新型聚醚醯亞胺及聯苯型各種聚醯亞胺/二氧化矽混合材之合成與性質

SYNTHESIS AND PROPERTIES OF NOVEL POLY(ETHER IMIDE)S AND VARIOUS BIPHENYLENE STRUCTURE OF POLYIMIDE/SILICA HYBRIDS

溫秀忠(Shiou-Jung Wen)

指導教授 ： 楊金平

大同大學/工程學院/化學工程學系所/碩士(2005年)

摘要

第一部份中，一系列色淡透明、易溶性之新芳香族聚醚醯亞胺(PEI) 6系列是由1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride (3)與各種含trifluoromethyl基之芳香族二胺在N,N-dimethylacetamide (DMAc)中開環聚加成成polyamic acid (PAA)後再分別以化學(C)或熱烤(H)閉環法之二步驟合成。6a-i(C)之分子量由GPC測定其數量平均分子量( )在1.6-2.5×104，重量平均分子量( )在2.8-4.4×104及polydispersity index ( / )在1.6-1.8之間。在溶解性方面，6系列易溶於amide型極性溶劑如N-methy-2-pyrrolidone、DMAc、N,N-dimethylformamide，醚類溶劑如Dioxane、tetrahydrofuran及含氯溶劑如dichloromethane、chloroform等皆達10% w/v以上之可溶性。6系列薄膜經由UV-visible光譜之透光率及Colorimeter 之參數測得截止波長(λ0)在366.0-375.0 nm之間，b*參數值在5.0-9.0之間具色淡透明特性，並測得其有良好之機械性質，且多數具降伏點強度在84-109 MPa之間。熱性質經由DSC與TMA測得玻璃轉移溫度(Tg)在186-266 ℃與軟化溫度(Ts)在163-244 ℃之間，由TGA之分析在氮氣與空氣中10%重量損失皆在485 ℃以上，在氮氣中800 ℃之熱重殘餘率在47.5-64.5%之間。6系列具有低介電常數在3.05-3.46 (at 1MHz)，吸濕率範圍在0.18-0.65 wt%之間。6系列並與相應不含CF3之7系列比較，除具高可溶及低著色性外，6系列亦具有低介電常數與低吸濕率之特性。第二部份中，一系列含氟而色淡具良好熱性質之PEI 6’系列是由1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (3’)與各種含trifluoromethyl基之芳香族二胺經開環聚加成反應成PAA後，以化學或熱烤閉環法所合成。聚合物6’a-h(C)之分子量經GPC測定，其數量平均分子量( )在1.5-2.1×104，重量平均分子量( )在2.2-3.3×104及polydispersity index ( / )在1.5-1.7之間。在溶解性方面，6’系列於amide型極性溶劑及含氯溶劑等皆達10% w/v以上之可溶性。6’系列趨近無色PI且較相應不含氟之7’系列色淡及高光學透明，經由UV-visible光譜之透光率及Colorimeter之參數測得λ0介於373.0-384.5 nm，b*參數值在6.2-9.4之間。測得6’系薄膜之機械性質，其斷裂點抗張強度，斷裂點伸長率及起始模數在83-100 MPa，7.8-17.1 %及1.8-2.3 GPa之間。熱性質由DSC測得玻璃轉移溫度(Tg)在174-288 ℃，由TGA之分析10%重量損失溫度(T10)在氮氣及空氣中各為487-559 ℃與492-545 ℃以及在氮氣中800 ℃之熱重殘餘率在47.0-59.1 %之間。6’系列具有低介電常數在2.79-3.49 (at 1MHz)間，吸濕率範圍在0.19-0.33 wt%之間。第三部份中，以四種組成合成PI / SiO2 hybrids，並以BPDA / ODA為PI成份在DMAc中生成PAA後，加入Si(OCH3)4 / H2O進行sol-gel反應後鑄膜醯亞胺化生成。前三種hybrids(IV、V及VI)是使用APrTMOS為coupling agent：其中IV系是改變PI之鏈段長，V系是改變SiO2含量。並以IR、UV-vis、掃描式電子顯微鏡(SEM)、DSC、TGA及萬能拉力機等測定光學、熱性質與機械等物性之變化。結果發現使用APrTMOS為coupling agent之PI / SiO2(IV、V及VI)，SiO2含量達50wt%仍可維持奈米顆粒透明之PI / SiO2 hybrids，而不加coupling agent之VI’皆呈霧狀不透明之薄膜。當SiO2固定20wt%而改變PI鏈段長時，其PI / SiO2 films之抗張強度，起始膜數與伸長率皆隨PI鏈段之增長而急速增加至m=10後，緩和下來而且斷裂點伸長率亦以m=10者最大。V系列是固定PI鏈段m為10而改變SiO2含量，即發現隨SiO2含量自0~50%增加，其起始膜數自1.9增加至4.3GPa，但抗張強度與斷裂點伸長率皆有最高點在含SiO2 20wt%時升至147MPa及24.2%，然後下降。VI系列是以高分子量之PAA經添加少量之APrTMOS所合成之PI / SiO2試片，其膜數與抗張強度與抗張強度亦皆隨含SiO2量之增加而增加，且增加值在某範圍內都高於V系列。至於未使用coupling agent之blend型VI’系列，除薄膜不透明外，其餘機械性質與V及VI之變化類似。但熱性質之Tg即VI’低於VI許多。而所有PI/SiO2 hybrids該會因添加SiO2提高T10與Tg，但與SiO2含量之多少關係不大。

關鍵字

含氟二胺 ； 二醚二酐 ； 二氧化矽 ； 聚醚醯亞胺

並列摘要

First, a series of novel poly(ether imide)s 6 series characterized by colorless, high transparency and highly solubility were synthesized from 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride (3) and various fluorinated diamines (4a-i) via ring-opening polyaddition at room temperature to poly(amic acid) (PAA), followed by thermal (H) or chemical (C) imidization to obtain polymers. The GPC data of 6a-i(C) indicated that the and values were available in the range of 1.6×104-2.5×104 and 2.8×104-4.4×104, and the polydispersity index (PDI) values were 1.6-1.8. In solubility, 6 series showed excellent solubility in a variety of organic solvents and they were soluble in a concentration more than 10% in the amide polar solvent such as N-methyl-2-pyrrolidone, N,N -dimethylformamide and N,N-dimethylacetamide (DMAc), ether-type solvents such as dioxane and tetrahydofuran, and chlorinated solvents such as dichloromethane and chloroform. Moreover, the 6 series polymers showed a high optical transparency and were essentially colorless, with an ultraviolet-visible absorption edge 366.0 to 375.0 nm and low b* values (a yellowness index) of 5.0-9.0. These films showed strength tensiles of 79-104 MPa, elongations at break of 5.8-15.8%, initial moduli of 1.8-2.3 GPa, and most of them had strength at yield of 84-109 MPa. The thermal properties of glass transition (Tg) and softening temperature (Ts) were recorded by DSC and TMA at 186-266 ℃ and 163-244 ℃, and the decomposition temperatures at 10% weight loss are all above 485 ℃ in air or nitrogen atmosphere, respectively, and they left within a range of 47.5-64.5% char yield at 800 ℃ in nitrogen. The 6 series showed low-dielectric constants of 3.05-3.46 (at 1MHz), with moisture absorption in the range of 0.18-0.65wt % than the analogous nonfluorinated polyimides 7 series. Second, a series of fluorine-containing, light-colored and thermal stability PEI 6’ series were synthesized from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (3’) and various fluorinated diamines via ring-opening polyaddition to form PAA, followed by thermal or chemical imidization to obtain polymers. In this study, the GPC data of and values of 6’(C) series were available in the range of 1.5×104-2.1×104 and 2.2×104-3.3×104, and the polydispersity index ( / ) values were 1.5-1.7. The 6’ series showed excellent solubility in a variety of organic solvents and they were soluble in a concentration more than 10% w/v in the amide polar solvent and chlorinated solvent. Moreover, 6’ series showed a high optical transparency and less color intensity than the analogous nonfluorinated polyimides 7’ series, with an ultraviolet-visible absorption cutoff wavelengths between 373.0 to 384.5 nm, and low b* values (a yellowness index) ranging from 6.2 to 9.4. These films showed strength tensiles of 83-100 MPa, elongations at break of 7.8-17.1%, initial moduli of 1.8-2.3 GPa, and a part of them had strength at yield of 96-101 MPa. The thermal properties of glass transition (Tg) was recorded by DSC at 174-288 ℃, and the decomposition temperatures at 10% weight loss were analyzed by TGA in nitrogen and air atmosphere ranging of 487-559 ℃ and 492-545 ℃, respectively. They left 47.0-59.1% char yield at 800 ℃ in nitrogen, and 6’ series showed low-dielectric constants of 2.79-3.49 (at 1MHz), with moisture absorption in the range of 0.19-0.33 wt %. Third, Four series (IV, V, VI, and VI’) of polyimide-silica hybrid (PI/SiO2) were prepared by the sol-gel reaction and characterized in this study. The viscous poly(amic acid)s were synthesized from biphenyltetracarboximide (BPDA) and oxydiphenyldiamine (ODA), then the hybrid composite films were obtained by the hydrolysis and polycondensation of tetramethylorthosilicate (TMOS) and H2O in PAA solution following by spin coating and multistep heating. The former three series were prepared through 3-aminopropyltrimethoxysilane (APrTMOS) as coupling agent. The IV series was changes in chain length of PI segment; the V series was changes in the contents of silica. The optical, thermal and mechanical properties of the PI/SiO2 hybrids were investigated. The results showed that PI/SiO2 hybrids (IV, V and VI) with APrTMOS as coupling agent showed a high transparence and nanocomposite of PI/SiO2 hybrids even at high silica content of about 50wt%. However, the VI’ series without coupling agent revealed opaque thin films. As the content of SiO2 was 20wt%, we changed the PI segment length (the IV series), the tensile strength, initial moduli, and the elongation at break increased with the PI segment length increased. When chain length (m) was larger than 10, the tensile strength increased unobvious, but the elongation at break was the largest as m=10. The V series were fixed PI segment and changed the contents of SiO2. As the contents of SiO2 changed from 0 to 50%, the moduli of the V series increased from 1.9 to 4.3 GPa, though the tensile strength and the elongation at break had the largest value at the content of SiO2 20wt%. Moreover, the VI series synthesized from high molecular weight of PAA was found that the tensile strength and initial modulus also increased more obvious than V series as the content of SiO2 increased. Concerned for the VI’ series without coupling agent, the Tg values were also lower than VI series but their mechanical properties was similar to the V and VI series. In addition, all T10 and Tg values of PI/SiO2 hybrids could be raised causing the content of silica, though the relation between the values of T10 and Tg and the various SiO2-contentind is not clear.

並列關鍵字

diamine ； dianhydride ； fluorinated diamines ； poly(ether imide)s ； Silica

參考文獻

2. Adadie, M. J. M. and Sillion, B., Eds., Polyimides and other High-Temperature Polymers; Elsevier: Amsterdam, 1991.

3. Mittal, K. L., Ed., Polyimide: Synthesis, Characterization, and Application, Vol. I＆II; Plemnum: New York, 1984.

Black＆Son: Glasgow, 1990.

9. S. Ando, T. Sawada, and Y. Inoue, Electron. Lett., 29, 2143 (1993).

10. Hsiao, S. H.; Yang, C. P.; Lin, W. L., Macromol. Chem. Phys., 200, 1428