TWI312790B - Polyimides containing second-order nonlinear optical group, their derivates and method for preparing the same - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimides having a nonlinear optical property and a method for producing the same, and particularly to a secondary non-containing A poly-imine of a second-order nonlinear optical group, a derivative thereof, and a process for the preparation thereof. [Prior Art]

With the continuous development of the optoelectronic industry, many materials for light transmission have been continuously developed and researched, and the discovery of nonlinear optical effects has made the industry's development goals shift to nonlinear optical materials. . A nonlinear optical material has the ability to change the frequency or color of light itself or has the effect of increasing or decreasing the frequency of two or more photo couples and is generally based on inorganic materials. For example, quartz, potassium dihydrogen phosphate, lithium niobate, cadmium sulfide, cadmium telluride, and the like. Although inorganic materials have the advantages of southern transparency, nonlinear optical coefficient and anti-abrasion, inorganic materials themselves are expensive, monocrystalline growth is difficult, and compatibility with other optical components is not easy. Disadvantages - resulting in limited application and development. Therefore, in recent years, most of the industry has been researching and developing toward polymer materials having a second-order nonlinear optic property. In view of the operating conditions of nonlinear optics from 1 〇〇 to 150 ° C, especially in the case of photonic integrated circuits package, 5 (s) is required.

1312790 has the characteristics of being able to withstand high temperatures of 250 ° C without cracking in a short period of time. Therefore, most of the current researches are directed to the preparation of nonlinear optical polymer materials using organic polymers having better thermal stability and mechanical properties. Most of the existing non-linear optical polymer materials are obtained by grafting a chromophore having nonlinear optical properties into a polymer main chain or a side chain by physical mixing or chemical bonding, and the chromophore is obtained. The structure generally needs to include an electron donor group, an electron acceptor group, and a molecular group having a conjugated system. The magnitude of the nonlinear optical coefficient may vary depending on the structure of the chromophore, such as the strength of the donor or acceptor group, the length of the common system, the electron induced effect, and the steric effect ( Steric effect) or aromatic level. Generally, the arrangement of organic nonlinear chromophores is limited by the disorder and electrical neutrality of the overall material. The electric field must be induced or the polar groups at both ends of the molecule must be modified to make the material appear in a regular arrangement and become non-central symmetric. (noncentrosymmetric) structure can exhibit secondary nonlinear optical properties. The secondary nonlinear optical properties can be judged by the height of the electrooptic coefficient (Γ33). In the study of chromophores, Seung-Hwan Lee et al. published a series of 2,6 in the paper "Lee, SH et al., J. C/zew (2002), 12, pp. 2187-2188. - Diphenylbenzo[l,2-d:4,5-d']bisthiazole (2,6-diphenylbenzo[l,2-d:4,5-d']bisthiazole) chromophore Synthesis from 2,5-diamino-l,4-benzenedithiol dihydrochloride as starting material: 6 (S'.1312790

In the above reaction formula, A is represented by CN or NO? and D is represented by N(CH3)2 or N(CH3CH2)2, and the chromophore disclosed in this document has high thermal stability (Td) and nonlinear optics, etc. Nature, but in actual use, it will limit its use due to poor solubility. Therefore, many people try to improve such chromophores or use such chromophores to study nonlinear optical polymer materials. . In the existing nonlinear optical polymer materials, the following four types can be distinguished according to the position of the chromophore in the polymer: a guest-host system, a main chain system, and a side chain type. (side chain system) and crosslinking system. In recent years, polyimine has been found to be applicable in the field of microelectronics, and can be combined with chromophores to form nonlinear optical polymer materials because polyimine has good thermal stability. Good chemical resistance, good adhesion, low dielectric constant, low moisture absorption, good mechanical properties, and low coefficient of thermal expansion, so many people try to Polyimine is used as the main chain, and the chromophore is grafted onto the polyimine to form a secondary nonlinear optical material with better thermal stability. For example, in the paper "Leng, W. N. et al., pp. 9253, a side chain type nonlinear optical polymer with polythenimine as the main chain is disclosed, which is caused by the following reaction Made by the formula: 7 1312790

The nonlinear optical polymer disclosed in this document has an electro-optic coefficient r33 of 21 pm/v (at 830 nm) and a glass transition temperature (Tg) of 248 °C. However, the nonlinear optical polymer of this document has an azo group in the structure of the chromophore, and has poor thermal stability, which greatly reduces the secondary nonlinear optical characteristics at high temperatures, and even loses twice. Nonlinear optical properties.

^ As can be seen from the above, how to develop a secondary nonlinear optical material with thermal stability and high electro-optic coefficient still exists in the industry. SUMMARY OF THE INVENTION <Summary of the Invention> In order to obtain better thermal stability and nonlinear optical characteristics, the present invention utilizes a compound having a good secondary nonlinearity (IV) and consisting of a benzobis(tetra) compound, a A poly-i-imine with good thermal stability, which combines the two to produce a secondary nonlinear optical material having both thermal stability and secondary nonlinear optical properties. .1312790 A non-linear optical group of a polyaniline containing a -(tetra)imine backbone and a chromophore as a side chain and represented by the following formula (c2):

R2

(C2) In the formula (C2), R2 represents a phenyl gr〇up or a phenylalkenyl group which is substituted with a substituent selected from the group consisting of: N〇2 , c〇CH3, CN, s〇2 bribe 2, b Bu and a combination of these. Since the bis(tetra) compound of the invention (4) is a chromophore of a high rod-shaped (ngld.n) d) structure, if it is directly grafted with the polyimine primary bond, it may be polarized at the electrode (PGling). It is not easy to cause the chromophore to form a polarization alignment, thereby reducing secondary non-optical properties. Therefore, the present invention attempts to design a "soft structure" between the main ==, that is, the chromophore is designed to be (C2): the steroid and as a trans-base bond between the main chain and the side chain (such as (4) What is not the new color of the hair color circle), and does not affect the thermal stability to enhance the secondary nonlinear optical characteristics. In addition, the present invention further provides a kind of polyimine for optical groups. - a human non-linear repeating unit, "two" 5-imine is represented by the lower copper. The following steps are included: (1) providing a unit of the following formula: Νη % _ 乂: () Polymer solution Ί312790

(η) provides a compound represented by the following formula (S2):

(S2) (111) grafting a polymer composed of the repeating monomer represented by the formula (S1) with the compound represented by the formula (S2) at a suitable temperature to obtain a formula The intermediate formed by the repeating unit shown in (S3):

y N In the formulae (S2) and (S3), 'R2 is represented by a phenyl or phenyl alkenyl group selected from a substituent selected from the group consisting of: COCH3, CN, S02NH2, Br, Cl, and These - the combination is 10.1312790

And in the formulas (S1) and (S3), and (iv) providing a solution containing the intermediate' and heating at a high temperature under vacuum to obtain a repeating unit represented by the following formula (11) Polyimine:

Further, the present invention provides a polyimine derivative composed of the repeating unit represented by the above formula (S3) and a compound represented by the above formula (S2).

In the polyimine imine containing a secondary nonlinear optical group of the present invention, in addition to having a novel chromophore as a side chain, a diamine containing a hydroxyl group and an anhydride are selected to synthesize a polyimine chain, and The functional group is more designed on the main chain to increase the solubility and transparency of the polyimide. <Detailed Description of the Invention> Accordingly, the polyiminimide group containing a secondary nonlinear optical group of the present invention comprises a polyimine chain and a side chain and is represented by the following formula (C2) Color group:

(C2) 11 • 1312790 In the formula (C2), 'R2 is represented by a phenyl or phenyl alkenyl group selected from a substituent selected from the group consisting of N〇2, COCH3, CN, SO2NH2. Br, Cl and a combination of these. Preferably, the polyimine backbone is composed of repeating units represented by the following formula (P1):

(PI Preferably, the polyamidene containing a secondary nonlinear optical group is composed of a repeating unit represented by the following formula (II):

-y In the formula (Π), R2 represents a phenyl or phenylfluorenyl group which is substituted with a substituent selected from the group consisting of N〇2, COCH3, CN, S02NH2, Br, Cl and One of these combinations, as well. In the formula (II), 'R2 is optionally a phenyl group substituted with a substituent selected from the group consisting of: no2, COCH3, CN, so2nh, 12 • 1312790, Br, C1 and the like. One combination; and preferably, a phenyl group substituted with N〇2; and more preferably, R2 is p-nitrophenyl gr〇up. In one embodiment of the present invention, R2 of the formula (Π) is p-nitrophenyl and y=l 〇 in the formula (II), and R 2 is selectively selected from the group consisting of a phenylalkenyl group substituted with a substituent: n〇2, c〇CH3, CN, SOAH2, Br, Cl, and combinations thereof; and preferably, R2 is a phenylenyl group substituted by n〇2 And, more preferably, for the p-nitrophenyl vinyl nitrophenylvinyl group). In one embodiment of the present invention, R 2 of the formula (II) is p-nitrophenylethyl group and y=1. In addition, the present invention is a method for preparing a polyimine containing a secondary nonlinear optical group. The polyimine is composed of a repeating unit represented by the above formula (π), and the method comprises the following steps: (1) Providing a solution of a polymer composed of a repeating unit represented by the following formula (S1)

(li) providing a compound represented by the following formula (S2):

(S2) 13 1312790 (in) grafting a polymer composed of the repeating unit represented by the formula (S1) with the compound of the formula (S2) at a suitable temperature and at a suitable temperature to obtain a An intermediate formed by a repeating unit represented by the following formula (S3):

In the formulae (S2) and (S3), & represents a phenyl or phenyl alkenyl group which is substituted with a substituent selected from the group consisting of N〇2, COCH3, CN, SO2·2. Br, Cl and the combination of these, and in the formulae (S1) and (S3), 〇<y^l; and (V) k for a solution of 3 intermediates and heating under vacuum high temperature And a polyimine consisting of the repeating unit represented by the formula (II) is obtained. It should be noted that the polyimine containing the secondary nonlinear optical group consisting of the repeating unit represented by the above formula („) of the present invention can also be synthesized by various conventional methods. , in the poly-sigma consisting of the repeating unit represented by the formula (si), y-1, which is a polymer composed of a repeating unit represented by the following formula (si-i): 14 1312790

The polymer composed of the repeating unit represented by the above formula (S1-1) can be produced by various conventional methods, and in one specific example of the present invention, the repeating unit represented by the above formula (S1-1) The polymer is composed of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (hereinafter referred to as "6FDA") and 2,4 -2,4-diaminophenol dihydrochloride (hereinafter abbreviated as "DAPD") is obtained by carrying out a reaction. It should be noted that in the formula (II), when 0 < y < l, the polymer composed of the repeating unit represented by the formula (S1) may be 6FDA, DAPD and m-phenylenediamine (m- Phenylenediamine (abbreviated as "m-PDA") is obtained by reaction, and by adjusting the molar ratio of the three starting materials, different y values can be obtained. The polymer composed of the repeating unit represented by the formula (S1) in the step (1) may be formulated into a solution by using various solvents. Preferably, the solvent may be: N-methylpyrrolidone (N-methylpyrrolidone) , hereinafter referred to as "NMP", N,N-dimethylacetamide (DMA, Ν-dimethylacetamide, DMAc), N,N-dimethylformamide (DMF) Or m-Cresol, and in one embodiment of the invention, the solvent is NMP. Preferably, in the step (ii), R2 of the compound represented by the formula (S2) is a phenyl group substituted by no2, and in one embodiment of the invention, the R2 is a p-nitrophenyl group, that is, Compound represented by the following formula (S2-1): 15 1312790

The compound of the formula (S2-1) can be produced by various conventional methods, and in one embodiment of the present invention, the compound of the formula (S2-1) is composed of 2,5-bis[(cyanide). Ethyl] thio]-1,4-phenylenediamine (Z'S-BisIXcyanoethyUthic^-lJ-phenylenediamine) in sequence with 4-nitrobenzoyl chloride and 4-hydroxybenzoic acid Obtained by carrying out a reaction, wherein the reactant 2,5-bis[(cyanoethyl)thio]-1,4-phenylenediamine is a salt of 2,5-diamino-1,4-benzenedithiol The acid salt is obtained by reacting with 3-bromopropionitrile. Preferably, R2 of the compound of the formula (S2) in the step (ii) is a N02-substituted phenylalkenyl group, and in one embodiment of the invention, the R2 is a p-nitrophenylvinyl group. , which is a compound represented by the following formula (S2-2):

(S2-2) NC

NO The compound represented by the formula (S2-2) can be produced by various conventional methods, and in one embodiment of the present invention, the compound represented by the formula (S2-2) is composed of 2,5-bis[( Cyanoethyl)thio]-1,4-phenylenediamine is obtained by reacting with trans-4-nitrocinnamoyl chloride and 4-benzoic acid. The catalyst used in this step (iii) can be selected as needed, and 16 vI312790 is a specific example of the present invention, and the catalyst used in the step (ίη) is triphenylphosphine (PPh3). The reaction temperature of the step S111 (111) can be carried out for 5 weeks depending on the catalyst and the actual reaction, and in one embodiment of the invention, the reaction temperature of the step (Hi) is room temperature. The intermediate of the step (iv) can be formulated into a solution by using various solvents. Preferably, the solvent can be: NMP, n, N-dimercaptoacetamide (7), ^-dimethylacetamide, DMAc), hydrazine, Dimethyl-dimethylformamide (DMF) or m-cresol (m_Cres〇1), and in one embodiment of the invention, the solvent is NMP. Optionally, the solution containing the intermediate in the step (iv) is first coated on a substrate, heated at a high temperature under vacuum to form a polyimide layer, and finally the substrate is removed. The polyimine which contains the repeating unit of the formula (π) and which is in the form of a film is prepared for subsequent testing and application. The reaction temperature of the step (iv) can be adjusted and changed as needed; The reaction temperature of the step (iv) is between 25 〇〇c and 35 〇〇c. In one embodiment of the invention, the reaction temperature of the step (iv) is 300. Hey. Furthermore, the present invention further provides a polyimine derivative composed of the repeating unit represented by the above formula (83), and the definitions of R2 and y in the formula (83) are as described above, and Add a statement. Preferably, the & is a phenyl group substituted with N〇2; and more preferably, represented by the formula (s3) R2 in the polyimine derivative of the unit is p-nonylphenyl 17 1312790, and in one embodiment of the present invention, the polyimine derivative derived from the repeating unit represented by the formula (S3) In the case of p-nitrophenyl group and y=1, that is, a polyfluorene imine derivative composed of a repeating unit represented by the following formula (S3-1):

Preferably, R2 in the polyimine derivative represented by the repeating unit represented by the formula (S3) is a N 〇 2 substituted phenylalkenyl group; more preferably, represented by the formula (S3) In the polyimine derivative formed by the repeating unit, R2 is a p-nitrophenylvinyl group, and in one embodiment of the present invention, the polyimine composed of the repeating unit represented by the formula (S3) In the derivative, R2 is a p-nitrophenylvinyl group and y=l' is a polyfluorene derivative represented by a repeating unit represented by the following formula (S3_2): 18 * 1312790

Further, the present invention also provides a compound represented by the above formula (82), and the definition of & in the formula (S2) is as described above, and will not be further described herein.

Preferably, r2 in the compound represented by the formula (S2) is a phenyl group substituted with n〇2, and in a specific example of the present invention, R2 in the compound represented by the formula (S2) is a pair. A nitrophenyl group is a compound represented by the above formula (S24). Preferably, r2 in the compound represented by the formula (S2) is a phenylenyl group substituted by n〇2, and in a specific example of the present invention, the compound represented by the formula (S2) h is p-nitrophenylvinyl group, that is, a compound represented by the above formula (S2_2). The present invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting. 19 1312790 School Products] 1. 6FDA: manufactured by Chriskev Corporation of the United States. 2. DAPD: manufactured by Aldrich. 3. Meta-phenylenediamine: manufactured by Acros. 4. NMP: manufactured by Tedia Corporation. 5. 4-Nitrobenzhydryl chloride: manufactured by Aldrich. 6. 4-Hydroxybenzoic acid: manufactured by Aldrich. 7. Trans-4-nitrocinnamyl chloride: manufactured by Aldrich.

8. Triphenylphosphine: manufactured by Lancaster. [Structural Analytical Instrument] The following preparation examples will be subjected to structural identification using the following instruments: 1. Nuclear Magnetic Resonance (NMR): manufactured by the American Varian company, model Varian Gemini NMR 200 MHz. 2. Element Analyzer (EA): manufactured by Elementar, Germany, model Elementar vario ELIII. The following examples will be used for structural identification using the following instruments: 1. Fourier Transform Infrared (FT-IR): manufactured by Perkin-Elemer, USA, model Perkin-Elemer 2000. [Examples] (Preparation of starting material 2,5-bis[(cyanoethyl)sulfide]-M-phenylenediamine) As shown in the reaction scheme of Figure 1, 200 g (1.85 mol) of p-benzene was used. The diamine is mixed with aqueous hydrochloric acid (1800 ml of water and 360 ml of hydrochloric acid) 20, 1312790, until the p-phenylenediamine is dissolved, then 13 g of activated carbon (charcoal) is added, and stirred at 50 ° C. After an hour, it was filtered to obtain a yellow solution. 580 g of ammonium thiocyanate (NH4SCN, manufactured by Merck) was added to the yellow solution, and the temperature was controlled at 90 to 100 ° C for stirring, followed by purification and drying to obtain p-phenylene double Thiourea (/?-phenylenebis (thiourea)). Then, 200 g of chloroform was added to 200 g (0.89 mol) of p-phenyl dithiourea, and then a solution consisting of 80 ml of bromine and 80 ml of chloroform was slowly dropped, and the solution was carried out at 50 ° C. The reaction is then stirred at room temperature overnight, then heated to reflux temperature 65-75 ° C for 24 hours, finally purified, recrystallized and dried to obtain 2,6-diaminobenzothiazole (2,6) -diamino-[ 1,2-d:4,5-d']benzobisthiazole) 0 Add an aqueous solution of potassium hydroxide to 50 g (0.23 mol) of 2,6-diaminobenzothiazole under argon. (mixed from 225 g of potassium hydroxide and 450 ml of water), and stirred at a temperature of 10 ° C, and then stirred at room temperature for a while, then heated to 150-160 ° C for 5 hours. Then, it was cooled to room temperature, and then a hydrochloric acid solution (375 ml of hydrochloric acid and 375 ml of water was mixed), and finally purified, recrystallized and dried to obtain 2,5-diamino-1,4-benzene. Mercaptan dihydrochloride. 13.2 g (53.80 mmol) of 2,5-diamino-1,4-benzenedithiol dihydrochloride was dissolved in an aqueous solution of sodium hydroxide (14.4 g of sodium hydroxide and 200 ml of water). In the solution, until completion of the dissolution, slowly add 15.93 g (118.81 mmol) of 3-bromopropionitrile at 0 °C. Further preparing a mixture of 0.42 g (1.32 mmol) of hexadecyltrimethylammonium chloride (cetyltrimethylammonium 21 1312790 chWide's manufactured by TCI) and 2 ml of an aqueous solution of sodium hydroxide, and This mixture was added, and stirred at room temperature for 5 hours, and finally purified, recrystallized and dried to obtain 2,5-dicyanoethyl)thio]-1,4-phenylenediamine. (Preparation Example 2,5-bis[(2-cyanoethyl)sulfide]_N•(p-hydroxybenzoyl)N,_(p-nitrobenzylidene)-p-phenylenediamine {(2, 5bisK2_cyanoethyl)thio].N-(p-hydroxybenzoyl).N^(p- nitrobenzoyl)-p_phenyienediamine, that is, the compound of the formula (S2 1) is prepared as shown in the reaction scheme of Figure 2, wherein & P-nitrophenyl. 7.65 g (27_26 mmol) of 2,5-bis[(cyanoethyl)sulfanyl]-p-phenylenediamine was mixed with 45 ml of hydrazine, and then the reaction temperature was controlled at 〇~5.匚, then add 10 ml (28,62 mmol) of triethylamine, and then slowly instill 4_nitrobenzhydryl chloride (5.4 g (28.62 mmol) of 4-nitrophenylhydrazine The helium gas was dissolved in 17 ml of NMP, and reacted in an ice bath for 2 hours, and then placed in 1000 ml of deionized water to produce a solid precipitate, followed by purification and drying to obtain 2,5-double [ (2-cyanoethyl)sulfide]_N_(4-nitrobenzhydryl)-1,4-phenylenediamine {(2,5-bis[(2-cyanoethyl)thio]-N-(4-nitrobenzoyl )-l,4-phenylenediamine). 1 g (2.34 mmol) of 2,5-bis[(2-cyanoethyl)sulfo]-N-(4-nitrobenzylidene)-1,4-phenylenediamine with 0.328 g ( 2_38 millimoles of 4-hydroxybenzoic acid was mixed, and then 11.7 ml of NMP was added, followed by 0.58 g of chlorinated clock (LiCl), 2.92 ml of triphenyl phosphite (TPP) and 2 - 92 ml. Pyridine (pyridine), and the temperature is raised to 1312790 80~95 °c and reacted for about 4 hours, and finally purified and dried to obtain 2,5-bis[(2-cyanoethyl)sulfide]-N- _n, _ (p-decyl benzhydryl)-p-phenylenediamine (S2-1), the yield was 76 3%. iAMRPMSO-WAppm) : i〇.39(s lH), 1〇i5(s, 冈, 9.76(S,m), 8.39~8.34(d,2H), 8.21~8.17(d,2H), 7.87~7.82 (d, 2H), 7'70 (S, 1H), 7.6 〇 (s lH), 6 87~6 83 (d 2H), 3.24~3.12 (d, 4H), 2·80~2.71 (d, 4H) );

Elemental analysis of C26H21N505S2: Theoretical value: c, 57.03; η, 387; N, 12.79; S, 11.71; actual value: C, 55 35; H, 414; n, 12.10; S, 11.02. (Preparation Example 2) N_[4-(p-hydroxybenzamide)]_2,5-biguanide (2-cyanoethylsulfonamide) phenyl]-trans-4-firmyl cinnamyl maleic acid amine {n_[ 4 gas p_ hydroxybenzoyl)]-2,5-bis[(2-cy a noethyls u If any 1) phenyl]-tr an s-4-nitrocinnamoyi formamide , that is, the preparation of the compound represented by the formula (S2-2) As shown in the reaction scheme of Figure 2, wherein A is p-nitrophenylvinyl. Mix 2.5 g (9.00 mmol) of 2,5-bis[(cyanoethyl)sulfan]-M-phenylenediamine with 15 ml of NMP, then control the reaction temperature at 0 °c, then slowly drip Into trans-4-nitrocinnamyl helium (2.0 g (9.45 mmol) of trans-4-nitrocinnamyl chloride dissolved in 3 ml of NMP), and placed in an ice bath The reaction was carried out for 2 hours and water was added to give a solid smear. Subsequent purification and drying' to obtain N-[4-amino-2,5-bis(2-cyanoethylsulfonyl)phenyl]-trans-4-nitrocinnamylcarbamamine {N-[4 -amino-2,5-bis(2- 23 *1312790 cyanoethylsulfanyl)phenyl]-trans-4-nitrocinnamomyl formamide} ° 1 g (2.20 mmol) of N-[4-amino 2,5·double (2-Cyanoethylsulfonamide) phenyl]-trans-4-nitrocinnamamine, 〇η克 (2 24 mmol) of 4-hydroxybenzoic acid and 11.7 ml of NMP were mixed, and then Add 〇58 g of lithium chloride. After complete dissolution, add 2.92 ml of triphenyl phosphite and 2.92 ml of pyridine, and warm to 8 〇~1 〇〇〇c and react for about 4 hours. To produce a solid precipitate, which is finally purified and dried to obtain N-[4-(p-hydroxyphenylhydrazino)]-2,5·bis[(2-cyanoethylsulfonyl)phenyl]-trans-4 - Nitrophenyl acrylamide (S2-2), yield 82%. 1H-NMR (DMSO-d6), 5 (ppm): 11.45 (s, lH), 9.84 (s, lH), 9.75 (s, lH), 8.35 to 8.21 (d, 2H), 7.96 to 7.80 (m, 4H), 7.78~7.68(d,lH), 7.32~7.18(m,2H),6_92~6.80(d,2H), 3.25~3.08(m,4H) >2.88~2.74(m,4H); C28H23N505S2 Elemental analysis: Theoretical value: C, 41.61; H, 4.07; N, 8.09; S, 18.50; actual value: C, 41.57; H, 4.05; N, 8.10; S, 18.48. (Preparation Example 3) The preparation of the polymer composed of the repeating unit represented by the formula (S1-1) is as shown in the reaction scheme of Fig. 3, and DAPD of 〇44 g (2·25 mmol) under nitrogen was used. 7.97 ml of hydrazine was mixed and then 6 ml of pyridine was added. Then, the reaction temperature was lowered to 0 to 5 ° C, and 1 g (2.25 mmol) of 6-FDA was further added, and stirred at room temperature for 12 hours to obtain a polyamic acid solution. Adding toluene to the polyamic acid solution 24

(S • 1312790 (toluene), and heating under reflux at 160. 0: for 48 hours, then poured into deionized water for solid sinking. Finally, purification and drying are obtained, which is obtained by the formula (S1-1). A polymer composed of the repeating unit shown. (Example 制备 Preparation of a polyimine film composed of a repeating unit represented by the formula (Π) (R2 is p-nonylphenyl group, y=l) 1. The polyimine derivative (hereinafter abbreviated as "S3-1") composed of the repeating unit represented by the formula (S3-1) is prepared as shown in the reaction scheme of FIG. 3, wherein I is a p-nitro group. Phenyl. 0.82 g (1.38 mmol) of the polymer of the repeating unit represented by the formula (si-i) obtained in the preparation example 3 was mixed with 18·4 ml of hydrazine under nitrogen. After completely mixing and dissolving, 〇·8 gram of triphenylphosphine and 0.83 g of the compound of the formula (S24) obtained in the preparation example 1 were added, followed by slowly dropping 〇.53 g of azo two. Diethyl azodicarboxylate (DEAD) and stirred at room temperature for 48 hours to obtain a solution. Then the solution was dropped. The (S34) polyimine derivative was obtained in deionized water, I to produce a precipitate, and finally filtered and dried to obtain a yield of 83.8%. IR (KBr). 1729 cm ^0 = 0); Cm-, decylamino); mo and 1373 cm·1 (N02); 1350 cm·1 (醯imino). 2. The polyimine film (hereinafter abbreviated as "11-1") composed of the repeating unit represented by the formula (II) is prepared as shown in the reaction scheme of FIG. 3, wherein p-nitrophenyl group . The polyimine derivative containing the repeating unit represented by the formula (S3-1) is dissolved in hydrazine to obtain a crude product solution. Next, the crude product solution was spin-coated on an indium tin oxide (ITO) substrate using a spin coating 25*1312790 spin coating machine, which was then placed in a vacuum oven at 3 Torr. c. The cyclization reaction is carried out under vacuum, and the (II-1) polyimine in a film form can be obtained after 9 hours. IR (KBr): 1730 cmlOO); 1487 em-1 (° sputum ring). (Example 2) Preparation of a polyimine film composed of the repeating unit represented by the formula (II) (R2 is a p-phenylene group, y=l) 1. From the formula (S3-2) The polyimine derivative (hereinafter abbreviated as "S3-2") composed of the repeating unit shown is prepared as shown in the reaction scheme of Figure 3, wherein I is p-nitrophenylvinyl. Under nitrogen, 72 g (0.19 mmol) of the polymer composed of the repeating unit represented by the formula (S1-1) obtained in the preparation example 3 and 2 5 · 0 ml of _ NMP After mixing, to be completely mixed and dissolved, 6.5 g of bis-mercaptophosphine and 0 · 71 g of the compound of the formula (S2-2) obtained in the preparation of Example 2 were further added. Then, 43 g of azobishydradic acid diethyl ester (DEAD) was slowly added dropwise, and stirred at room temperature for 48 hours to obtain a solution. Then, the solution was dropped into deionized water to produce a precipitate, which was finally filtered and dried to obtain the (S3-2) polyimide derivative, and the yield was 92%. IR (KBr): 2254 cm (CN); 1672 〇 «1_1 (0 = 0); 1534 '1344 cm-1 (N02). 2. The polyimine film (hereinafter referred to as "11-2") composed of the repeating unit represented by the formula (Π) is prepared as shown in the reaction scheme of FIG. 3, wherein I is p-nitrobenzene. The vinylidene 26 derivative is dissolved in NMP by a polyimine derivative composed of the repeating unit represented by the formula (S3_2) to obtain a crude product solution. Next, the crude product solution is spin-coated on a steel oxide substrate by a spin coater, placed in a vacuum oven, and subjected to a cyclization reaction at 3 ° C under vacuum. The (11_2) polyimine in a film form can be obtained in an hour. IR (KBr): 1534, 1344 em_1 (N〇2). (Test analysis) Solubility test: The solubility test of S3_2 and π_2 prepared in Example 2 was carried out. The results are summarized in Table 1 below. Table 1 Chloroform tetrahydrofuran (THF) Monomethyl 1 (DMSO) 三氟 Trifluoroacetic acid (TFA) Methanesulfonic acid (MSA) S3-2 — X + — ++ + + + + + + ΙΙ-2 ^-- - XXX + — + ++ (Results) In Table 1, the above symbols represent: “++” can be solved at room temperature; “+” can be dissolved after heating; “+_” is heated After the partial solution, and the X" system is still insoluble after heating. From the comparison of Table 1, the head S3 2 1 11_2 has suitable solubility, which should be sufficient for the subsequent use, and the solubility of S3_2 is better than π_2 because it has a cyclized side chain compared to ΙΙ-2. As a result, the rigidity of the polymer is increased to reduce its degree of freedom, and the solubility is lowered. In contrast, S3-2 has a better solubility because the side chain is not cyclized. .1312790 2·Inherent viscosity (test: S3-1, II-1, S3-2 and II-2 prepared in Examples 1 and 2 were respectively prepared to a concentration of 0.5 g/cm using NMP as a solvent. The solution of (g/dl) was measured by a viscometer (Ubbelohde) and the results were summarized in Table 2. 3. Thermal properties test: 3-1. Glass transition temperature (Tg) measurement:

Using a thermomechanical analysis (TMA) manufactured by Perkin-elemer, USA and model TA 2940 TMA, with macro expansion probe and tensile probe (tensi〇n, respectively) The glass transition temperature measurements of II-l and II-2 obtained in the first and second embodiments were carried out, and the results were separately summarized in Table 2 below. 3_2·thermogravimetric annaly sis: A Thermogravimetric Analyzer (TGA) manufactured by Perkin-Elemer, USA, model TGA-7, and 1 Torr under a nitrogen flow rate of 2 〇 ml/min. The temperature of (:/min is increased, and the thermal decomposition temperature (d and "dd") of S3-1, II-1, S3-2 and Π-2 obtained in Examples 1 and 2 was measured. The results are separately summarized in the following Table 2. 4. Measurement of refractive index: The refractive index was measured in the manner of "R. Swanepoel, 乂〇ρί J J 1985, 2, 1339", and the first embodiment was measured. 2 prepared II-1 and 11_2 at an incident angle of 90. The UV transmission spectrum is then measured at 28 • 1312790 with an incident angle of 30. The UV penetration spectrum is then selected and the peak in the spectrum is selected. And trough 'and use the following equation to calculate the refractive index: -ik_ one. sin/ sin 30° nw = m = 'sinr (in terms of incident angle 30.) In the above formula, 'r is the angle of refraction, measured The results will be compiled in Table 2 'and will be used as the basis for calculating the electro-optic coefficient (r33). Table 2 Polymer ^]inh (dl/g) Tg (°C) Tdi (°C) Td2 (°C) at 800 Coking yield at °C (char yield, %) Refractive index n / wavelength (nm) S3-1 0.415 209 570 45 II-1 - 324 355 576 51 1.55/630 S3-2 0.398 286 536 42 II-2 - 327 376 547 5 8 1.48/830 (Results) A. Viscosity: As shown in Table 2, the viscosity of both S3-1 and S3-2 is greater than 3.3 dl/g, so it can be further prepared into film-like II-1 and Ϊ1· 2, and is conducive to the use of the following applications. B. Thermal properties: B-1. Glass transition temperature: In Table 2, 'II-1 of the embodiment 1 and Π-2 of the embodiment 2 have higher than 300 The glass transition temperature of °C can meet the requirements of subsequent applications (Tg> 200oC) B-2. Thermogravimetric analysis: 29 • 1312790 / / 3-1 and (1) 1 results, because it is called ... ethyl and The bond energy of the nitro group is smaller, so the thermal stability is poor, so the first thermal cracking starts at .c and the second thermal cracking starts at the gamma c. In the result of w, because 仏1 The structure of the side chain chromophore is formed by the rigid heterocyclic group of materials, so the heat stability is high, but N〇2 is susceptible to cracking at high temperature, and the first thermal cracking starts at 355 C.

From the results of S3-2 and n_2 in Table 2, since the domain bond of S3_2, cyanoethyl and nitrate, the bond energy of the base is small, the thermal stability is poor, so the first time at 286 〇C is started. Thermal cracking, which accounts for about 11% of the total pyrolysis weight, begins to produce a second thermal cracking at 536 gamma 1 overall pyrolysis weight of about 30%. In the result of π_2, since the structure of the side chain chromophore of η_2 is composed of a relatively rigid heterocyclic aromatic, the heat stability is high, but Ν〇2 is susceptible to cracking at a high temperature, so 376. (: The first thermal cracking begins, accounting for the overall pyrolysis weight

And a second thermal cracking started at 547 ° C, accounting for about 15% of the total pyrolysis weight. It can be seen from the above analysis that both Π_ι and π_2 of the first and second embodiments have a high glass transition temperature' and the thermal cracking temperature is much higher than 250 ° C. Therefore, the secondary nonlinear optical system prepared by the invention The polyimine of the group does have good thermal properties. 5. Measurement of electro-optic coefficient (r33): According to the test method of ''Yoshito Shuto, Michiyuki Amano, J. Appl. phys 1995, Vol_77, No. 9, 4632-4638', respectively, in the 30 '1312790 Example 1 2 on a 1 Τ〇 substrate, which is in the form of a film of ΙΙ·1 and ΙΙ·2 polyimine, and then re-steamed it as an electrode layer to form a nonlinear optical film sheet (from bottom to top structure). a sequence layer, a polyimide film and a substrate), and then applying a modulation voltage to the test piece, and causing the laser light of the wavelength to be incident on the Ι1Ό substrate at a Θ angle, and then passing through the 聚亚亚The amine film 'finishes the reflected laser light from the (four) layer and then passes through a phase retarder, analyzer and lock-in Amplifier.

'To convert the light wave into an electronic signal, the light intensity 1 value is obtained, and finally the electro-optic coefficient is calculated by the following equation: sin20 Γ33 = (5^) (seven-, medium λ is the incident wavelength of the field light, η is the embodiment 1, 2, the refractive index of II-1 and II-2, Ic is the light intensity when adjusted to circular polarization, L is the light intensity measured by the photodetector, and 0 is the angle at which light is incident on the film. The result is shown in Figures 4 and 5. In the above test, it should be noted that the thickness of the film formed by the 11-; 1 and H-2 is preferably μηη, because if the film thickness is too thin, it may be at a high temperature. The voltage cannot be withstood by the voltage applied by the polarization, and the film is broken down. (Result) In Fig. 4, the electro-optic coefficient of the embodiment is increased by the voltage of 180V or more as the voltage increases until 34〇v Since the thin crucible is broken by the polarization voltage, the r33 is lowered. The optimum electro-optic coefficient (r33=6 62 pm/v) is obtained when the polarization voltage is 320 V. In the embodiment 2, The electro-optical coefficient of π_2 has the best electro-optic coefficient (r33=7.99 pm/V) when the polarization voltage is 6〇V. 31 131279 It can be seen from the above results that the electro-optic coefficients of II-1 and H_2 of the first embodiment and the second embodiment are larger than those required for general use in the industry (r33 > 3), and therefore, the secondary nonlinear optical group of the present invention is contained. The polyimine is indeed required by the industry. In summary, the polyimine of the present invention containing a secondary nonlinear optical group is grafted by a novel chromophore derived from a benzobiscarbazole compound. It has good thermal stability on polyimine, and therefore has good thermal stability, viscosity suitable for film formation, and solubility and electro-optical coefficient in line with industry requirements. The preferred embodiments of the invention are not intended to limit the scope of the invention, and the equivalent equivalents and modifications of the invention in accordance with the invention are still covered by the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a reaction flow diagram illustrating the reaction scheme of the starting material of the present invention for preparing the polyimine containing a secondary nonlinear optical group. 2 is a reaction flow chart illustrating the reaction scheme of one of the preparation methods of the present invention for preparing the poly-2-imine containing the secondary nonlinear optical group; FIG. 3 is a reaction flow chart illustrating the present invention. The reaction scheme of one of the specific methods for preparing the poly-2-imine containing the secondary nonlinear optical group; FIG. 4 is a distribution diagram illustrating the secondary nonlinear optical 32 1312790 based on the present invention. The relationship between the electro-optic coefficient and the polarization voltage of a specific example of the polyimine of the group and FIG. 5 is a distribution diagram illustrating another specific example of the polyimine containing the secondary nonlinear optical group of the present invention. The relationship between electro-optic coefficient and polarization voltage. 33 1312790 [Explanation of main component symbols] None 34 (8

Claims (1)

1312790 X. Patent application scope: 1. A polyimine containing a secondary nonlinear optical group, an imide main chain and a chromophore as a side chain and represented by the following formula (C2): In the formula (C2), I represents a phenyl or phenyl alkenyl group substituted with a substituent selected from the group consisting of N〇2, C〇CH3, CN, S02NH2, Br, Cl and One of these combinations. 2. Polyimine iodide containing a secondary nonlinear optical group as described in the scope of the patent application, wherein the polyimine is composed of repeating units represented by the following formula: 3. Polyimine containing a secondary nonlinear optical group according to the scope of the patent application 帛 2, which is composed of a repeating unit represented by the following formula (π): 35 1312790 In the formula (II), R2 represents a phenyl or phenyl alkenyl group substituted with a substituent selected from the group consisting of N02, COCH3, CN, SO2NH2, Br, Cl, and the like. One combination, and 0 < y $ 1. 4. Polyimine containing a secondary nonlinear optical group according to claim 3, wherein R2 of the formula (II) is substituted with a substituent selected from the group consisting of the following: Phenyl group: no2, coch3, CN, S02NH2, Br, ci, and combinations of these. 5. The polyamidene containing a secondary nonlinear optical group P group according to claim 4, wherein the formula (II) is a stupid group substituted with N〇2. 6. Polyimine iodide containing a secondary nonlinear optical group as described in claim 5, wherein R2 of the formula (II) is a p-nitrophenyl group. 7. Polyimine iodide containing a secondary nonlinear optical group as described in claim 6 wherein R2 of the formula (II) is p-nitrophenyl group and y=l. 8. The polyimine imine containing a secondary nonlinear optical group according to claim 3, wherein R2 of the formula (Π) is a substituent selected from the group consisting of the following: Substituted phenylalkenyl groups: N〇2, COCH3, CN, S02NH2, Br, Cl, and combinations of these. 9 _ Polyimine containing a secondary nonlinear optical group according to claim 8 of the patent application, wherein the <RTIgt;>> of the formula (II) is a N 〇 2 substituted phenyl group. 1〇_ Polyimine containing a secondary nonlinear optical group as described in claim 9 wherein R2 of the formula (II) is p-nitrophenylethylene 36 • 1312790. The second-order nonlinear optical group is p-nitrophenylacetonitrile. The polyimine containing a group according to the first aspect of the patent application, wherein the R2 group of the formula (11) and y=l . 12. A method for preparing a polyimine containing a secondary nonlinear optical group as described in claim 3 of the patent application, comprising the steps of: (1) providing - a repeating unit represented by the following formula (III) a solution of the polymer: (Π) provides a compound represented by the following formula (S2): (S1) (iii) grafting a polymer composed of the repeating unit represented by the formula (S1) with the compound of the formula (S2) at a suitable temperature and at a suitable temperature to obtain a formula (S3) The intermediate formed by the repeating unit shown: 37 (8 • 1312790 'y N NC c=o NH S NH c=o CN In the formulae (S2) and (S3), R2 represents a phenyl or phenylalkenyl group substituted with a substituent selected from the group consisting of Nc, (:OCH3, CN, S02NH2, Br, CI and one of the groups ^, and in the formulas (S1) and (S3), 〇<y$1; and (iv) provide a solution containing the intermediate, and under vacuum high temperature The heat of the heat produces a quinone imine consisting of the repeating unit represented by the formula (II). 13. For preparing a secondary non-neo optical group according to the scope of claim 12 The method of polyimine, wherein the solution of the step (iv) containing the substrate is first coated on a substrate, heated at a high temperature in a vacuum to form a polyimine layer, and finally The substrate is removed, and a poly-imine composed of the repeating unit represented by the formula (11) and having a film shape is obtained. The preparation of the second aspect of the patent is described in claim 12 The method of the polyimine of the group is y=1 in the polymer composed of the repeating unit represented by the formula (S1) in the step (1) 38 1312790. 5. The method for preparing a polyfluorene imine containing a secondary nonlinear optical group according to the invention of claim 14 wherein the step (1) consists of the non-repeating unit of the formula (S1) The polymer is obtained by the reaction of 4,4,-(hexafluoroisopropylidene)|monophthalic anhydride and 2,4-diaminophenol dihydrochloride. The method for preparing a polyfluorene imine containing a secondary nonlinear optical group, wherein the compound represented by the formula (S2) is a p-nitrophenyl group in the step (9). Please prepare a method for preparing a polyimine of a secondary non-linear group by using the material of the 16th item, wherein the compound represented by the formula (S2) is 2,5_double [(Cyanoethyl)sulfide H,4-phenylenediamine is obtained by the reaction of 4-nitrobenzhydryl chloride and 4· mercaptobenzoic acid. 18. According to the scope of the patent application, A method for producing a polyanilin containing a secondary nonlinear optical group, wherein the compound of the formula (S2) and the compound represented by the formula (S2) are a fluorenyl phenylethylene group. According to the method of claim 18, the method for preparing a polyaniline containing a secondary nonlinear optical group, wherein the step (n) is carried out by the compound of the formula (S2)仏 bis [(cyanoethyl) sulfenyl] 丨, 4- phenylenediamine is obtained by reacting with trans _4_ Shi Xiaoji Cinnamon oxime and 4 _ benzoic acid. 2 〇 · According to the application patent (4) 12 items The method of preparing a polyimine containing a secondary non-organic optical group, wherein the catalyst of the step (IV) is a tri-phenylphosphine. 39 1312790 21. The second optical group according to the patent application scope The method of brewing the imine, = preparing the secondary non-linear temperature system to room temperature. In the middle of step (iii), the polyimine of the optical group according to claim 12 of the patent application scope/preparation contains a secondary non-linear system between 25 〇 < ^ 350 〇 c 〃 The temperature of the step (4) is 23 (a kind of polyimine derivative composed of the complex unit of the following formula (S3)) y In the formula (S3), 'r2 is represented by a phenyl group or a streptoyl group selected from a substituent selected from the group consisting of N〇2 'COCH3 ' CN S02NH2, Br, ci and the like. A combination, and 〇<yg 1. 24. The polyimine derivative represented by the repeating unit represented by the formula (s3) according to the 23rd item of the patent application, wherein R2 of the formula (Lu 3) is substituted by N〇2 Phenyl. 25. The polyimine derivative according to the formula (S3), wherein the compound of the formula (S3) is p-nitrobenzene, according to the claim 24 of the patent application, wherein the compound of the formula (S3) is a compound of the formula (S3) base. 26. The polyimine derivative represented by the repeating unit represented by the formula (83) according to claim 25, wherein the formula (S3) is a p-nitrophenyl group and y= 1. 27. The polyimine derivative according to the formula (S3), wherein the formula (S3) is a N-substituted benzene. Alkenyl. 28. The polyimine derivative represented by the formula (S3), wherein the formula (S3) is a p-nitrophenylvinyl group, according to claim 27, in the formula (S3) . 29. The polyimine derivative represented by the repeating unit represented by the formula (83) according to the scope of claim 28, wherein the formula 2 (S3) is a bismuth phenylethylene group And y== 1. 30. A compound represented by the following formula (S2): In the formula (S2), I represents a phenyl or phenyl alkenyl group substituted with a substituent selected from the group consisting of N〇2, COCH3, CN, S02NH2, Br, Cl, and the like. One combination. 3 1 _ The compound represented by the formula (S2) according to the third aspect of the patent application, wherein r2 of the formula (S2) is a phenyl group substituted by n〇2. 41 1312790 3 2. According to the scope of the patent application 篦3, e is a compound represented by the formula (S2) as described in Item 31, wherein the compound of the formula (S2) is a nitrophenyl group. 33. The compound of the formula (s2) according to the third aspect of the patent application, wherein the <>> of the formula (S2) is a phenyl fluorenyl group substituted with N〇2. 34. The compound of the formula (S2), wherein the &> is a p-nitrophenyl group, according to the scope of claim 33. 42 (S