent agreement with experimental data. This model was able to capture some interesting features of the addition of triblock copolymers in an epoxy resin. © 2018 Society of Chemical Industry     

Synthesis and biodegradation of copolyesterether of copoly(succinic anhydride/ethylene oxide) with polyether

The thermal properties and biodegradability of block copolyesterethers based on copoly[succinic anhydride (SA)/ethylene oxide (EO)] (polymer composition range SA/EO 42/58–49/51 mol %), synthesized by ring-opening copolymerization and poly(ethylene glycol) (PEG) or poly(propylene glycol) (PPG), were studied. The block copolyesterethers synthesized from higher than 7000 molecular weight (M_n) or high SA content copoly(SA/EO), SA/EO = 48/52 or 49/51, and PEG showed melting points and fusion heats (ΔH) similar to those of the prepolymers without leading to a microphase-separation structure. Enzymatic degradability of the block copolyesterethers synthesized from biodegradable copoly(SA/EO) with a low SA content (SA/EO = 42/58 mol %) and PEG was significantly smaller compared to that of the chain-extended copoly(SA/EO) used as a prepolymer. On the other hand, the block copolymers synthesized by an equimolar amount of copoly(SA/EO) and PPG showed evidence of a microphase-separation structure. An increase in propylene glycol (PG) content interfered with the formation of a microphase-separation structure. However, the block copolyesterethers including nonbiodegradable copoly(SA/EO), with a high SA content (SA/EO = 49/51 mol %), and PPG were found to be enzymatically degradable. In the biodegradation testing with standard activated sludge, the block copolyesterethers were degraded by microorganisms in activated sludge. The relationship between polymer composition and the biodegradation rate by activated sludge shows a similar trend to that of enzymatic hydrolysis. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 2095–2106, 1998     

SPTES-b-PI质子交换膜的制备及表征

质子交换膜作为质子交换膜燃料电池的核心部件具有提供离子通道传递质子和隔绝两极气体的双重作用,其性能的好坏直接影响着电池性能的优劣。主链引入亲水和疏水段的嵌段芳香族共聚物,由于各嵌段之间具有热力学不相容性会产生微相分离结构,进而形成高效的质子传导通道。本文以磺化双（4-氟苯基）砜（SDFDPS）和4,4'-硫代双苯硫酚（TBBT）为单体,以间羟基苯胺为封端剂合成了带有氨端基的磺化聚芳硫醚砜（SPTES-NH₂）。嵌段聚合物SPTES-b-PI通过亲水段SPTES-NH₂与以1,4,5,8-萘四羧酸二酐（NDA）和4,4'-双（3-氨基苯氧基）二苯基砜（m-BAPS）为单体缩聚而成的疏水段聚酰亚胺（PI）的酰亚胺化偶联反应来合成,制备出了PI分子量不同的SPTES-b-PIx（x=5~20kg/mol）。SPTES-b-PIx膜显示出优异的热力学稳定性,SPTES-b-PIx膜的脱磺化反应开始于290℃高于260℃的SPTES膜,与SPTES-70相比吸水率降低。随着聚酰亚胺分子量的增大,热稳定性增加,质子传导率增加。SPTES-b-PIx的质子传导率25℃下达到0.045~0.124S/cm。