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1.
Copolyimide derivatives were prepared from two carboxylic dianhydrides [3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) and pyromellitic anhydride (PMDA)] and a single diamine (bis[4‐(3‐aminophenoxy)phenyl]sulfone [BAPS]) following one‐step polymerization. Copolymers could be arranged in sequence through different molar ratios of dianhydride compounds. These polymers were characterized by viscosity, thermal and mechanical properties, solubility, etc. To understand the behavior of the properties, according to the ratio of the dianhydride compound, a copolymer having various properties could be obtained. Further, it was proved that their properties could be determined from the compositions. The solubility of copolyimides with a large molecular weight was moderately improved. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 853–859, 2003  相似文献   

2.
Fluorinated polyimides were prepared from 2,2′,6,6′-tetrafluorobenzidine and four conventional dianhydride monomers by a solution polycondensation reaction followed by a chemical imidization. Polyimide based on 2,2′,6,6′-tetrafluorobenzidine and hexafluoroisopropylidene bis(3,4-phthalic anhydride) (6FDA) is soluble in organic solvents such as NMP, DMA, DMF, THF, chloroform, and acetone while those based on 2,2′,6,6′-tetrafluorobenzidine and pyromellitic dianhydride (PMDA), benzophenone-3,3′,4,4′-tetracarboxylic acid dianhydride (BTDA), diphenylether-3,3′,4,4′-tetracarboxylic acid dianhydride (ETDA) are not. Polyimide from 2,2′,6,6′-tetrafluorobenzidine and 6FDA possesses high optical transparency at 350–700 nm and has a in-plane refractive index of 1.558 at 632.8 nm. All polyimides exhibit glass transition temperatures above 350°C. They also possess very high thermal stability. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1605–1609, 1998  相似文献   

3.
A novel dianhydride, trans‐1,2‐bis(3,4‐dicarboxyphenoxy)cyclohexane dianhydride (1,2‐CHDPA), was prepared through aromatic nucleophilic substitution reaction of 4‐nitrophthalonitrile with trans‐cyclohexane‐1,2‐diol followed by hydrolysis and dehydration. A series of polyimides (PIs) were synthesized from one‐step polycondensation of 1,2‐CHDPA with several aromatic diamines, such as 2,2′‐bis(trifluoromethyl)biphenyl‐4,4′‐diamine (TFDB), bis(4‐amino‐2‐trifluoromethylphenyl)ether (TFODA), 4,4′‐diaminodiphenyl ether (ODA), 1,4‐bis(4‐aminophenoxy)benzene (TPEQ), 4,4′‐(1,3‐phenylenedioxy)dianiline (TPER), 2,2′‐bis[4‐(3‐aminodiphenoxy)phenyl]sulfone (m‐BAPS), and 2,2′‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]sulfone (6F‐BAPS). The glass transition temperatures (Tgs) of the polymers were higher than 198°C, and the 5% weight loss temperatures (Td5%s) were in the range of 424–445°C in nitrogen and 415–430°C in air, respectively. All the PIs were endowed with high solubility in common organic solvents and could be cast into tough and flexible films, which exhibited good mechanical properties with tensile strengths of 76–105 MPa, elongations at break of 4.7–7.6%, and tensile moduli of 1.9–2.6 GPa. In particular, the PI films showed excellent optical transparency in the visible region with the cut‐off wavelengths of 369–375 nm owing to the introduction of trans‐1,2‐cyclohexane moiety into the main chain. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42317.  相似文献   

4.
Polyimides were prepared from diamines: 2,4,6-trimethyl-1,3-phenylenediamine (3MPDA) and 2,3,4,5-tetramethyl-1,4-phenylenediamine (4MPDA). 1,4-Bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA), 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 3,3′-4,4′-diphenylsulphone tetracarboxylic dianhydride (SO2PDA), 3,3′,4,4′-diphenylsulphide tetracarboxylic dianhydride (SPDA), pyromellitic dianhydride (PMDA), and 2,2′-bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride (6FDA) were used as dianhydride. The gas permeabilities of H2, O2 and N2 through the polyimides were measured at temperatures from 30 °C to 90 °C. The results show that as methyl and trifluoromethyl substitution groups densities increase from 7.73 × 10−3 mol cm−3 to 13.50 × 10−3 mol cm−3, the peameability of H2 increases 10-fold at 60% loss of permselectivity of H2/N2; however, the permeability of O2 increases 20-fold at 20% loss of permselectivity of O2/N2. For O2/N2 separation, PMDA-3MPDA has similar performance to 6FDA-3MPDA and 6FDA-4MPDA; all have higher permeabilities for O2 than normal polyimides, and the P(O2)/α(O2/N2) trade-off relationships lie on the upper bound line for polymers. © 1999 Society of Chemical Industry  相似文献   

5.
A series of novel phenylethynyl‐endcapped polyimide oligomers were prepared by polycondensation of an aromatic diamine mixture of 1,3‐bis(4‐aminophenoxy) benzene (1,3,4‐APB) and 3,4′‐oxydianiline (3,4′‐ODA) with different aromatic dianhydrides including 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐(hexafluoro isopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), and 4,4′‐[2,2,2‐trifluoro‐1‐(3′,5′‐bis‐(trifluoro‐methyl)phenyl)ethylidene]diphthalic anhydride (9FDA) in the presence of 4‐phenyl‐ethynylaniline (PEA) as endcapping agent in aprotic solvent at elevated temperature. The chemical structures, thermal behavior, and melt rheological properties of the synthesized polyimide oligomers were investigated. Experimental results indicated that the fluorinated polyimide oligomers derived from 6FDA (PI‐2) and 9FDA (PI‐4) are amorphous solid resins and exhibited lower melt viscosities than those prepared from the unfluorinated aromatic dianhydrides such as BPDA and ODPA. The BPDA‐based polyimide oligomers with a molar ratio of 1,3,4‐APB/3,4′‐ODA = 50:50 (PI‐5) showed lower melt viscosity than those derived from a mixture of 1,3,4‐APB and 3,4′‐ODA with molar ratios of 75:25 and 100:0, respectively. In addition, the melt viscosity of the polyimide oligomers increased obviously with increasing of the polymer calculated molecular weights. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers  相似文献   

6.
New aromatic polyetherimides containing the 1,1′-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane dianhydride unit were prepared by a conventional two-step method from 1,1′-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1-phenyl-2,2,2-trifluoroethane dianhydride and several diamines. This procedure yielded high molecular weight polyetherimides with inherent viscosities of 0.22–1.29 dL/g. Most of the corresponding polyetherimides were soluble in organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N,N-dimethylacetamide, and methylene chloride under ambient temperature. The glass transition temperatures (Tg) of these polymers were in the range of 207–264°C and the temperatures of 10% weight loss were over 520°C at a heating rate 20°C/min in nitrogen. © 1996 John Wiley & Sons, Inc.  相似文献   

7.
Ten nadicimide/methyl nadicimide end-capped oligomeric resins were prepared by reacting endo-5-norbornene-2,3-dicarboxylic acid anhydride (methyl nadic anhydride), pyromellitic dianhydride (PMDA)/3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA)/2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6F), and bis(3-aminophenyl) methyl phospine oxide (BAP) in glacial acetic acid/acetone. Structural characterization of the resins was done by elemental analysis, IR, and 1H-NMR. Multistep decomposition was observed in the TG scan of uncured resins in a nitrogen atmosphere. Residual weight at 800°C depended on the structure and ranged between 25 and 51%. Isothermal curing of the resins was done at 300°C for 1 h in an air atmosphere. These cured resins were stable to 350 ± 30°C and decomposed in a single step above this temperature. The char yield of the resins increased on curing and was in the range 34–70%. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:861–869, 1997  相似文献   

8.
用自制的叔丁基二胺单体1,4-双(4-氨基苯氧基)-2-叔丁基苯(BATB)与三种二酐3,3’,4,4’-二苯醚四酸二酐(ODPA)、3,3’,4,4’-二苯甲酮四酸二酐(BTDA)、2,2’-双[4-(3,4-二羧苯氧基)苯基]丙烷四酸二酐(BPADA)反应,以马来酸酐作为封端剂得到了一系列链中含酰亚胺环的内扩链双马来酰亚胺,齐聚物的相对分子质量控制为4000~10000。将所得的溶解性好的双马来酰亚胺固体粉末溶于极性溶剂后,直接涂覆铜箔形成20μm涂层,干燥,再经程序升温固化,可以得无胶型挠性覆铜板,具有优异的耐热性、尺寸稳定性及低的吸水性。  相似文献   

9.
A soluble polyimide was synthesized from 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) and 3,3′‐dimethyl‐4,4′‐diaminodiphenylmethane (DMMDA) by a two‐step method, and it had good solubility both in strong bipolar solvents and in common low‐boiling‐point solvents. The BPADA–DMMDA polyimide was dissolved in chloroform (CHCl3) and cast onto a glass substrate in a humid atmosphere. The BPADA–DMMDA/CHCl3 solution easily formed honeycomb films. Some affecting factors, such as the polymer solution concentration, atmospheric humidity, and solvent volatility, were tested. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

10.
为了研究偶联剂对聚酰亚胺/SiO2杂化膜相分离及热分解温度的影响,以聚酰亚胺(HQDPA-ODA)为基体,正硅酸乙酯(TEOS)为添加剂,γ-缩水甘油丙氧基三甲氧基硅烷(GOTMS)为偶联剂,在共溶剂N,N′-二甲基甲酰胺(DMF)中,通过溶胶-凝胶法,制备出厚度约为30μm,不同SiO2质量分数的PI/SiO2杂化膜,采用傅立叶红外光谱FT-IR、热重分析TG-DTG、扫描电镜SEM等手段对膜材料的微观结构和耐热性能进行了表征。结果表明,加入GOTMS以后,SiO2粒径减小,由1 000 nm减小到200—400 nm,相分离产生的空腔结构消失,质量分数10%SiO2的杂化材料的热分解温度升高了21℃;杂化材料的热分解温度随SiO2质量分数的增加而升高。  相似文献   

11.
A pyromellitic dianhydride (benzene‐1,2,4,5‐tetracarboxylic dianhydride) was reacted with L ‐isoleucine in acetic acid, and the resulting imide acid [N,N′‐(pyromellitoyl)‐bis‐L ‐isoleucine] (4) was obtained in a high yield. 4 was converted into N,N′‐(pyromellitoyl)‐bis‐L ‐isoleucine diacid chloride by a reaction with thionyl chloride. The polycondensation reaction of this diacid chloride with several aromatic diamines, including 1,4‐phenylenediamine, 4,4′‐diaminodiphenyl methane, 4,4′‐diaminodiphenylsulfone (4,4′‐sulfonyldianiline), 4,4′‐diaminodiphenylether, 2,4‐diaminotoluene, and 1,3‐phenylenediamine, was developed with two methods. The first method was polymerization under microwave irradiation, and the second method was low‐temperature solution polymerization, with trimethylsilyl chloride used as an activating agent for the diamines. The polymerization reactions proceeded quickly and produced a series of optically active poly(amide imide)s with good yields and moderate inherent viscosities of 0.17–0.25 dL/g. All of the aforementioned polymers were fully characterized by IR, elemental analyses, and specific rotation. Some structural characterization and physical properties of these optically active poly(amide imide)s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 951–959, 2004  相似文献   

12.
Two series of aromatic polyimides containing various linkage groups based on 2,7‐bis(4‐aminophenoxy)naphthalene or 3,3′‐dimethyl‐4,4′‐diaminodiphenylmethane and different aromatic dianhydrides, namely 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride), 4,4′‐(hexafluoroisopropylidene)bis(phthalic anhydride), 3,3′,4,4′ benzophenonetetracarboxylic dianhydride, 9,9‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]fluorene dianhydride and 4,4′‐(4,4′‐hexafluoroisopropylidenediphenoxy)bis(phthalic anhydride), were synthesized and compared with regard to their thermal, mechanical and gas permeation properties. All these polymers showed high thermal stability with initial decomposition temperature in the range 475–525 °C and glass transition temperature between 208 and 286 °C. Also, the polymer films presented good mechanical characteristics with tensile strength in the range 60–91 MPa and storage modulus in the range 1700–2375 MPa. The macromolecular chain packing induced by dianhydride and diamine segments was investigated by examining gas permeation through the polymer films. The relationships between chain mobility and interchain distance and the obtained values for gas permeability are discussed. © 2014 Society of Chemical Industry  相似文献   

13.
Two novel bis(amine anhydride) monomers, N,N′-bis(3,4-dicarboxyphenyl)-1,4-phenylenediamine dianhydride I and N,N′-bis(3,4-dicarboxyphenyl)-1,3-phenylenediamine dianhydride II, were prepared via palladium-catalyzed amination reaction of 4-chloro-N-methylphthalimide with 1,4-phenylenediamine or 1,3-phenylenediamine, followed by alkaline hydrolysis of the intermediate bis(amine imide)s and subsequent dehydration of the resulting tetraacids. A series of new poly(amine imide)s were prepared from the synthesized dianhydride monomers with various diamines in NMP via conventional two-step method. FT-IR spectra of the poly(amine imide)s revealed that in the solid state, intermolecular and intramolecular hydrogen bonding (N-H?OC) are present. These polymers had glass transition temperatures in the range of 250-295 °C. The 10% weight loss temperature of the resulting poly(amine imide)s ranged from 539 to 560 °C in nitrogen. The poly(amine imide)s have the peel strength values ranging from 283 to 358 N/m. The poly(amine imide)s films were found to be transparent, flexible, and tough. The films had a tensile strength, elongation at break, and tensile modulus in the ranges 102-152 MPa, 11.3-19.6%, and 1.04-2.08 GPa, respectively.  相似文献   

14.
This article describes the synthesis and characterization of several methyl nadimides endcapped resins based on tris(3-aminophenyl)phosphine oxide. These resins were prepared by reacting methyl-5-norbornene 2,3-dicarboxylic anhydride (methyl nadic anhydride) (MNA), pyromellitic dianhydride (PMDA)/3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA)/2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6F), and tris(3-aminophenyl)phosphine oxide (TAP) in glacial acetic acid/acetone. Structural characterization of the resins was done by elemental analysis, IR, and 1H-NMR. Thermal characterization of uncured resins using DSC and TGA techniques revealed an exothermic transition accompanied by a weight loss in the temperature range of 200–350°C. Residual weight at 800°C in nitrogen was found to be 47–55%. Isothermal curing of the resins was done at 340°C for 1 h in an air atmosphere. The cured resins were stable up to 400 ± 20°C. © 1994 John Wiley & Sons, Inc.  相似文献   

15.
采用自制的叔丁基二胺单体1,4-双(4-氨基苯氧基)-2-叔丁基苯(BATB)与双酚A二酐(BPADA)反应,并以马来酸酐作为封端剂得到了一系列链中含酰亚胺环的内扩链双马来酰亚胺,将所得双马来酰亚胺混合双烯丙基双酚A(BBA)制得无胶型挠性覆铜板。采用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)、示差扫描量热法(DSC)和热重分析(TGA)对合成的封端聚酰亚胺树脂的结构进行了表征并测试了其性能,研究了BBA用量及加入前后对封端聚酰亚胺基膜力学性能、热性能、聚酰亚胺树脂固化性能的影响。结果表明,BBA与封端聚酰亚胺物质的量比为1∶1时,其增韧改性效果最佳。加入BBA后的薄膜在不降低热性能的情况下,力学性能提高(拉伸强度可达到67.14 MPa,弹性模量达到1 449.73 MPa,断裂伸长率最大达到6.17%)。所得两层型挠性覆铜板具有优异的耐热性、尺寸稳定性、低吸水率。  相似文献   

16.
A novel diimidodialcohol monomer, 1,4‐bis[2′‐trifluoromethyl‐4′‐(4″‐glycolformate)‐ trimellitimidophenoxy]benzene (BGTB), was synthesized and characterized. It was reacted with isophthalic acid, maleic anhydride and propylene glycol to produce a novel unsaturated poly(ester‐imide) (BGTB‐UPEI) with imide and trifluoromethyl groups in the polymer backbone. The BGTB‐UPEI resin was diluted with reactive monomer (styrene) to give a low‐viscous poly(ester‐imide)/styrene (BGTB‐UPEI/St) mixed solution, which was then thermally cured to yield thermosetting BGTB‐UPEI/St composite. The effect of processing parameters such as the curing temperature and curing time, reactive monomer concentration and initiator amount on the curing reaction was systematically investigated. Experimental results indicated that the thermally cured BGTB‐UPEI/St composite exhibited much better thermal, mechanical, electrical insulating properties and chemical resistance than the standard unsaturated polyester/polystyrene composite. Copyright © 2006 Society of Chemical Industry  相似文献   

17.
2,2′‐Position aryl‐substituted tetracarboxylic dianhydrides including 2,2′‐bis(biphenyl)‐4,4′,5,5′‐biphenyl tetracarboxylic dianhydride and 2,2′‐bis[4‐(naphthalen‐1‐yl)phenyl)]‐4,4′,5,5′‐biphenyl tetracarboxylic dianhydride were synthesized. A new series of aromatic polyimides (PIs) were synthesized via a two‐step procedure from 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride and the newly synthesized tetracarboxylic dianhydrides monomers reacting with 2,2′‐bis[4′‐(3″,4″,5″‐trifluorophenyl)phenyl]‐4,4′‐biphenyl diamine. The resulting polymers exhibited excellent organosolubility and thermal properties associated with Tg at 264 °C and high initial thermal decomposition temperatures (T5%) exceeding 500 °C in argon. Moreover, the fabricated sandwich structured memory devices of Al/PI‐a/ITO was determined to present a flash‐type memory behaviour, while Al/PI‐b/ITO and Al/PI‐c/ITO exhibited write‐once read‐many‐times memory capability with different threshold voltages. In addition, Al/polymer/ITO devices showed high stability under a constant stress or continuous read pulse voltage of ? 1.0 V. Copyright © 2011 Society of Chemical Industry  相似文献   

18.
Soluble copolysulfoneimides were synthesized by thermal two‐step method in solution of N‐methyl‐2‐pyrrolidone. The used aromatic diamines were bis[4‐(3‐aminophenoxy)phenyl]sulfone (BAPS‐m) and 3,3′‐diaminosulfone, and dianhydrides were pyromellitic dianhydride, 4,4′‐oxyphthalic anhydride, and 3,3′,4,4′‐diphenylsulfone tetracarboxylic dianhydride. The molar ratio of diamines was changed to reduce the content of BAPS‐m. The thermal and mechanical properties of polyimides were investigated. The polyimide ultrafiltration membrane with molecular weight cut‐off of 10 kDa could be successfully prepared by phase‐inversion method. Various solvent (water, alcohols, acetone, and hexane) fluxes were measured to investigate solvent‐resistance and membrane behavior during solvent permeation. The activation energy relationship between hexane flux and viscosity with temperature was also studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1024–1030, 2002  相似文献   

19.
Silicon‐containing polyimides were synthesized by solution polycondensation of bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride with 3,4‐oxydianiline and 4,4′‐oxydianiline, respectively. All the poly(amic acid) films could be obtained by solution‐casting from N,N‐dimethylacetamide solutions and thermally converted into transparent and tough polyimide films. The physical properties of thin films of those polyimides were compared by DSC, TGA, UV–visible spectroscopy, and dynamic mechanical analysis. The polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 3,4‐oxydianiline exhibited superior energy‐damping characteristic, mechanical properties, and optical transparency, whereas that from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 4,4′‐oxydianiline possessed higher glass‐transition temperature and thermal stability. Because of the unsymmetric structure of the polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 3,4‐oxydianiline, its increasing rate of linear coefficient of thermal expansion with temperature was quicker than that of the polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 4,4′‐oxydianiline. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2363–2367, 2004  相似文献   

20.
Soluble polyimides were synthesized and characterized from two diamines and four dianhydrides by the two- and the one-step method. Most of the polyimides could be soluble by one-step method except α,α′-bis(4-aminophenyl)-1,4-diisopropyl benzene/3,3′,4,4′-benzophenonetetracarboxylic dianhydride system in limited organic solvents. Glass transition temperatures ranged from 186 to 233°C and crystalline melt temperatures were not observed. All the soluble polyimides showed good thermal, mechanical, and electrical properties. The polyimides did not have crystalline structure and limited solubilities. The effective solvent had a medium dispersion component associated with weak polar and hydrogen components. The polymer from one-step polymerization had a narrower molecular weight distribution than the two-step method. Polyimide synthesized with 4,4′-oxydiphthalic anhydride and bis[4-(3-aminophenoxy)phenyl]sulfone by two-step method could only be prepared by the typical phase inversion method. Other membranes except this polyimide membrane could not be prepared by the typical phase-inversion method because of poor solubility about polar solvents. The flux of this ultrafiltration membrane was very high, and this membrane could especially retain polymer having a molecular weight 20,000 to above 90%. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 907–918, 1999  相似文献   

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