TWI290153B - Noncoplanar diamine monomer containing fluorine, its derived polymer, and method for manufacturing the same - Google Patents

Abstract

The invention is related to noncoplanar monomer containing trifluoromethyl group. Aromatic diamine substituted with a trifluoromethyl group on either side was synthesized and used to prepare polyamide and polyimide by polycondensation. The synthesis and characterization of these polymers are also investigated and described. In addition, the effect of the fluorine-containing substitution to the aromatic condensation polymer is described.

Description

1290153 发明, invention description: [Technical field of invention] The present invention relates to a high performance material of polyamine and polyimine, in particular to a diamine monomer having a fluorine-containing non-coplanar structure and preparation thereof A method and a polymer of polyamine and polyimine derived therefrom. [Prior Art] Polyimine and polyamide are important engineering plastics today. They are widely used in various industries. These engineering plastics have good mechanical properties and thermal stability, so they are very Excellent performance. In terms of aromatic polyimine, it has excellent thermal stability, high mechanical strength, high tensile strength, high stretchability, good electrical and chemical properties, and is a kind of high performance resin, which is applied to aviation. In the automotive, precision machinery, optoelectronics industry, semiconductor industry and other high-level products; in recent years, due to the rapid development of liquid crystal display with the optoelectronic industry, (4) imine can also be applied to various film materials such as alignment film and compensation film of liquid crystal display. . However, the disadvantage of aromatic polyimine is that the processability is very poor, because their melting temperature is not condolence, and it cannot be processed by heating and melting, and its solubility is very poor, and it cannot be dissolved and used to process into &; Most of the polyimide resins have high glass transition temperatures (Tg), and their properties are better than traditional engineering plastics. The literature also reports that the copolymerization reaction can effectively change the structure of polyimine. A different functional group is introduced into a polymer backbone to obtain another polymer with better properties, thereby improving its processability. 0 1290153 In addition, in the case of aromatic polyamines, it has excellent heat resistance, It has the advantages of mechanical properties, chemical resistance, low friction coefficient and good electrical insulation. It is light in weight and has the potential to replace traditional metal parts. It is an eye-catching advanced high-performance polymer material, mostly used in electrical and electronic parts. , automotive parts, engineering plastic parts and general mechanical parts. However, until now, aromatic polyamines still have some problems that are difficult to process or difficult to prepare. In addition to being difficult to prepare, the solubility of aromatic polyamines is generally poor, although polyamines can also be used in solvents. It can be used directly after polymerization, such as the patent JP44, 19274, that is, the varnish type is used as a coating, but these varnishes need to use a highly polar solvent containing no active hydrogen such as pyridine and N-methyl-2-pyrrolidone (NMP). Or a solvent such as N,N-dimethylacetamide (DMAc). This varnish also has a problem of storage. Once exposed to air, it will become cloudy and suspected of gelation. Moreover, these active hydrogen-free catalysts are expensive, which limits the practicality of the varnish I industry. In order to solve the problem of solvent use, there have been some patents, such as the patents Jp5i23999, JP 5617374, JP 5622330 and JP 5634210, which use a solvent to replace the polar solvent of the aforementioned non-active hydrogen to make a varnish, but the effect is still limited. . Although aromatic polyamines and polyimines have very excellent properties, they have the disadvantage of very poor processability, that is, poor processing because of the high melting temperature and the inability to utilize hot melt processing. , and its solubility is very poor, it can not be dissolved by a solvent for processing. Therefore, in order to improve the processability of the engineering plastic and improve its application, the present invention introduces a fluorine-containing group and a non-coplanar structure to prepare a diamine monomer having a fluorine-containing 1290153 non-planar structure and prepared therefrom. Polyamide and polyaniline polymer. SUMMARY OF THE INVENTION The main object of the present invention is to provide a fluorine-containing non-coplanar structure, a diamine monomer, a material thereof, and a poly-axis and a poly-imine polymer derived therefrom. The I group and the non-coplanar structure are used to effectively improve the processability and solubility of the polyamine copolymer, so as to solve the disadvantages of the prior art that the preparation of the specific non-coplanar structure material is limited. Another object of the present invention is to provide a process and a low cost process for preparing a soluble and easily modified polyamine and polyimine using a fluorine-containing diamine monomer. A further object of the present invention is to provide a polymer for preparing a fluorine-containing polyamine and a polyimine having a non-coplanar structure, which is an excellent heat-resistant photoelectric material and has a lower dielectric layer. The electric constant and the high glass transition temperature (Tg) also have the advantages of high mechanical strength, high tensile strength and high transparency. The invention discloses a preparation method of a diamine monomer having a fluorine-containing non-coplanar structure, which comprises the following steps: First, 2,2,-dimethylbiphenyl-diol, 2-gas-5 -nitrotrifluorotoluene and potassium complexate are dissolved in a solvent of dimercaptocaramine (DMF) to form a reactant solution; the reactant solution is further heated to carry out a reaction; and the solution after the reaction is added to methanol The mixture is mixed with water (1 · 1 ), and the dihydrate monomer is filtered out; finally, the dinitrogen monomer is reacted with the hydrazine to obtain a di-monomer containing 1290153 amine monomer. The present invention discloses an embodiment of a trifluoromethyl-containing diamine monomer, the structure of which comprises the following compound of formula (I):

(I)

The present invention discloses another implementation of a trifluoromethyl-containing diamine monomer. The structure thereof includes the following formula (π) compound··

(Π) The present invention discloses a process for preparing polyamine from a diamine monomer having a fluorine-containing non-coplanar structure, which utilizes a diamine monomer containing trifluoromethyl group and two

The acid compound is reacted in the presence of calcium chloride, triphenyl phosphite (τρρ), pyridine and Ν-methyl-2-pyrrole_(ΝΜρ) to give a polyamine polymer. The present invention discloses a quinone iminodicarboxylic acid monomer having a fluorine-containing non-coplanar structure, the structure of which comprises a compound of the following formula (IC):

1290153 The present invention discloses a polyamine which is derived from a diamine monomer having a fluorine-containing non-coplanar structure, the structure of which comprises the following compound _

I

(1) (2)

(3) (〇4)

(5), and a group consisting of the same. The present invention discloses a method for preparing a polyimine from a diamine monomer having a fluorine-containing non-coplanar structure, which utilizes a triamine monomer containing a trifluoromethyl group. The reaction with the dianhydride compound in a solvent of N,N-dimethylacetamide (DMAc) is carried out by slowly adding a mixture of acetic anhydride and acridine to obtain a polyimine polymer. The present invention discloses a polyimine derived from a diamine monomer having a fluorine-containing non-coplanar structure, the structure of which comprises a compound of the following formula (jy): 9 1290153

a group consisting of; and the Ar' is selected from the group consisting of: 1290153

(11) (12)

(13)

(14)

11 1290153, and the group of its combination. Preferably, the Ar' is selected from the group consisting of:

(5) ‘ & (6), and the group of its combination. The present invention also discloses a polyamine copolymer having a structure comprising the following compound of formula (VI):

(VI) wherein the Ar is selected from the group consisting of the following compounds:

12 1290153 and the group consisting of the same The present invention also discloses a polyamidene copolymer having a structure comprising the following compound of formula (w):

CF, (W) wherein the At is selected from the following compounds:

(1) (2) (3) (4)

F3cx xcf; c

ο

ο

(5)

(6) (7) Ink q

(9)

(11)

F3C, CF:

Cr v v o (12) (10)

H3c .ch3

(13) (14) 13 1290153, and the group of its combination. The present invention further discloses a trifluoromethyl polymer-polyamide-醯亚月女'

ArM,-N-C

An effective amount of a compound of formula (V), wherein the Ar', is selected from

〇

BACKGROUND OF THE INVENTION The present invention is directed to the production of soluble Q by a polymerization % of polyamines and polyimines which are simple in process and low in cost and which are easily modified. The present invention discloses a diamine monomer compound containing difluoromethyl group, and utilizes the compound and a different diacid or monoanhydride compound to utilize a condensing agent, triphenyl sulfite (Tpp), N-methyl- 2_pyrrolidone (NMP), pyridine (Pyridine), N,N-dimethylacetamide (DMAc) are subjected to direct polycondensation reaction to obtain a series of polytrimethylene-containing polydecylamine and polyfluorene A polymer such as an amine. Firstly, it is necessary to synthesize a diamine-containing diamine monomer, wherein the diamine monomer can be polycondensed with a different diacid or dianhydride compound, so that the monomer can be produced separately. Properties of polyamines and polyimine materials. Before synthesizing the diamine monomer, the diphenol compound is reacted with p-chloronitrobenzene to form a dinitro compound (DBTFNPB), and then the dinitro group is reduced to a diamine monomer, wherein the DBTFAPB contains three gases. The methyl substituent can make the molecular chain non-coplanar, that is, reduce the force between the molecular chains, so that the molecular chain can not be closely packed, thereby lowering the crystallinity of the polymer, and then reducing the solubility of the polymer. Increasing, the melting point will also decrease, so the processability will be improved; in addition, the benzene ring group is a heat-resistant group, so the thermal properties of the polymer will be very good, and the high-performance and processability can be prepared from the diamine monomer. Good engineering plastic with high thermal stability. The introduction of a double-branched double bond in the polymer bond segment of the row bond reduces the interaction force in the polymer segment, thereby lowering the molecular force, thereby causing a significant decrease in crystallinity and an increase in solubility. In addition, it can be seen from the experimental records that P〇ly(eSter-imide)S containing 2,2,-dimethyl-4,4,_biphenylene segment will exhibit good heat resistance properties, also due to the same row of linked double benzene. The presence of an alkene can thus be achieved by introducing a non-coplanar structure or substituent. The diamine monomer is a fluorine-containing group with a non-coplanar 15 1290153 surface. Therefore, the heat resistance, mechanical properties and processability of the polyamine and polyimine synthesized are expected to be expected. of. Further, the introduction of the difluoromethyl group has the characteristics of good solubility, good thermal stability, low dielectric constant (which is a good insulator), and high transparency, making it useful in the photovoltaic industry. Because of &, it is possible to prepare an engineering plastic which is high in properties, good in workability, and high in thermal stability by a diamine monomer. The invention will be described in detail below with reference to specific embodiments, while the purpose of the invention, the technical contents and the features thereof are more readily understood. Example 1 Two-nitrate single-stranding of a double-branched group containing a difluoromethyl structure on a gold chain l^-dimethyl_4,4-bis (2-trifluoromethvl-4-nitr〇Dhennn)

Mphenvl ( DBTFNPB ^ will be 8.00 g of 2,2'-dimethylbiphenyl-4,4,diol (2,2'-dimethylbiphenyl-4,4, diol), 17.54 g of 2-chloro-5- 2-Chloro-5-nitrobenzotrifluoride, 15.20 g of potassium carbonate (K2C〇3) and 65 ml of N,N-dimethylformamide (DMF) solvent were added to the reaction flask. After 8 hours of reaction, the reaction was carried out for 8 hours. After cooling, water and methanol were mixed (volume ratio of m) in a precipitant to be filtered to obtain a pale yellow solid, which was recrystallized from glacial acetic acid to obtain a dinitrous crystal. The melting point is 236 ° C, the yield is 70 %. The infrared spectrum appears 1590 and 1333 (:11^^02), 1266 (:11^((^0-0 characteristic absorption peak. Hydrogen spectrum of nuclear magnetic resonance spectroscopy) Gh-nmr) (solvent CDC13) accounted for 16 1290153 (ppm) = 2.01 (6H), 7·03-7 〇 5 (2H), 7 〇 8 7 ι〇 ie), 7.23-7.27 (2H), 8.35- 8.37 (2H), 8.59-8.60 (2H) Hydrogen spectrum of nuclear magnetic resonance spectroscopy (i3c_nmr) (solvent is cDCid (ppm) 20.3, 117·4, n81, 119 2, u〇6, ·9, 129.1, 122.2, 124.1, 124.2, 125.8, 126 2 131.6, 138.6, 139.3, i42 〇 , i53 6, elemental analysis: theoretical value C: 56.77 %; Η: 3.06 %; Ν: 4·74%; and its analytical value is c: 56·42%; Η: 3 〇 9%; n: 4 55 % The reaction formula for this synthesis is as follows:

Example 2 Synthesis of a di-alkenyl group-containing diamine monomer having a trifluoromethyl structure on the chain 2<>2-dimethvl-4<t4-bis(2-trifluoromethyl-4-amin〇phenoxy) biphenyl (DBTFAPB ) Add 5.5 g of dinitrogen compound (DBTFNPB), 0.060 g of 10% activated carbon palladium (Pd/C) and 20 ml of ethanol to the reaction flask; warm to 130 17 1290153 c and slowly add 12 ml of the solution. Amine (h2NNH2 · H20). After the addition of the hydrazine, the reaction was carried out for 24 hours. After the completion of the reaction, the mixture was cooled to room temperature, and the solid was filtered. After drying, the activated carbon palladium (Pd/C) was removed by recrystallization from ethanol (C^HsOH) to obtain a white solid. Recrystallization once to obtain a diamine monomer; its melting point was 147. (:, infrared spectrum shows 3437, 3339 cm-i (NH), 1230 cm·1 (COC) characteristic absorption peak. Nuclear magnetic resonance spectroscopy analysis of hydrogen spectrum Chamr) (solvent is CDC13) 5 (ppm) = 2.03 (6H 6.78-6.82 (4H) > 6.88 (2H)^ 6.93-6.95 (2H), 6.98 (2H), 7·02 (2Η). Hydrogen spectrum of nuclear magnetic resonance spectroscopy (nc _NMR) (solvent is cdci 5) (ppm) = 20.01, 113.11, 113.15, 113.18, 113.22, 114.93 ^ 119.15, 122.78, 122.97, 130, 96, 135.95, 119.65 5 120.33 123.22,123 46 138.19 ^ 142.66 ^ ,122.50 , 122.72 , ,124.67,126.84 , 146.54 Alizarin analysis: theoretical value c: 6316%; H: 4 i6 %; n: 5.26%·' and its analytical value is C: 62 72%; H: 4 23%; n: 52i %. The reaction formula is as follows:

Diamine ethanol, activated carbon palladium 18 1290153

Example 3 Synthetic chain of di-methylene group containing trifluoromethyl structure is indeed a single Bisf4-(2-trifIuoromethy I~4-nitrophenoxy) phenvll diphenylmethane (BTFANPPM) will be 8·00 g of double [(4- Hydroxy)phenyl]diphenylmethane, n 4 gram of 2-chloro-5-nitrobenzotrifluoride, 13 g of K2C03 and 60 ml of DMF were added to the reaction flask. After heating to 180 ° C, the reaction was allowed to proceed for 8 hours. After cooling, water and methanol were added to the precipitant, and filtered to obtain a pale yellow solid. Recrystallization from glacial acetic acid gave a crystalline dinitrogen monomer. The dilute monomer measured a glare of 235-236 ° C and a yield of 70 %. Infrared spectra showed 159 〇 and 1333 cm 1 (N02), 1266 cm 1 (C-O-C) characteristic absorption peaks. Hydrogen NMR spectroscopy (OH-NMR) (solvent: CDC13): 5 (Ppm) = 7.00-7.04 (6H); 7.22-7.24 (6H); 7.27-7.29 (4H); 7.32-7.35 (4H); 8.28-8.31 (2H) ; 8·53-8·54(2Η). Hydrogen spectrum (C-NMR) of nuclear magnetic resonance spectroscopy (solvent is cdci3): 5 (Ppm) = 64.5, 117·48, 120.93, 12119 , 12134, 123.51, 124·15, 128.15' 129.07, 13113, 133 36, 142.05, 144.82, 146.24, 152·44, 161〇6 19 1290153 Elemental analysis: theoretical value C · · 64.11 % ; Η : 3.31 % ; N: 3.83%; and its analytical value is C: 64.25%; Η: 3.01%; Ν: 3.73%. The reaction formula for this synthesis is as follows:

Example 4 Synthesis of dibenzylidene diamine monomer Bisf4-(2"trifluoromethyl-4-aminophenoxy phenyl) diphenylmethane (BTFAPDM) containing a trifluoromethyl structure on a chain 5. 4 g of a dinitrogen compound (BTFNPDM) 0.054 g of 10% Pd/C and 40 ml of ethanol were added to the reaction flask, which was warmed to 130 ° C and slowly added dropwise to 10 ml of hydrazine (H2NNH2 · H20). After the addition of the hydrazine, the reaction was carried out for 24 hours. After the completion of the reaction, the mixture was cooled to room temperature, and the solid was filtered. After drying, the crystals were recrystallized from C2H5OH to remove Pd/C to obtain a white solid, which was recrystallized once to obtain a diamine monomer. The measured melting point was 1981, and the infrared spectrum showed 3410, 3332 and 1597 cm·1 (N-H), 1230 cm·1 (C-0-C) characteristic absorption peaks. The hydrogen spectrum of nuclear magnetic resonance spectroscopy is "CD- ΝΜΙΙΜ-ΝΜΙΙΜ solvent": 5 (ppm) 2 3.71 (4H); 6·73- 6·75 (2H); 6.82,6·84 (2H); ·87, 20 1290153 6.89 (2H); 6.93 (4H); 7.13-7.28 (14H). Hydrogen spectrum (13C-NMR) of nuclear magnetic resonance spectroscopy (solvent is CDC13): occupies (ppm) two 62.9, 112.95, 116.49 , 119.35, 121.97, 122.75 ' 123.10,124.69,127.60,131.11,132.35, 142.57 ' 146.0,146.93,159.35 . Elemental analysis: theoretical value C : 69.85 % ; Η : 4.21 % ; Ν : 4.18

〇/〇, and its analytical value is C: 69.14%; Η: 4.40%; Ν: 4.72%. The reaction formula of this synthesis is as follows...

Example 5 2,2'-Dimethyl-4,4'-bis(2-trifluoromethyl-4-aminomethyl oxime > di-diamine compound f 2,2'-dimethyl-4, 4'-bis (2-trifIuoromethyI-4-aminophenoxy) biphenvll (DBTFAPB) and 4,4'_sulfonvldiphthalic anhydride diacid fiber compound to prepare polyamidiamine 0.3565 g (〇.6695 mmol) of 2,2,-dimethyl -4,4,-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl diamine compound is dissolved in 3 ml of dimethylacetamide (DMAc) solvent. 21 1290153 4,4'-sulfonyldiphthalic anhydride dianhydride monomer, added to the feminine bath in February, "pay for about 2 hours", pay the viscous poly-glycolic acid (acid) solution; Imine (ρι ), the intrinsic viscosity of this polyimine in N,N-dimethylacetamide (DM Ac ) is 0·69 gdL·1 (solution concentration is 〇·5 g dL·1, measurement The temperature is 3 (rc). The infrared spectrum shows that the absorption peak of the enamine-based C=Ο characteristic is at 17 21 c ητΓ1 and 1777 cm 1 , and the cN characteristic absorption peak of the quinone imine group is at 1370 cm·1.

Elemental analysis · · Theoretical value C : 61.83 % ; Η : 2.83 % ; Ν : 3.28 %; and its analytical value is c: 61.00 %; Η: 2.46 %; Ν: 3.53 %. Solubility: This polyimine polymer is soluble in Ν-methyl·pyrrolidone (ΝΜΡ), hydrazine, Ν-dimethylacetamide (DMAc), hydrazine, hydrazine-dimethylformamide (DMF) ) _ methyl Asian satire (DMSO), 吼. Solvents such as Pyridine and tetrahydrofuran (THF).

Thermal properties: The glass transition temperature was 242. The temperature at which 〇% was cleaved under nitrogen was 462. (:; and the temperature of cracking 1% in air is 464. . Mechanical properties of the film: tensile strength of 89 Mpa; elongation of 5%; and tensile modulus of 2.3 Gpa. Dielectric constant (IKHz) : 2.85. The reaction formula for this synthesis is as follows:

1290153

Example 6 utilizes 2,2'-dimethyl-4,4,-螫α-'牟.A-4-amino group stupid base) di-diamine compound (DBTFAPB^ai 1.4-mosaic acid) jTerephthalic acid) 备 0.5324 g of 2,2,-dimethyl-4,4, bis(2-trifluoromethyl-4-amine basic oxy)-one amine compound and 0.1661 Teresic 1,4-phthalic acid (Teephthalic acid), and added 3 ml of Ν-methyl-2-° ratio ( (NMP), 0.75 ml of triphenyl phosphite (abbreviated as ΤΡΡ), 75·75 ml of pyridine and 0.35 g of CaCl 2 are subjected to a condensation reaction, and when it becomes viscous, it is necessary to further add appropriate N-methyl-2-pyrrolidone to complete the polymerization. Then, it is cooled again, and after cooling, water and methanol are mixed (volume ratio is 1/1). The polymer is precipitated in a precipitating agent, and then washed with hot water to dry to obtain polyamine. The polyamine is in N, N. The intrinsic viscosity in 曱-decyl acetamide (DMAc) is 〇77gdL-i (solution concentration is 〇.5 g dL 1, measurement temperature is 3〇〇c) Solubility··This polyamide polymer is soluble N-methyl-2·pyrrole with 23 1290153 (NMP ), hydrazine, hydrazine dimethylacetamide (DMAc), n,N-dimethylformamide (DMF), dimethyl sulfoxide In solvents such as (DMSO), hexahexanone, and pyridine. Thermal properties: glass transition temperature was 241 °C; pyrolysis at air was 1% at 474 °C; and 10% at nitrogen was 479 °C. Mechanical properties of the film: tensile strength of 81 Mpa; elongation of 3%; and tensile modulus of 3.3 GPa. Dielectric constant (ΙΚΗζ): 3.20. The reaction formula for this preparation is as follows:

Using 2,2,-dimethyl-4.4,-Ting (2-trifluoromethyl-4.amine-based bis-diamine compound (DBTFAPB) and 1,3-phthalic acid (Isophthalic acid) 0.52 g (1 mmol) of 2,2'-dimethyl-4,4'-bis(2,trifluoromethyl-4-aminophenoxy)diphenyl Amine compound with 166·1661 g (1 mmol) of 1,3-phthalic acid, and adding 3 ml of N-methyl-2, pyrrolidone (NMP), 0.75 ml of triphenyl phosphite (Iphenyl) Phosphide (TPP), 0.75 ml of pyridine and 〇35 g of CaCh for 1290153 condensation reaction. When it becomes viscous, it is necessary to add appropriate N-methyl to each ketone (ΝΜΡ) to complete the polymerization. After cooling, add water and methanol (volume ratio of 1/1) to precipitate the polymer in the sinking agent, then wash it with hot water and dry to obtain polyamide. Solubility: The polyamide polymer can be Soluble in methyl·2_ σ pyrrolidone (ΝΜΡ), Ν, Ν-dimethylacetamide (DMAc), hydrazine, Ν-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) Solvents such as cyclohexanone and pyridine. · Glass transition temperature is 230 ° C; 10 % cracking under air is 460 ° C; and cracking 1 % by temperature under nitrogen is 482 ° C. Mechanical properties of the film: tensile strength is 72 MPa; elongation It is 7%; and the tensile modulus is 2.9 GPa. Dielectric constant (ΙΚΗζ): 3.33 The reaction formula of this preparation is as follows:

Example 8_J^2,2'-dimethyl-4.4'-indole (2-trifluoromethyl-4-amino stupyl) diphenyl diamine compound (DBTFAPB) and 5-tert- Butvlisophthalic 25 1290153 gcid 2,2'-dimethyl-4,4,-bis(2-difluoromethyl-4-aminophenoxy) having 0.5324 g (1 mmol) of polyamine Diphenyl diamine compound with 0 2222 g (1 mmol) of 5-tert-butylisophthalic acid, and 3 ml of N-methyl-2-pyrrolidone (NMP), 0.7 ml of triphenyl vinegar (0.7 ml) TPP), 0.6 ml of pyridine and 〇35 g of CaCl2 are subjected to a condensation reaction. When the viscosity is changed, the appropriate N-methyl-2-σ ratio (NMP) must be added to complete the polymerization. Then, it is cooled again, and after cooling, water and methanol are mixed (volume ratio of 1/1) to precipitate a polymer, which is then washed with hot water and dried to obtain a polyamine. Solubility··This polyamide polymer is soluble in Ν-methyl-2-pyrrolidone (ΝΜΡ), Ν, Ν-dimethylacetamide (DMAc), hydrazine, Ν-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexahexanone and acridine. Thermal properties: glass transition temperature of 236 ° C; pyrolysis of 1 〇 % of air at 442 ° C; and lysis of 10 % of nitrogen at 486 ° C under nitrogen. Mechanical properties of the film: tensile strength of 74 MPa; elongation of 6%; and tensile modulus of 2.2 GPa. Dielectric constant (ΙΚΗζ): 3.22. The reaction formula for this preparation is as follows: 26 1290153

Example 9 utilizes 2,2'-dimethyl-4,4,-bis(2-trifluoromethyl-4- benzoquinone, diammonium diamine compound (DBTFAPB) 舆2,6-Naphthalenedicarboxvlic Acid 2,2'-dimercapto-4,4,-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl, 0.5324 g (1 mmol) Diamine compound with 0.2162 g (1 mmol) of 2,6-NaphthalenedicarboxyliCacid, and added 3 ml of N-methyl-2-pyrrolidone (NMP), 0.7 ml of triphenyl phosphite (ΤΡΡ), 0.77 ml Pyridine and hydrazine · 35 grams of CaCl 2 for condensation reaction, when changing to the viscosity must be added to the appropriate N-methyl-2-pyrrolidone (NMP) to complete the polymerization. Then cooled, cooled, added water and methanol Mixing (volume ratio of 1/1) Precipitant to precipitate the polymer, then washing with hot water, drying to obtain polyamide. Solubility: This polyamide polymer is soluble in N-mercapto-2 - piroxime (NMP), N,N-dimethylacetamide (DMAc), N,N-dimercaptocarboxamide (DMF), dimethyl sulfoxide (DMSO), hexahexanone and Solvent such as pyridine. Thermal properties: glass transition temperature 286 t ; cracking under air 10 〇 / 〇 27 1290153 temperature is 460 ° C; and nitriding under nitrogen is 482 ° C. Film mechanical properties: tensile strength 103 MPa; elongation 7 % ; and the tensile modulus is 2.9 GPa. Dielectric constant (ΙΚΗζ): 3.75. The reaction formula of this preparation is as follows:

Example ten

Grade J 2,2,_Dimethyl _4-4,-bis(2-trifluoromethyl_4-amine oxime benzene D-diphenyl compound fDBTFAPB) 舆14'-Biphenyldicarboxvlic acid Μ The amine is 0.5324 g (mole) of 2,2,-dimethyl-4,4,-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl diamine compound with 0.2422 g (1 耄 Mo ear) of 4,4'-Biphenyldicarboxylic acid, and added 3 ml of N-methyl-2-pyrrolidone (NMP), 0.7 ml of triphenyl phosphite (TPP), 0.7 ml of pyridine and hydrazine 35 grams of CaCl2 is subjected to a condensation reaction; when it becomes viscous, it is necessary to add an appropriate N-methyl-2-pyrrolidone (NMP) to complete the polymerization. Then, it was cooled again, and after cooling, water and methanol were mixed (volume ratio of 1/1) to precipitate the polymer, and then washed with hot water to remove 28 129 153 to obtain polydecylamine. Solubility; the polyamide polymer is soluble in methylpyrrolidone (NMP), N,N-dimethylacetamide (dmAc), N,N-dimethylformamide (DMF), Solvents such as dimethyl sulfoxide (DMSO), cyclohexanone, and pyridine. Thermal properties·· The glass transition temperature was 241 ° C; the temperature of cracking 1 〇 % under air was 457 ° C; and the temperature of cracking 10 % under nitrogen was 466 ° C. Mechanical properties of the film: tensile strength of 85 MPa; elongation of 6%; and tensile modulus of 2.9 GPa. Dielectric constant (ΙΚΗζ): 3.52. The reaction formula for this preparation is as follows:

Example 11 using 2,2'-dimethyl-4,4,-bis(2-trifluoromethyl-4-amine oxime) a stupid diamine compound (DBTFAPB) and 4,4 '-Sulfonyldibenoic acid to prepare polyacrylamide to take 0.5324 g (1 mmol) of 2,2'-dimethyl-4,4,-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl Diamine compound with 0.3062 g (1 mmol) of 4,4'-Sulfonyldibenoic acid, and add 4 ml of 29 1290153 N-methyl-2-furanosone (NMP), 〇·7 亚 sub-scale Triphenyl ester (ΤΡΡ), 〇7 ml of pyridine and 〇35 g of condensation reaction; when the viscosity is changed, it is necessary to add an appropriate N-methyl 嘻gig (NMP) to complete the polymerization. Then, it is cooled again, and after cooling, water and methanol are mixed (volume ratio of 1/1) to precipitate a polymer, which is then washed with hot water and dried to obtain polyamine. Solubility··This polyamine polymer is soluble in N_mercapto-2_ σ pyrrolidone (ΝΜΡ), Ν, Ν-dimercaptoacetamide (dmAc), Ν, Ν-dimethyl hydrazine Sol (DMF), dimethyl ferrous (DMSO), hexahexanone and 吼η 定. Thermal properties: glass transition temperature was 255 t; cracking at 10 〇/〇 under air was 453 ° C; and cracking at 10% under nitrogen was 465 °. Hey. Mechanical properties of the film: tensile strength of 96 MPa; elongation of 7 %; tensile modulus of 2.7 GPa. Dielectric constant (ΙΚΗζ): 3.07. The preparation reaction is as follows:

Example 12 jLS-j^2'-dimethyl-4,4'-bis(2-trifluoromethyl-4-amine A joxy) 30 1290153 Dimosa diamine compound (DBTFAPB) and 2 , 2_BisM-carboxvDhenvlVhexafluoropropane Preparation of polyacrylamide 0.5324 g (1 mmol) of 2,2, dimethyl-4,4'-bis(2-difluoromethyl-4-aminophenoxy)diphenyl The diamine compound is mixed with 0.3922 g (1 mmol) of 2,2_Bis(4_carboxyphenyl)-hexafluoropropane, and 3 ml of N-methyl-2-indolone (NMP), 0.6 ml of triphenyl phosphite ( TPP), 0.6 ml of pyridine and 0.30 g of CaCl 2 were subjected to a condensation reaction; when it became viscous, it was necessary to add an appropriate N-methyl-2-pyrrolidone (NMP) to complete the polymerization. Then, it is cooled again, and after cooling, water and methanol are mixed (volume ratio is 1/1) to precipitate the polymer, and then washed with hot water, and dried to obtain polystyrene. 0 Solubility: Polyamide polymerization Soluble in N-methyl-2-pyrone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl Solvents such as sulfone (DMSO), cyclohexanone, and pyridine. Thermal properties: glass transition temperature is 264 ° C; cracking 10% under air is 456. (:; and the temperature of cracking 1% by weight under nitrogen is 488 ° C. Mechanical properties of the film: tensile strength of 89 MPa; elongation of 7%; and tensile modulus of 2·8 GPa. ΙΚΗζ) : 2.86. The reaction formula for this preparation is as follows: 31 1290153

FsC Ο

HOOC

COOH

CICIC

-N--Η VC- Example 13 utilizes 2,2'-dimethyl-4,4'-bis(2-trifluoromethyl-4-aminophenoxy)di-diamine compound ( DBTFAPB) and Bis丨4_(2_ trifluoromethyl-4-aminophenoxy) phenyl! diphenylmethane with 2,2-Bis (4-carboxyphenvn-hexafluoropropane prepared by copolymerization of polyamidamine, 0.5324 g (1 mmol) of 2,2'- Dimethyl-4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl diamine compound and 0.6707 g (1 mmol) Bis[4-(2-trifluoromethyl-) 4-aminophenoxy) phenyl] diphenylmethane (BTFAPDM) with 0.7844 g (1 mmol) of 2,2-Bis(4-carboxyphenyl)-hexafluoropropane ' and 6 ml of N-methyl-2-pyrrolidone (NMP) ), 1.2 ml of triphenyl phosphite (TPP), 1.2 ml of pyridine and 0.6 g of CaCl 2 for condensation reaction; when changing the viscosity, it is necessary to add appropriate N-methyl-2-nonanone (NMP) The polymerization reaction is complete. Then, it is cooled again. After cooling, water and methanol are mixed (volume ratio of 1/1) to precipitate the polymer, which is then washed with hot 32 1290153 water and dried to obtain copolymerization. Polyamide. Solubility: This copolymerized polyamine is soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethyl Solvents such as methotrexate (DMF), dimethyl sulfoxide (DMSO), hexahexanone, and pyridine. The reaction formula of this preparation is as follows: η2ν·

H2N

<〇>-^P>-nh2 f3c >

+ 2 HOC

N-mercapto-2 "pyrrolidone 0 than bite _ triphenyl phosphite reflux reaction for 3 hours

Example 14 utilizes 2,2'-dimethyl-4·4,-bis(2-trifluoromethyl-4-amine-stupyl)diphenyldiamine compound (DBTFAPB) and Bis丨4- (2-trifluoromethyl~4-_aminophenoxy)_phenyll diphenylmethane (BTFAPDM)舆4,4'-hexafluoro isopropylidenedi -nhathalic anhydride (6FDA) Preparation of copolymerized polyiminide taken at 0.5 324 g (1 mmol) 2,2 Dimethyl-4,4'-bis(2-trifluorodecyl-4-aminophenoxy)diphenyl diamine compound and 0.6707 g (1 mmol) bis[4-(2-trifluoro) Methyl-4-aminophenoxy)phenyl]diphenylmethane with 0.888 g (2 mmol) of dianhydride monomer 33 1290153 4,4'-hexafluoroisopropyli-denediphathalic anhydride dissolved in 5 ml of dimercapto In acetamide (DM Ac ) solvent. Stirring for about 2 hours gave a viscous polyamic acid solution. Polyimine (PI) can be obtained by cyclization dehydration. The reaction formula for this preparation is as follows:

Example 15 Synthesis of diammonium amino-dicarboxylic acid monomer having a trifluoromethyl structure on the synthetic chain 2,2'-dimethvl-4.4'-bis(2-trifluoromethvl-4-trimellitimido phenoxv) biphenyl (DBTFTPB) 1.5 g of 2, 2'-dimethyl-4,4'-bis(2-trifluoromethyl-4-aminophenoxy)diphenyl 2,2'-(1丨11161:1^b 4,4'-1^3 (2-trifluoromethyl-4-aminophenoxy) biphenyl (DBTFAPB), 1 · 4 g of trimellitic anhydride (TMA) 34 1290153 and 20 ml of glacial acetic acid were added to the reaction flask. Heated to 130 ° After C, the reaction was carried out for 10 hours, and after cooling, it was added to a methanol precipitating agent, and the obtained solid was filtered, and recrystallized by mixing N,N-dimethylformamide (DMF) with water (volume ratio of 4:1) to obtain two. Carboxylic acid monomer (DBTFTPB), melting point is 236 ° C, yield 70 %. Infrared spectrum appears 2500-3500 (: 11 ^ (-011), 1715, 1773 cm -1 (C = 0) characteristic absorption peak Elemental analysis: Theoretical value: C: 62.73 %; H: 2.98 %; N: 3.18 %; Analytical value: C: 62.27 %; Η: 2.79 %; Ν: 3·28 %· The reaction formula is as follows:

Cooh glacial acetic acid reflux

Example 16 utilizes 2,2'-dimethyl-4,4'-bis(2-trifluoromethyl-4-stuptentyloxy)di-dimethylenediamine-dicarboxylic acid Compound 2,2"-dimethvl-4,4'-bis(2-trifluoromethvl-4-trimellitimido phenoxy) biphenyl (DBTFTPB) and diamines were prepared to prepare a novel polyamine-imine in a two-neck bottle of 7.5 milligrams. Mohr diamine, 7.5 mmoles of bis-indenyl-dicarboxylic acid monomer (DBTFTPB), 4 ml of N-methyl-2-pyrrolidinine (NMP), 1 ml of yttrium 3}^^!^), 1 35 1290153 ml of triphenyl phosphite (TPP) and 0.35 g of calcium chloride (CaCh), and refluxed at 130 ° C for 3 hours. The polyamine-niobium solution was poured into a large amount of methanol to kill. The polymer was washed alternately with hot water and methanol, and dried under vacuum at 100 ° C. Elemental analysis: Theoretical value: C: 65.26 %; H: 3.65 %; N: 4.23 % . Analytical value: C: 65.62 %; H: 3.74 %; N: 4.07 % · Solubility: This polymer is soluble in N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF) Solvents such as dimethoprim (DMSO), pyridine and tetrahydrofuran (THF). Thermal properties: glass transition temperature is 250 ° C; pyrolysis under nitrogen is 1% by temperature at 500 ° C; The temperature at 10% cracking under air is 459 ° C. Mechanical properties of the film: tensile strength of 112 Mpa; elongation of 9 ° / 〇; and tensile modulus of 2.5 Gpa. Dielectric constant (ΙΚΗζ): 3.59 This synthesis The reaction formula is as follows:

N-mercapto-2-pyridinone oxime ratio ^____

Sub-acid triphenyl vinegar reflux reaction for 3 hours 36 1290153

The present invention provides a diamine monomer having a fluorine-containing non-coplanar structure and a gas preparation method, and a polymer such as polyamine and 2 imine derived from the preparation of a diamine monomer, which is attached to a polymer. The middle lead contains fluorine groups and non-structures to effectively improve the processing and dissolution of polyamines and polyimines.

The solution is therefore effective in solving the disadvantages of the prior art that only 35 restrictively prepares a particular non-coplanar structural material. It is to be understood that the technical idea of the present invention and the specific purpose thereof are to enable those skilled in the art to understand the contents of the present invention and to implement the present invention. That is, the equal change or modification made by the sophomore in accordance with the spirit of the present invention should still be within the scope of the patent of the present invention.

37

Claims (1)

1290153 Pickup, Patent Application Range: A method for preparing a trifluoromethyl-containing sulfhydryl-mono-fluoric acid monomer having a fluorine-containing non-coplanar structure, which comprises the following steps: 2, 2'- Dimethylbiphenyl_4,4, diol, 2-chloro- 5 nitrobenzotrifluoride and potassium carbonate are dissolved in a solvent of N,N-dimethylformamide (DMF) to form a reaction a solution; heating the reactant solution to carry out a reaction; adding the solution after the reaction to a precipitant mixed with methanol and water to form a solid nitrate monomer, and removing the dinitrogen monomer; The monoterpene monomer is reacted with a hydrazine to obtain a trifluoromethylamine-containing amine monomer; ^ the trifluoromethyl-containing diamine monomer and trimellitic anhydride (TMA) are dissolved In the solvent of glacial acetic acid, 1...the reactant solution; heating the reactant solution to carry out the reaction; and adding the solution after the reaction to the methanol precipitating agent to obtain one of the human fluoromethyl melamine A base-dicarboxylic acid monomer, which comprises ^ _ / CH3 f3c p - er loan. Good you c_ 0 cf3 ί (IC) An effective amount of the compound of formula (1C). 2. A method for preparing a diamine monomer having a fluorine-containing non-coplanar structure, the system 38 1290153 comprising the following steps: bis[(4-hydroxy)phenyl]diphenylmethane, 2-chloro- 5-nitrobenzotrifluoride and potassium carbonate are dissolved in a solvent of N,N-dimethylformamide (DMF) to form a reactant solution; heating the reactant solution to carry out a reaction; The solution is added to a precipitant mixed with methanol and water to form a solid dinitrogen monomer, and the dinitrogen monomer is removed by filtration; and the dinitrogen monomer is reacted with a hydrazine to obtain a trifluoromethyl group. A diamine monomer. 3. The method for preparing a diamine monomer according to claim 2, wherein the trifluoromethyl-containing diamine single system comprises: NH2 An effective amount of a compound of the formula (Π). 4. The method for producing a diamine monomer according to claim 2, wherein the ratio of the sterol to water is 1:1. 5 · A fluorinated non-coplanar structure of quinone imine dicarboxylic acid monomer, the structure of which is: 9 ch3 f3c λ R^x^COOH 39 1290153 6 · — A dinitrogen monomer with a fluorine-containing twist structure, the structure of which: 7 · A diamine monomer with a fluorine-containing twist structure, the structure is: 8. A method for preparing polyamine from a diamine monomer having a fluorine-containing non-coplanar structure, which utilizes a diamine monomer containing a trifluoromethyl group and a diacid compound in calcium chloride, triphenyl phosphite The reaction is carried out in the presence of an ester (TPP), pyridine and N-methyl-2.pyrrolidone (NMP) to obtain a polyamine polymer, wherein the polyamine polymer comprises: (ΠΙ) an effective amount of a compound of the formula (ΠΤ), wherein the Ar is selected from the group consisting of 40 1290153 The group of people formed. (1) (2) 9 - A method for preparing a polyimine from a diamine monomer having a trifluoromethyl group, which utilizes a triamine-containing diamine monomer and a dianhydride compound in N, N- In a solvent of dimethylacetamide (DMAc), a mixture of acetic anhydride and pyridine is slowly added to carry out a reaction to obtain a polyimine polymer, wherein the polyimine polymer system comprises: An effective amount of a compound of formula (IV), wherein the Ar" is selected from the group consisting of a group consisting of; and the Ar' is selected from the following compounds·· 1290153 The group of people formed. 10. A process for preparing polyamidoquinone imines from a diammonium-dicarboxylic acid monomer having a trifluoromethyl group, which utilizes a diindolyl-dicarboxylic acid containing a trifluoromethyl group The monomer and the diamine compound are added to the solvent of N-methyl-2-pyridone, and then the σ ratio is determined by adding σ, and the anti-42 1290153 is reacted in the presence of the phthalic acid triphenyl vinegar to obtain a polydecylamine. a quinone imine polymer, wherein the polyamidoximine polymer system comprises: (V) an effective amount of a compound of formula (V) wherein the Ar"' is selected from the group consisting of: CH. 11 · A trifluoromethyl-containing polyamine, the structure of which is: 43 1290153 3 3 F _ F cIC-丨C The group of people formed. (1) (2) 12 · A trifluoromethyl-containing polyimine, its structure O- Ar — ο ft Ο 0 II II /CWC\ \c, II IIο ο Ν- , where the Ar" is selected from CH3 a population consisting of h3c and combinations thereof; and the Ar' is selected from the group consisting of 44 1290153 , and the group of its combination. 13 · A trifluoromethyl-containing polyamine-quinone imine, the structure of which is: -Ar"' Η Ο I II -N-C Where 45 (V) 1290153 the Ar’’' is selected from 14 · A polyamine copolymer having a trifluoromethyl non-coplanar structure, the structure of which is: U 〇au CHa F^C tj ο γϊ μ ^ V Ρ ^ >ρς\ I II II I NC—Αγ-〇N-^Q)~ 〇\〇/—(〇/~ 〇\〇/一 NC— Ar-CN-- cf3 h3c , wherein the Ar is selected from 46 1290153 , and the group of its combination. 15 · A polyamine copolymer with a trifluoromethyl non-coplanar structure, the structure is: ◎ Cf3 h3c Where the Ar’ stands for 47 1290153 48