TW482764B - Preparation of soluble polyimides from various novel dianhydrides - Google Patents
Preparation of soluble polyimides from various novel dianhydrides Download PDFInfo
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482764 A7482764 A7
經濟部智慧財產局員工消費合作社印製 五、發明說明() 發明背景 聚醯亞胺具有優良機械性、尺寸安定性、耐熱性、耐 燃性及電氣絕緣性,所以聚醯亞胺被大量應用於電子及航 太工業,聚醯亞胺的兩耐熱性可充份滿足這些工業所需的 嚴格要求。但是大部份的聚醯亞胺不溶解且不融化,造成 加工困難,例如美國杜邦公司所生產的聚均笨内酸二酐亞 胺(Kapton)普遍應用於半導體工業的電子零件,但是這種 聚酿亞胺成形加工相當麻煩,若欲製成薄膜和金屬塗膜的時 候,需由聚醯亞胺的前趨體聚醯胺酸的溶液先形成薄膜,再 經過乾燥、脫水閉環製成聚醯亞胺膜。在成形品時,由於溶 劑的去除和閉環時生成的水難以去除,所以此方法不適用。 故需將它加熱到450 C左右進行熱壓或是將粉末加壓成形再 高溫燒結而成。 除了加工不易的問題外,電子工業也希望找到一種可溶 性又耐熱的聚醯亞胺,如果電子零件壞掉後可以將用來當封 裝材料的聚醯亞胺加以回收再利用,如此一來暨可降低成本又 可兼顧環保問題,然而現今使用最大量的K ap t ο η 並無法達成此目的,因此可溶性聚醯亞胺成為目前最重要 的工程塑膠之一。 為了提高聚醯亞胺的溶解性及加工性,有些專利揭示 了藉由分子鏈中導入柔軟的基團,例如醚基(-〇-) [ΕΡ 0565352 Α2, JP 05262705],直鏈烷基(-CH2-) [ΕΡ 0483954 Α1],石Jil基 (-S02-) [JP 05295262],丙烷基[-C(CH3)2_] [USP 4410684, JP04183721],及矽氧基(-Si-O) [ JP 052141000, JP 04189867 ] 4 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) '·---:---------裝-----*---訂---------線 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 482764 A7 ______B7 五、發明說明() 等柔軟的基團來降低它們分子鏈的堅硬度,提高聚醯亞胺 或聚醯胺的溶解性。另外在一些文獻(Stille et al·,Macromolecles, Vol· 14, ρ· 486(1981); Korshak et al·,J. Macromol. Sci., Rev. Macromol· Chem.,Vol. 11,p. 45-142 (1974))指出,導入環狀側鏈 基團(cardo)可有效增加聚合物溶解度,同時保有良好的熱安定 性。 本發明揭示了一系列具有非共平面之聯苯及多脂肪環 狀結構基團之新型二酸酐單體,其中這些非共平面之基團 及龐大的側鏈基團,可妨礙聚合物分子鏈緊密堆積及分子 間作用力,降低聚合物結晶度,進而提高聚合物溶解性,提高 加工性。同時龐大基團的導入也有助於提高聚合物熱安定性, 例如玻璃轉移溫度可被提高。 在 USP 3,517,071,USP 4,438,241 及 EP 0,391,303 等專利 中揭示了聚酯或聚碳酸酯中導入這類多脂肪環結構的側鏈 基團得到的聚合物,具有高耐熱性◊至目前為止並沒有專 利或文獻曾將這類多脂肪環基團導入聚醯亞胺分子鏈中, 所以本發明利用含多脂肪環基團二胺單體所術生的聚醯亞 胺為新型的可溶性及耐熱性聚醯亞胺。 發明總結Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () Background of the invention Polyimide has excellent mechanical properties, dimensional stability, heat resistance, flame resistance and electrical insulation, so polyimide is widely used in In the electronics and aerospace industries, the two heat resistances of polyimide can fully meet the stringent requirements required by these industries. However, most of polyimide does not dissolve and does not melt, which causes processing difficulties. For example, the poly (kapton) dianhydride imide (Kapton) produced by DuPont of the United States is widely used in electronic parts of the semiconductor industry. Polyimide is very troublesome in forming and processing. If you want to make thin films and metal coatings, you need to form a thin film from a solution of polyimide precursor, polyamic acid, and then dry and dehydrate the closed loop to make a poly.醯 imine film. This method is not suitable for the removal of solvents during molding and the water generated during the ring closure is difficult to remove. Therefore, it needs to be heated to about 450 C for hot pressing or powder compaction and high temperature sintering. In addition to the difficulty of processing, the electronics industry also hopes to find a soluble and heat-resistant polyimide. If the electronic parts are broken, the polyimide used as a packaging material can be recycled and reused. Reducing costs can also take into account environmental protection issues. However, the use of the largest amount of K ap t ο η can not achieve this purpose, so soluble polyimide has become one of the most important engineering plastics. In order to improve the solubility and processability of polyimide, some patents disclose the introduction of soft groups into the molecular chain, such as ether groups (-〇-) [EP 0565352 A2, JP 05262705], linear alkyl groups ( -CH2-) [EP 0483954 Α1], Jilyl (-S02-) [JP 05295262], propane [-C (CH3) 2_] [USP 4410684, JP04183721], and silane (-Si-O) [JP 052141000, JP 04189867] 4 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) '· ---: --------- install ----- *- --Order --------- line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 482764 A7 ______B7 V. Description of invention () and other soft groups To reduce the rigidity of their molecular chains and improve the solubility of polyimide or polyimide. In addition, in some literatures (Stille et al., Macromolecles, Vol. 14, ρ 486 (1981); Korshak et al., J. Macromol. Sci., Rev. Macromol. Chem., Vol. 11, p. 45- 142 (1974)) pointed out that the introduction of cyclic side chain groups (cardo) can effectively increase the solubility of polymers while maintaining good thermal stability. The present invention discloses a series of novel dianhydride monomers having non-coplanar biphenyl and polyalicyclic structure groups, wherein these non-coplanar groups and large side chain groups can hinder polymer molecular chains Tight packing and intermolecular forces reduce the crystallinity of the polymer, thereby improving the solubility of the polymer and improving the processability. At the same time, the introduction of large groups also helps to improve the thermal stability of the polymer, for example, the glass transition temperature can be increased. USP 3,517,071, USP 4,438,241 and EP 0,391,303 and other patents disclose that polymers obtained by introducing such a polyalicyclic structure side chain group into a polyester or polycarbonate have high heat resistance. Until now, there has been no polymer. The patent or literature has introduced such polyalicyclic groups into the polyfluorene imine molecular chain. Therefore, the polyfluorene imide produced by using a polyalicyclic group-containing diamine monomer in the present invention is a new type of solubility and heat resistance. Polyimide. Summary of invention
本發明揭示一系列具有優異溶解性、加工性、熱安定 性及機械強度的新型含非共平面基團及龐大側鏈基的聚醯 亞胺材料。這些材料是由新型的酸酐化合物與不同二胺化 合物聚縮合而得到Q 5 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) --^-------丨 — 裝·----*---訂---------線"^^1" f請先閱讀背面之注意事項再填寫本頁} 482764 A7 B7 五、發明説明() 以這些新型二酸化合物分別與不同的二胺單體進行聚 縮合反應,可以得到各種新型聚醯亞胺,這些聚合物具有 下式之通結構如下:The present invention discloses a series of new polyfluorene imide materials containing non-coplanar groups and bulky side chain groups with excellent solubility, processability, thermal stability and mechanical strength. These materials are obtained by the polycondensation of a new type of acid anhydride compound with different diamine compounds. Q 5 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-^ ------- 丨- Install · ---- * --- Order --------- line " ^^ 1 " f Please read the notes on the back before filling out this page} 482764 A7 B7 V. Description of the invention () These new diacid compounds are respectively subjected to polycondensation reaction with different diamine monomers to obtain various new polyfluorene imines. These polymers have the following general structure:
其中Ar代表: τ〇τ ? 5 ,? 5 , (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製Among them, Ar stands for: τ〇τ? 5,? 5 (Please read the notes on the back before filling this page) Printed by the Employees' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs
^_ 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) …‘/〇4 A7 B7 五、 發明説明() CH〇_ CF3發翁0^办〇修 Ch3 Cf3^ _ This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm)… ‘/ 〇4 A7 B7 V. Description of the invention () CH〇_ CF3 发 翁 0 ^ 办 〇 修 Ch3 Cf3
ο H3cN ch3ο H3cN ch3
-O-cHO^-o^ -Qr^^r^Qr h3c o -^-〇CH2CH2〇^h^-^-〇CH2CH2〇^- 或 鎚濟部智慧財產局員工消費合作社印製 O"〇CH2CH2CH^>^OCH2CH2(>0~ 0h3 。 發明詳細内容 本發明中的新型二酸酐化合物分別為:(A) 2,2L二甲基 •4,4’-雙[4-(3,4-二羧酸基苯氧基)聯苯二酸酐[2,2’-(1把1611以1-4,4\ bis[4-(3,4-dicarboxyphenoxy)]biphenyl dianhydride] ; (B)雙 [4-(4_(3,4-二羧酸基苯氧基)二苯亞甲基二酸酐[bis[4-(4-dicarbo xyphenoxy)phenyl]dipheny!methane dianhydride]; (C)3,3,,5,5,- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閱讀背面之注意事項再填寫本頁)-O-cHO ^ -o ^ -Qr ^^ r ^ Qr h3c o-^-〇CH2CH2〇 ^ h ^-^-〇CH2CH2〇 ^-or printed by O " 〇CH2CH2CH, a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. ^ > ^ OCH2CH2 (> 0 ~ 0h3. Detailed description of the invention The new dianhydride compounds in the present invention are: (A) 2,2L dimethyl • 4,4'-bis [4- (3,4- Dicarboxylic acid phenoxy) biphenylanhydride [2,2 '-(1 to 1611 to 1-4,4 \ bis [4- (3,4-dicarboxyphenoxy)] biphenyl dianhydride]; (B) bis [ 4- (4_ (3,4-dicarboxylic acid phenoxy) diphenylmethylene dianhydride [bis [4- (4-dicarbo xyphenoxy) phenyl] dipheny! Methane dianhydride]; (C) 3,3, , 5,5 ,-This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)
482764 A 7 ____B7_ 五、發明説明() 四曱基雙[4-(4-(3,4-苯三曱醯亞基笨氧基)苯基)丙 院二酸 Sf [3,3’,5,5’,tetramethyl,2,2-bis[4«(4,(3,4,dicarboxypheno xy)phenyl)propane dianhydride]; (D) 1,1-雙[4-(4-(3,4-二羧酸 基苯氧基)苯基>4-特-丁基環六烷酸酐[l,l-bis[4-(4-(3,4-dicarb oxyphenoxy)phenyl)»4_fe"-biitylcyclohexane dianhydride]等四 種。它們是由四種二紛化合物和4-nitrophthalonitrile合成四氰 化合物,再把四氰化合物以氫氧化鉀進行水解,製得四酸匕合 物’再經由醋酸酐閉環脫水轉變成具有醚基的四酸基雙酐,其 反應式如下: (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製482764 A 7 ____B7_ V. Description of the invention () Tetrafluorenylbis [4- (4- (3,4-benzenetrifluorenylideneoxy) phenyl) propanedioic acid Sf [3,3 ', 5 , 5 ', tetramethyl, 2,2-bis [4 «(4, (3,4, dicarboxypheno xy) phenyl) propane dianhydride]; (D) 1,1-bis [4- (4- (3,4- Dicarboxylic acid phenoxy) phenyl > 4-tert-butylcyclohexaane anhydride [l, l-bis [4- (4- (3,4-dicarb oxyphenoxy) phenyl) »4_fe " -biitylcyclohexane dianhydride ] And four. They are four tetracyano compounds synthesized from four dipentan compounds and 4-nitrophthalonitrile, and the tetracyano compound is hydrolyzed with potassium hydroxide to obtain a tetraacid compound. Tetraacid dianhydride with ether group, the reaction formula is as follows: (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs
_____ _______5_ 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X297公釐) 482764 A7 B7 五、發明説明() 其中R代表_____ _______5_ This paper size applies to Chinese National Standard (CNS) A4 specification (210 X297 mm) 482764 A7 B7 V. Description of invention () where R stands for
本發明中的聚醯亞胺是由各種二胺化合物與不同的二 酸酐化合物在適當的不含活性氫的極性溶劑如N,N-二甲基乙 醢胺(DMAc)或是間位-甲基齡(w_cresol)中進行聚加成反應形 成聚醯胺酸[poly(amicacid)]的前學物。然後再添加脫水劑進 行閉環反應得到聚醯亞胺。其化學反應如下列所示:The polyfluorene imine in the present invention is composed of various diamine compounds and different dianhydride compounds in a suitable polar solvent containing no active hydrogen such as N, N-dimethylacetamide (DMAc) or meta-formaldehyde. A polyaddition reaction is performed in the base age (w_cresol) to form a precursor of poly (amicacid). Then, a dehydrating agent is added for ring closure reaction to obtain polyfluorene imine. Its chemical reaction is shown below:
經濟部智慧財產局員工消費合作社印製 娜 i.i4 H20Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs i.i4 H20
A 準 標 家A standard bidder
ArAr
-V | one9"o η 經濟部智慧財產局員工消費合作社印製 482764 A7 ________B7 _ 五、發明説明() 這些聚醒亞胺的固有黏度(inherent viscosity)範圍為0.78〜0.93 dL/g ° 以下將詳細列出各種二酸酐單體及聚醯亞胺的實施例。 實施例一 合成2,2,-二甲基·4,4’_雙[4-(3,4-二羧酸基苯氧基)聯苯二酸酐 在一個100毫升的反應瓶中加入7.39克(34.5 mmol) of 2>二 甲基聯苯基-4,4’-二醇 and 12.2 克(70 mmol) of 4-nitrophthalonitrile, 1〇·1克(73 mmol)無水碳酸鉀及80毫升之除過水的DMF在室 溫度下攪拌2天。反應完畢倒入500亳升的水中,過濾,烘 乾並以乙月青做2次再結晶,得到四氰化合物。產率為83 % ;熔點為 227 —228 °C· IR (KBr): 2222 (C三 N) and 1240 cm·1 (C—〇)· ^-NMR (CDCls): δ (ppm)=7.80 (d? 2H); 7.37 (d5 4H); 7.29 (t5 2H); 7.05 (s,2H); 7·01 (d,2H); 2· 15 (s5 6H) 〇 取5.41克(11.6 mmol)的四氮化合物,12.9克(0·23 mol)的 KOH,加入反應器,並加入40亳升的水及40亳升的乙醇β在 迴流下攪拌2天,溶液由混濁變成澄清,冷卻過濾心’漆 液加入鹽酸使pH值達到3左右,會有白色固體析出,過遽 收集白色固體,並以純水清洗收次,所得的四酸化合物的產 率為92 %,此種四酸化合物在165 °C時會有昇華現象。瓜(0疗 2500-3600 (C(O)O-H), 1690 (C-0)5 and 1271 cm*1 (C-O-C). --—---Ιύ---- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁)-V | one9 " o η Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 482764 A7 ________B7 _ V. Description of the invention () The inherent viscosity of these polyimines ranges from 0.78 to 0.93 dL / g ° Examples of various dianhydride monomers and polyfluorene imines are listed in detail. Example 1 Synthesis of 2,2, -dimethyl · 4,4'_bis [4- (3,4-dicarboxylic acid phenoxy) biphenylenedihydride In a 100 ml reaction bottle, 7.39 g (34.5 mmol) of 2 > Dimethylbiphenyl-4,4'-diol and 12.2 g (70 mmol) of 4-nitrophthalonitrile, 10.1 g (73 mmol) of anhydrous potassium carbonate and 80 ml DMF over water was stirred at room temperature for 2 days. After completion of the reaction, it was poured into 500 liters of water, filtered, dried, and recrystallized twice with ethyl cyanide to obtain a tetracyanide compound. Yield: 83%; melting point: 227-228 ° C · IR (KBr): 2222 (C-N) and 1240 cm · 1 (C—〇) · ^ -NMR (CDCls): δ (ppm) = 7.80 ( d? 2H); 7.37 (d5 4H); 7.29 (t5 2H); 7.05 (s, 2H); 7.01 (d, 2H); 2.15 (s5 6H) 〇 Take 5.41 grams (11.6 mmol) of four Nitrogen compound, 12.9 g (0.23 mol) of KOH, was added to the reactor, and 40 liters of water and 40 liters of ethanol β were added and stirred under reflux for 2 days. The solution changed from turbid to clear, and the filter core was cooled. Adding hydrochloric acid to the solution to achieve a pH of about 3, a white solid will precipitate. The white solid will be collected and washed with pure water. The yield of the obtained tetraacid compound is 92%. At C, there will be sublimation. Melon (0 treatment 2500-3600 (C (O) OH), 1690 (C-0) 5 and 1271 cm * 1 (COC). ------ Ιύ) This paper size applies to Chinese national standards ( CNS) A4 size (210X297mm) (Please read the precautions on the back before filling this page)
經濟部智慧財產局員工消費合作社印製 482764 A7 B7 五、發明說明() MR (DMSO-^5): δ(ppm) = 7.79 (d5 2H); 7.15-6.98 (m, 10H); 2.02 (s, 6H). 取3.7克的四酸化合物及35毫升的醋酸酐在迴流下反應 1天,溶液由混濁變成澄清,趁熱過濾後,濾液會有晶狀 二酸酐化合物析出,過濾後,以除水過的甲苯清洗,並在 70 °C下真空乾燥1天,得到純的二酸酐化合物,產率為81 %, 熔點為 217—218 °C· IR(KBr): 1837, 1767(00),1254, 1226cm-1 (C-O). ^NMR (OMSO^d6): δ(ppm)=7.79 (d5 2H); 7.18-6.97 (m5 10H); 2·02 (s,6H)。 實施例二 合成雙[4-(4-(3,4-二羧酸基苯氧基)二苯亞甲基二酸酐 以二苯亞甲基二酚為起始物,重覆實施例一的步驟合 成含二苯亞甲基之四氰化合物,四酸化合物及二酸酐化合 物。所製得之四氰化合物之產率為78°/❶,熔點為:219-220 °C。 所製得之四酸化合物之產率為81 %,熔點為:17〇乞。所製 得之二酸酐化合物之產率為73 %,熔點為·· 263°C。 實施例三 合成3,3,,5,5,-四甲基雙【叫讲苯王甲班亞基苯氧基)苯基)丙貌二 酸酐 以3,3,5,5’-四曱基苯基丙烷二紛為起始物,重覆實施例一的步 成新型四氟化合物,四酸化合物及二酸針化合物。所 製得之四氰化合物之產率為80%,您點為:1%·1971。所製得 之四酸化合物之產率為79 %,嫁點為m。所製得之二 本紙張-__ ------------------Ί--^-------------^---^---------- (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 482764 A7 B7 V. Description of Invention () MR (DMSO- ^ 5): δ (ppm) = 7.79 (d5 2H); 7.15-6.98 (m, 10H); 2.02 (s , 6H). Take 3.7 g of the tetraacid compound and 35 ml of acetic anhydride under reflux for 1 day. The solution changes from turbid to clear. After hot filtration, the filtrate will precipitate a crystalline diacid anhydride compound. After filtration, remove It was washed with water and dried under vacuum at 70 ° C for 1 day to obtain a pure dianhydride compound with a yield of 81% and a melting point of 217-218 ° C. IR (KBr): 1837, 1767 (00), 1254, 1226 cm-1 (CO). ^ NMR (OMSO ^ d6): δ (ppm) = 7.79 (d5 2H); 7.18-6.97 (m5 10H); 2.02 (s, 6H). Example 2 Synthesis of bis [4- (4- (3,4-dicarboxylic acid phenoxy) diphenylmethylene diacid anhydride using diphenylmethylene diphenol as a starting material, The steps are to synthesize a tetracyanide compound, a tetraacid compound and a diacid anhydride compound containing diphenylmethylene. The yield of the obtained tetracyano compound is 78 ° / ❶, and the melting point is: 219-220 ° C. The yield of the tetraacid compound is 81%, and the melting point is 17 ° C. The yield of the prepared diacid anhydride compound is 73%, and the melting point is 263 ° C. Example 3 Synthesis 3, 3, 5, 5, 5, -tetramethylbis (called benzylbenzylphenoxy) phenyl) propanedioic anhydride starting with 3,3,5,5'-tetramethylphenylpropane The steps of Example 1 were repeated to form a new tetrafluoro compound, a tetraacid compound and a diacid needle compound. The yield of the obtained tetracyano compound is 80%. Your point is: 1% · 1971. The yield of the tetracarboxylic acid compound was 79%, and the graft point was m. Two papers produced -__ ------------------ Ί-^ ------------- ^ --- ^- --------- (Please read the notes on the back before filling this page)
—i n I J 482764 A7 五、發明說明() 酸酐化合物之產率為71 %,賴為:165 °C。 實施例四 合成1,1-雙【4-(4-(3,4·二羧酸基苯氧基)苯基)冬特-丁基環六烷酸酐 以丨,1-雙笨基_4_特-丁基環六烷二酚為起始物,重覆實 施例一的步驟合成新型四氟化合物,四酸化合物及二酸酐 化合物。所製得之四氰化合物之產率為74 %,熔點為:21〇 - 212 °C。所製得之四酸化合物之產率為70 %,熔點為:192。(: 0 所製得之二酸酐化合物之產率為75%,熔點為:165 °C。 實施例五 以2,2’-二甲基4,4’-雙【4*(3,4_二羧酸基苯氧基)聯苯二酸酐製備聚 殖胺醯亞胺 反應器中加入0.220克(0.11 mmol)的氧苯二胺,5毫升的 DMAc,等二胺化合物溶解後,慢慢加入2,2’-二甲基《4,4’-雙[4-(3,4-二羧酸基苯氧基)聯苯二酸酐(0.557 g克,0.11 mmol),在室溫下攪 拌2小時,溶劑會變得黏稠,將3毫升的DMAc及1毫升的口比 口定加入此種聚醯胺酸前驅物中進行閉環脫水,在室溫下攪拌1 小時,再於迴流下反應2小時,冷卻後,將聚醯亞胺溶液 倒入甲醇中沈殿,得到黃色沈殿物,以曱醇及熱水反覆清 12 ΐ紙張尺度適用中國國家鮮(CNS)A4規格(210 X 297公爱) ·:—:-------- (請先閱讀背面之注意事項再填寫本頁) 訂---------線丨一 經濟部智慧財產局員工消費合作社印製 -n n ϋ ϋ ϋ ϋ 1 ϋ ϋ ϋ ϋ βϋ · 482764 A7 ______B7_ 五、發明説明() 洗,並在120°C及真空下乾燥12小時。此聚合物的產率為96 %, 固有黏度為 〇·82 dL*g-1。ir : 1778, 1720 (imide 0=0) and 1372 cm-1 (C-N). 溶解性:此聚合物可溶於N-甲基-2-0比#酮(NMP), N,N-二甲基乙 醯胺(DMAc),N,N-二甲基甲醯胺(DMF),二甲亞石風(DMSO), 間位-甲基酚,r-丁内酿,四氫口夫口南及d比口定等溶劑。 熱性質:玻璃轉移溫度:278 °C; 在氮氣下裂解10%的溫度:512°C; 在空氣下裂解10%的溫度:489°C; 在氮氣下800°C時的殘餘量:60 %。 經濟部智慧財產局員工消費合作社印製 -紙 本 A4 \7 Ns 6 /|\ 準 標 家 一國 I國 中 I用 Μ I釐 29—I n I J 482764 A7 V. Description of the invention () The yield of the acid anhydride compound is 71%, and it depends on: 165 ° C. Example 4 Synthesis of 1,1-bis [4- (4- (4- (3,4 · dicarboxylic acid phenoxy) phenyl) dong-butylcyclohexaane anhydride with 1,1-bisbenzyl-4 Tert-butylcyclohexadiphenol was used as a starting material, and the steps of Example 1 were repeated to synthesize a novel tetrafluoro compound, a tetraacid compound, and a dianhydride compound. The yield of the prepared tetracyano compound is 74%, and the melting point is: 21 °-212 ° C. The yield of the tetra-acid compound was 70%, and the melting point was 192. (: 0 The yield of the diacid anhydride compound is 75%, and the melting point is: 165 ° C. Example 5 uses 2,2'-dimethyl 4,4'-bis [4 * (3,4_ Dicarboxylic acid phenoxy) biphenylenedihydride to prepare a chloramine imine reactor. Add 0.220 g (0.11 mmol) of oxyphenylenediamine, 5 ml of DMAc. After the diamine compound is dissolved, slowly add 2,2'-dimethyl [4,4'-bis [4- (3,4-dicarboxylic acid phenoxy) biphenylenedihydride (0.557 g, 0.11 mmol), stirred at room temperature for 2 Hours, the solvent will become viscous. Add 3 ml of DMAc and 1 ml of mouth to mouth to this polyamine precursor to perform closed-loop dehydration, stir at room temperature for 1 hour, and then react at reflux for 2 hours. After cooling, pour the polyimide solution into the Shen Dian of methanol to get the yellow Shen Dian thing, and repeat the cleaning with alcohol and hot water 12 ΐ The paper size is applicable to China National Fresh (CNS) A4 specification (210 X 297 public love) · : —: -------- (Please read the notes on the back before filling out this page) Order --------- line 丨 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-nn ϋ ϋ ϋ ϋ 1 ϋ ϋ ϋ ϋ βϋ · 482764 A7 ______B7_ V. Description of the invention () Wash and dry at 120 ° C under vacuum for 12 hours. The yield of this polymer is 96%, and the intrinsic viscosity is 0.82 dL * g-1. Ir: 1778, 1720 ( imide 0 = 0) and 1372 cm-1 (CN). Solubility: This polymer is soluble in N-methyl-2-0 than #ketone (NMP), N, N-dimethylacetamide (DMAc ), N, N-dimethylformamide (DMF), dimethylphosphine (DMSO), meta-methylphenol, r-butane, tetrahydrocarburide and d-bitone Solvents Thermal properties: Glass transition temperature: 278 ° C; Temperature of 10% cracking under nitrogen: 512 ° C; Temperature of 10% cracking under air: 489 ° C; Residual amount at 800 ° C under nitrogen: 60%. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-paper A4 \ 7 Ns 6 / | \
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