TW482764B - Preparation of soluble polyimides from various novel dianhydrides - Google Patents

Abstract

Described herein are novel soluble polyimides derived from new dianhydride containing noncoplanar conformation, bulky pendent groups. These polymers have excellent solubility combined with high thermal stability and good mechanical performance. These new polymers could be considered as processable high performance engineering plastics.

Description

482764 A7

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

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:

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

^ _ 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 ch3

-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_ 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_ 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

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:

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs i.i4 H20

A standard bidder

Ar

-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)

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 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 / | \

Claims (1)

A non-coplanar biphenyl dianhydride compound with the following structure: 2. A dibenzomethylene dianhydride compound with the following structure: 3. An isopropanyl dianhydride compound with the following structure: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4. A dianhydride compound with a large side chain group, the structure is as follows: 482764 8 8 8 8 ABCD patent application scope 5. A polyimide with the following structure: 0 • AI * 〆 Where Ar is selected from: ^ " 0 " -Q ^ rO-??,? ^ 〇-S〇2 ^ >-s h3c H3C0 H3, Cl : h3 H3C0 OChhbp ^ ^ < 〇 > < 〇) HO3SSO3H c \ c \ H3CCH3 CH, 6h3 cf3 h3c o ch3 o, send 0 ^ 0 ° · 〇Γ ° Ι 15 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 482764 A8 B8 C8 D8 6. Scope of patent application σ ^^) ~ OCH2CH2〇 ~ ^^^ 〒- ~ · ^) ~ 〇〇Η2〇Η2〇 ^^ ~ ^ > " 0CH2CH2CH ^^ Q ^ 0CH2CH2CH ^ Chh- ^ HDCH2CH2CH ^ (! > < ^ 〇CH2CH2CHQh 0h3 and the combination thereof, wherein R is selected from: ch3 HP HaC CHo CH3 S, ΛΑΗ3 (Please read the precautions on the back before filling out this page) ¾ Ethnic group line composed by the combination · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 16 This paper size applies to China National Standard (CNS) A4 (210 X 297) Mm)