TW201540723A - Amine-containing benzoxazines, polymer thereof, and preparation of the same - Google Patents

Abstract

The subject invention provides an amine-containing benzoxazines, polymer thereof, and preparation methods of the same. The compounds of the subject invention can be used in manufacture of many kinds of cross-linking polymer material, and the obtained material is improved in terms of many properties. Moreover, the preparation method of the subject invention can simplify the steps, and can also precisely synthesize the targeted products.

Description

Amine-based oxoazobenzocyclohexane, polymer thereof and methods for producing same

The invention provides an oxo-nitrobenzocyclohexane containing an amine functional group and a preparation method thereof, and the compound of the invention can be directly applied to preparing a cross-linked polymer material and improving various properties of the material.

Phenol formaldehyde resin is a commonly used thermosetting resin obtained by polycondensation of a phenolic monomer and an aldehyde monomer. Recently developed benzooxazine compound (Benzoxazine) compound is also one of phenolic resins, which has a monomer to undergo ring-opening polymerization after being heated to form a cross-linked cured product, and has no curing process. Catalyst and no by-product formation, and its cured product has high glass transition temperature (Tg), high modulus (Modulus), low moisture absorption rate, good electrical properties, and better compared with traditional phenolic resin. Excellent characteristics such as flame resistance and high yield, so there is a tendency to gradually replace the traditional phenolic resin.

Taking the synthesis of oxo-nitrobenzocyclohexane Ba which is currently used as an example, the method is prepared by reacting bisphenol A, formaldehyde and aniline in a 1:4:2 reaction. The equation is as follows:

By changing the phenolic compound and the amine compound, the oxoazobenzocyclohexane compound ^1-12 containing various groups can be synthesized to obtain a special applicability, and therefore, the compound has a relatively large molecule. Design space.

However, the study of the changes in the synthesis process of compounds, as can be seen from the literature ¹³ , in the process of the amine compound will be pre-formed with formaldehyde containing three The intermediate product of the (Triazine) structure is then reacted with a phenolic compound to obtain the target product, and the reaction formula is as follows:

Therefore, in order to obtain an oxoazobenzocyclohexane monomer containing a primary amine functional group, it is necessary to overcome the problem that the amine compound is previously reacted with formaldehyde to synthesize an amine group-containing oxoazobenzocyclohexane. Compounds are quite difficult.

Looking at the development of such compounds, only one of the literatures ^{14 has} successfully synthesized an oxo-nitrobenzoxyl monomer with a primary amine functional group. This article protects the amine group and synthesizes oxo-nitrobenzene. After the cyclohexane compound is deprotected, the target product is successfully obtained. The equation is as follows:

However, this method is cumbersome and the process still has considerable room for improvement. Therefore, the present invention discloses a simple and precise method for synthesizing an amine group-containing oxobenzobenzocyclohexane compound, which utilizes a steric hindrance caused by a bulky group to reduce the reactivity of the amine group and achieve a protective effect. And the high-purity target product can be obtained through a simple synthesis step without going through a deprotection process.

In addition, recently, the literature has been applied to a variety of polymer materials by synthesizing an oxocarbobenzocyclohexane compound containing a special functional group to prepare a crosslinked novel material.

For example, in the literature ^15, 2010, previously synthesized scholars Yagci terminal bifunctional alcohols having an oxo group monomer of N-substituted benzo-cyclohexane, further oxo and N-substituted benzo ring to give the acid anhydride-containing polycondensation The hexane-structured polyester (Polyesters) material has excellent flexibility due to the introduction of a soft long carbon segment and an ester group, and because the cured polymer has phenolic groups (Phenolic hydroxyls). And a Carboxylic acid structure, which has good adhesion to tin plates.

The document published in 2011, ^16, will also be of the mentioned amino group-containing N-substituted benzo-oxo-cyclohexane acyl chloride monomer compound ¹⁴ and polycondensation to produce the main chain containing N-substituted benzo-oxo-cyclohexane structures Polyamide film material, and can obtain more excellent thermal stability by temperature crosslinking.

In summary, the introduction of an oxonitrobenzocyclohexane compound into a polymer material has considerable development, and therefore, the present invention is in addition to the monomer synthesis mentioned above. A method for the development of polyimide (PI) materials was developed to obtain a novel high performance material poly(benzoxazine imide)/(Poly(benzoxazine imide)/ PBzI).

references:

1. Chernykh, A.; Agag, T.; Ishida, H. Macromolecules 2009, 42, 5121.

2. Dogan Demir, K.; Kiskan, B.; Yagci, Y. Macromolecules 2011, 44, 1801.

3. Liu, Y.-L.; Chou, C.-I. Journal of Polymer Science Part A: Polymer Chemistry 2005, 43, 5267.

4. Agag, T.; Takeichi, T. Macromolecules 2003, 36, 6010.

5. Agag, T.; Takeichi, T. Macromolecules 2001, 34, 7257.

6. Takeichi, T.; Thongpradith, S.; Hirai, S.; Takiguchi, T.; Kawauchi, T. High Performance Polymers 2012.

7. Agag, T.; Liu, J.; Graf, R.; Spiess, H. W.; Ishida, H. Macromolecules 2012.

8. Oie, H.; Mori, A.; Sudo, A.; Endo, T. Journal of Polymer Science Part A: Polymer Chemistry 2012, 50, 4756.

9. Liu, Y.-L.; Yu, J.-M. Journal of Polymer Science Part A: Polymer Chemistry 2006, 44, 1890.

10. Andreu, R.; Reina, J. A.; Ronda, J. C. Journal of Polymer Science Part A: Polymer Chemistry 2008, 46, 6091.

11. Jin, L.; Agag, T.; Yagci, Y.; Ishida, H. Macromolecules 2011, 44, 767.

12. Hu, W.-H.; Huang, K.-W.; Kuo, S.-W. Polymer Chemistry 2012, 3, 1546.

13. Brunovska, Z.; Liu, J.-P.; Ishida, H. Macromol. Chem. Phys. 1999, 200, 1745.

14. Agag, T.; Arza, C. R.; Maurer, F. H. J.; Ishida, H. Macromolecules 2010, 43, 2748.

15. Tuzun, A.; Kiskan, B.; Alemdar, N.; Erciyes, A. T.; Yagci, Y. J. Polym. Sci. Part A: Polym. Chem. 2010, 48, 4279.

16. Agag, T.; Arza, C. R.; Maurer, F. H. J.; Ishida, H. Polym. Chem. 2011, 49, 4335.

SUMMARY OF THE INVENTION The object of the present invention is to provide an oxonitrobenzocyclohexane resin containing a primary amine functional group, and a process for the preparation thereof. The compound of the present invention can be directly applied to the preparation of a crosslinked polymer material and improve various properties of the material.

It is to be understood that any range of values recited in this specification is intended to include all sub-ranges For example, the range from "50 ° C to 70 ° C" includes all sub-ranges between the stated minimum value of 50 ° C and the stated maximum value of 70 ° C (eg from 58 ° C to 67 ° C, 53 ° C to 62 ° C, 60 ° C or 78 ° C) and includes the two values, that is, a range including a minimum value equal to or greater than 50 ° C and a maximum value equal to or less than 70 ° C. Because the ranges of values disclosed are continuous, they contain each value between the minimum and maximum values. Unless otherwise stated, the various numerical ranges indicated in this specification are approximate.

Oxo-nitrobenzocyclohexane resin

The oxobenzobenzocyclohexane resin disclosed in the present invention has the structure of the following (VI): Wherein R ₁ and R ₂ are independently C ₁ -C ₆ alkyl; R ₃ is selected from hydrogen, C ₁ -C ₆ alkyl, phenyl, C ₁ -C ₆ alkoxy, phenylalkyl, benzene a group consisting of an oxy group, a C ₁ -C ₆ haloalkyl group, a C ₃ -C ₇ cycloalkyl group, a -CF ₃ group and a halogen atom; B is H or ; R ₄ is a C ₁ -C ₆ alkylene group.

When B of the compound of the above formula (VI) is H, the oxoazobenzocyclohexane resin is a compound of the formula (VIi)

When R ₁ and R ₂ of the compound of the above formula (VIi) are ethyl and R ₃ is methyl, the oxobenzobenzocyclohexane resin is a compound of the formula (VIia)

When the compound of the above formula (VI) B is When the oxobenzobenzocyclohexane resin is a compound of the formula (VI-ii)

When R ₁ and R ₂ of the compound of the above formula (VI-ii) are ethyl, R ₃ is methyl, and R ₄ is a methyl group, the oxobenzobenzocyclohexane resin is a compound of the formula (V).

Method for preparing oxo-nitrobenzocyclohexane resin

The present invention provides a process for producing an oxynitrobenzocyclohexane resin of the compound of the above formula (VI), which comprises the steps of: (a) asymmetric bisamine compound (I) and 2-hydroxybenzene-containing a compound of a formaldehyde functional group undergoes a condensation reaction, (b) reducing the product obtained in the step (a) with a reducing agent; (c) mixing the product obtained in the step (b) with paraformaldehyde and heating to carry out a reaction to obtain an oxonitrobenzobenzene ring of the compound of the formula (VI) Hexane resin.

In the above method of the present invention, the compound containing a 2-hydroxybenzaldehyde functional group may be 2-hydroxybenzaldehyde or 5,5'-methyl-bis(2-hydroxybenzaldehyde).

In the above method of the present invention, the reducing agent may be NaBH ₄ .

In the above method of the present invention, palladium carbon catalyst (Pd/C) can be used for reduction under a high pressure hydrogen atmosphere.

In the above method of the present invention, the step (c) is heated to about 50 ° C to 70 ° C, preferably The reaction is carried out at about 55 ° C to 65 ° C.

In the above process of the present invention, the reaction time of the step (c) is about 10 to 14 hours, preferably about 11 to 13 hours.

Polyimine material

The present invention provides a crosslinked polyimine material of the formula (VII-I),

Wherein R ₁ to R ₄ are as defined above; and Ar ₁ is selected from the group consisting of: m is selected from an integer from 1 to 100; Ar ₂ is selected from the group consisting of the following groups: , And x and y are independently selected from an integer of from 30 to 300.

When the R ₃ of the crosslinked polyimine material of the above formula (VII-I) is a methyl group and R ₄ is a methyl group, the crosslinked polyimine material is a compound of the formula (VII-Ia).

When the cross-linked polyimine material of the above formula (VII-Ia) is R ₁ and R ₂ is an ethyl group, Ar ₁ is And Ar ₂ is When the crosslinked polyimine material is a compound of the formula (VII-Ian)

Preparation method of polyimine material

The present invention provides a process for preparing a crosslinked polyimine material of the above formula (VII-I), which comprises the steps of: (a) oxynazabenzoxacyclohexane of the above formula (VI-ii) The resin is mixed with the bisamine monomer of formula (A) and the dianhydride monomer of formula (B),

To form a polyamic acid viscous solution; and (b) to cure the viscous solution at elevated temperature to obtain the crosslinked polyimine material; wherein the Ar ₁ and Ar ₂ systems are as defined above.

In the above method of the present invention, the reaction ratio of the oxynitrobenzoxylcyclohexane resin of the formula (VI-ii) to the bisamine monomer of the formula (A) is, in a total of 10, at 0:10. Up to 6:4, preferably in the range of 0:10 to 3:7.

In the above method of the present invention, the proportion of the diamine monomer of the formula (A) and the dianhydride monomer of the formula (B) It is about 1:1.

In the above process for producing a crosslinked polyimine material of the present invention, the step (a) is carried out by an ice bath method at a low temperature of about 0 °C.

In the above method of the present invention, the oxonitrobenzocyclohexane resin of the formula (VI-ii) is a compound of the formula (V), and the crosslinked polyimine material obtained by the method is of the formula (VII-Ian). The compound; wherein the n-form in the compound code of the cross-linked polyimine material indicates the molar ratio of the compound (V) to the total bisamine monomer in terms of a total of 10. For example: compound (V): when the bisamine monomer is 0:10, the code is (VII-Ia-0) in the embodiment; the compound (V): when the bisamine monomer is 1:9, the code is In the examples (VII-Ia-1); compound (V): when the bisamine monomer is 2:8, the code number is (VII-Ia-2) in the embodiment; the compound (V): diamine monomer When it is 3:7, the code number is (VII-Ia-3) in the examples.

Figure 1 is a ¹ H-NMR spectrum of the compound of the formula (II-a).

Figure 2 is a ¹ H-NMR spectrum chart of the compound of the formula (III-a).

Figure 3 is a ¹³ C-NMR spectrum chart of the compound of the formula (III-a).

Figure 4 is a ¹ H-NMR spectrum chart of the compound of the formula (IV-a).

Figure 5 is a ¹ H-NMR spectrum chart of the compound of the formula (Va).

Figure 6 is a ¹³ C-NMR spectrum chart of the compound of the formula (Va).

Figure 7 is a dynamic mechanical analysis (DMA) analysis of a material of formula (VII-I-a-n).

Figure 8 is a thermomechanical analysis (TMA) analysis of a material of formula (VII-I-a-n).

Figure 9 is a thermogravimetric analysis (TGA) analysis of the material of formula (VII-I-a-n).

Figure 10 is a graph showing the mechanical properties (stress-strain) of the material of the formula (VII-I-a-n).

Figure 11 is a schematic view showing the contact angle test of a film of the formula (VII-I-a-n).

The following examples are intended to further illustrate the invention, and are not intended to limit the scope of the invention, The modifications and variations achieved are within the scope of the invention.

The implementation of the above related inventions can be expressed by Equation 1 and Equation 2, and we will be described in the following specific examples.

Reaction material

The asymmetric diamine monomer (I-a) and 5,5'-Methylenebis (2-hydroxybenzaldehyde) used in the examples of the present invention were published by the inventors of the present invention. The literature "Lin, C.-H.; Chang, S.-L.; Peng, L.-A.; Peng, S.-P.; Chuang, Y.-H. Polymer 2010, 51, 3899" and "Lin, C.-H.; Feng, Y.-R.; Dai, K.-H.; Chang, H.-C.; Juan, T.-YJPolym. Sci. Part A: Polym. The method disclosed in 2013, 51, 2, 686. is incorporated herein by reference.

The compounds used in the examples of this case and their source manufacturers are listed below: 2-hydroxybenzaldehyde, purchased from Showa; paraformaldehyde, purchased from TCI; NaBH ₄ , purchased from Acros; 4, 4'-4,4'-diaminodiphenyl ether (ODA), purchased from Chriskev, and recrystallized from methanol; 4,4'-oxydiphthalic anhydride , ODPA), purchased from Chriskev, and recrystallized from acetic anhydride; and N,N-dimethylacetamide (DMAc), purchased from TEDIA, under reduced pressure and hydrogenated Purified by distillation of calcium (purchased from Acros) and stored as molecular sieves.

The other solvents of the present invention are all commercial products (HPLC grade) and are used without further purification.

Example 1

Compound (II-a) (in Equation 1, R is C ₂ H ₅ Synthesis

The compound (II-a) is obtained by reacting an asymmetric bisamine compound (Ia) (in the formula 1, R is C ₂ H ₅ ) with 2-hydroxybenzaldehyde and then using NaBH ₄ reduction, and the synthesis steps are as follows: In a 0.25 liter three-necked reactor, 5 g (0.010 mol) of compound (Ia), 1.3919 g (0.011 mol) of 2-hydroxybenzaldehyde were dissolved in 50 ml of DMAc, and reacted at room temperature for 12 hours under nitrogen until the reaction was completed. After adding 0.6272 g (0.017 mol) of NaBH ₄ , stirring at room temperature for 12 hours, the reaction was finished by dropping into deionized water to precipitate the product. After suction filtration, the filter cake was vacuum dried in a vacuum oven at 105 ° C to obtain a milky white powder. 4.8 g, the yield was 80%.

Compound (II-a) was dissolved in DMSO-d ₆ solvent, and the results of analysis by superconducting nuclear magnetic resonance spectrometry ( ¹ H-NMR) are shown in Fig. 1. The chemical shifts are as follows: δ = 0.99 (6H, H ² ), 1.55 (3H, H ²⁰ ), 2.31 (4H, H ³ ), 4.17 (2H, H ²⁵ ), 4.41 (2H, NH ₂ ), 5.96 (1H, NH), 6.41 (2H, H ²³ ), 6.77 (1H, H ²⁸ ), 6.81 (2H, H ⁵ ), 6.83 (1H, H ³⁰ ), 7.01 (2H, H ²² ), 7.06 (2H, H ⁸ , H ²⁹ ), 7.10 (2H, H ¹⁰ , H ¹⁴ ), 7.18 (1H, H ²⁷ ), 7.27 (1H, H ¹⁵ ), 7.31 (1H, H ⁹ ), 7.63 (1H, H ¹⁶ ), 7.88 (1H , H ¹¹ ), 8.00 (1H, H ¹⁷ ), 9.48 (1H, OH). The salt tablets uniformly mixed with the compound (II-a) and the KBr salt were analyzed by Fourier transform infrared spectroscopy (FTIR) as follows: 1191 cm ^-1 (CN stretch), 3223 cm ^-1 (OH stretch), 3394 cm ^-1 (NH stretch) .

Example 2

Compound (III-a) (in Equation 1, R is C ₂ H ₅ Synthesis

The compound (III-a) is obtained by reacting the above-mentioned synthesized compound (II-a) with paraformaldehyde, and the synthesis procedure is as follows: 5 g is added to a 0.25 liter three-neck reactor equipped with a temperature indicating device ( The compound (II-a) and 0.2806 g (0.009 mol) of paraformaldehyde were dissolved in 30 ml of chloroform, heated to 60 ° C (reflux temperature), and the reaction was continuously stirred for 12 hours.

After the reaction was completed, the mixture was cooled to room temperature, and the solution was dropped into n-hexane (n-Hexane) to precipitate a powder. After filtration, the cake was vacuum dried in a vacuum oven at 60 ° C to obtain 3.6 g of a white powder in a yield of 70. %.

The differential scanning card count (DSC) scan shows that the synthesized compound (III-a) has a melting point of 184 ° C and an exothermic peak of 245 ° C.

The compound (III-a) was dissolved in a DMSO-d ₆ solvent and analyzed by a superconducting nuclear magnetic resonance spectrometer ( ¹ H-NMR, ¹³ C-NMR) as shown in Fig. 2 and Fig. 3 . Its ¹ H-NMR chemical shift is as follows: δ = 0.94 (6H, H ² ), 1.66 (3H, H ²⁰ ), 2.26 (4H, H ³ ), 4.42 (2H, NH ₂ ), 4.61 (2H, H ²⁵ ) , 5.40 (2H, H ³² ), 6.74 (2H, H ⁵ ), 6.78 (1H, H ³⁰ ), 6.89 (1H, H ²⁸ ), 6.93 (2H, H ²³ ), 6.95 (1H, H ¹⁰ ), 7.00 (1H, H ⁸ ), 7.12 (2H, H ²⁷ , H ²⁹ ), 7.18 (2H, H ²² ), 7.23 (3H, H ⁹ , H ¹⁴ , H ¹⁵ ), 7.61 (1H, H ¹⁶ ), 7.76 ( 1H, H ¹¹ ), 7.95 (1H, H ¹⁷ ); ¹³ C-NMR chemical shifts are: δ = 13.10 (C ² ), 23.82 (C ³ ), 24.41 (C ²⁰ ), 48.72 (C ²⁵ ), 52.01 ( C ¹⁹ ), 78.17 (C ³² ), 115.98 (C ²³ ), 116.22 (C ³⁰ ), 118.70 (C ⁸ ), 120.40 (C ²⁸ ), 120.71 (C ¹² ), 121.33 (C ¹³ ), 122.54 (C ¹⁸ ), 123.11 (C ¹⁷ ), 123.45 (C ¹⁰ ), 125.04 (C ¹¹ ), 125.68 (C ²⁶ ), 126.05 (C ⁵ ), 127.18 (C ²⁷ ), 127.60 (C ²⁹ ), 127.67 (C ⁹ ), 128.56(C ⁴ ), 130.13(C ²² ), 130.24(C ¹⁵ ), 131.72(C ¹⁴ ), 131.77(C ⁶ ), 133.06(C ¹⁶ ), 136.13(C ²¹ ), 141.35(C ¹ ), 146.25( C ²⁴ ), 150.78 (C ⁷ ), 153.97 (C ³¹ ). The salt tablets uniformly mixed with the compound (III-a) and the KBr salt were analyzed by Fourier transform infrared spectroscopy (FTIR) as follows: 970 cm ^-1 (NCO stretch), 1034 cm ^-1 (Ar-OC symmetric stretch), 1297 cm ^-1 ( Ar-OC asymmetric stretch), 1370 cm ^-1 (CN stretch), 3351, 3448 cm ^-1 (NH stretch).

Example 3

Compound (IV-a) (in Equation 1, R is C ₂ H ₅ Synthesis

The compound (IV-a) is obtained by reacting an asymmetric bisamine compound (Ia) with 5,5'-methyl bis(2-hydroxybenzaldehyde) and then reducing it with NaBH ₄ , and the synthesis steps are as follows: In a 0.25 liter three-neck reactor, add 5 g (0.010 mol) of compound (Ia), 1.3276 g (0.005 m01) of 5,5'-methyl bis(2-hydroxybenzaldehyde) dissolved in 50 ml of DMAc, nitrogen. After reacting at room temperature for 12 hours, 0.4312 g (0.011 mol) of NaBH ₄ was added after the reaction was completed, and the reaction was continued for 12 hours at room temperature. The reaction was finished by dropping into deionized water to precipitate a product, and the filter cake was placed in a vacuum oven after suction filtration. Drying at 105 ° C under vacuum gave 4.6 g of a white powder, yield 75%.

Compound (IV-a) was dissolved in DMSO-d ₆ solvent and analyzed by superconducting nuclear magnetic resonance spectrometer ( ¹ H-NMR) as shown in Figure 4. The chemical shift was as follows: δ = 0.99 (12H, H ² ), 1.55 ( 6H, H ²⁰ ), 2.31 (8H, H ³ ), 3.70 (2H, H ³² ), 4.17 (4H, H ²⁵ ), 4.41 (4H, NH ₂ ), 5.90 (2H, NH), 6.41-8.00 (34H , Ar-H), 9.30 (2H, OH). The salt tablets uniformly mixed with the compound (IV-a) and the KBr salt were analyzed by Fourier transform infrared spectroscopy (FTIR) as follows: 1198 cm ^-1 (CN stretch), 3223 cm ^-1 (OH stretch), 3384 cm ^-1 (NH stretch) .

Example 4

Compound (V-a) (in Equation 1, R is C ₂ H ₅ Synthesis

The compound (Va) is obtained by reacting the above-mentioned synthesized compound (IV-a) with paraformaldehyde, and the synthesis procedure is as follows: 5 g of a compound (0.004) is added to a 0.25 liter three-neck reactor equipped with a temperature indicating device. Mol) (IV-a) and 0.2777 g (0.009 mol) of paraformaldehyde were dissolved in 30 ml of chloroform, purged with nitrogen, heated to 60 ° C (reflux temperature), and the reaction was continuously stirred for 12 hours.

After the reaction was completed, the mixture was cooled to room temperature, and the solution was dropped into n-hexane (n-Hexane) to precipitate a powder. After filtration, the filter cake was vacuum-dried at 60 ° C in a vacuum oven to obtain 3.4 g of a white powder in a yield of 70. %.

The differential scanning card count (DSC) scan shows that the synthesized compound (V-a) has a melting point of 120 ° C and an exothermic peak of 255 ° C.

The compound (Va) was dissolved in a DMSO-d ₆ solvent and analyzed by a superconducting nuclear magnetic resonance spectrometer ( ¹ H-NMR, ¹³ C-NMR) as shown in Figs. 5 and 6 . Its ¹ H-NMR chemical shift is as follows: δ = 0.94 (12H, H ₂ ), 1.63 (6H, H ₂₀ ), 2.26 (8H, H ₃ ), 3.77 (2H, H ₃₃ ), 4.42 (4H, NH ₂ ) , 4.52 (4H, H ₂₅ ), 5.33 (4H, H ₃₂ ), 6.69 (2H, H ₃₀ ), 6.74 (4H, H ₅ ), 6.88 (4H, H ₂₃ ), 6.91 (2H, H ₁₀ ), 6.97 (6H, H ₈ , H ₂₇ , H ₂₉ ), 7.13 (4H, H ₂₂ ), 7.19 (6H, H ₉ , H ₁₄ , H ₁₅ ), 7.58 (2H, H ₁₆ ), 7.73 (2H, H ₁₁ ) , 7.93 (2H, H ₁₇ ). ¹³ C-NMR chemical shifts are: δ = 13.12 (C ₂ ), 23.82 (C ₃ ), 24.38 (C ₂₀ ), 48.85 (C ₂₅ ), 52.01 (C ₁₉ ), 77.96 (C ₃₂ ), 115.86 (C ₂₃ ), 116.16 (C ₃₀ ), 118.71 (C ₈ ), 120.69 (C ₁₂ ), 121.10 (C ₁₃ ), 122.56 (C ₁₈ ), 123.04 (C ₁₇ ), 123.44 (C ₁₀ ), 125.00 (C ₁₁ ), 125.69 (C ₂₆ ), 126.00 (C ₅ ), 127.02 (C ₂₇ ), 127.61 (C ₉ ), 127.84 (C ₂₉ ), 128.62 (C ₄ ), 130.15 (C ₂₂ ), 130.21 (C ₁₅ ), 131.51 ( C ₁₄ ), 131.73 (C ₆ ), 133.03 (C ₁₆ ), 136.56 (C ₂₈ ), 136.14 (C ₂₁ ), 141.34 (C ₁ ), 146.26 (C ₂₄ ), 150.76 (C ₇ ), 152.16 (C ₃₁ ). The salt tablets uniformly mixed with the compound (Va) and the KBr salt were analyzed by Fourier transform infrared spectroscopy (FTIR) as follows: 950 cm ^-1 (NCO stretch), 1044 cm ^-1 (Ar-OC symmetric stretch), 1228 cm ^-1 (Ar- OC asymmetric stretch), 1374 cm ^-1 (CN stretch), 3368, 3474 cm ^-1 (NH stretch).

Polymer material preparation method

Taking the polymer (VII-I-a-3) as an example, 0.3 g (0.25 mmol) of the aforementioned synthesized compound (V-a) and ODA 0.1155 g (0.58 mmol) were placed in a 100 mL three-necked reactor to 2.68 g of water (20 wt% of total amount) of DMAc was stirred in an ice bath under nitrogen until completely dissolved, and 0.2557 g (0.82 mmol) of ODPA was added, and the mixture was reacted for 12 hours in an ice bath.

After forming a polyamic acid viscous solution, it was coated on a glass substrate by a coater to control a film thickness of about 15 μm, and heat-treated at 60 ° C for 12 hours in a circulating oven to remove most of the solvent, and the temperature was raised by 100 ° C. Thermal imidization and ring-opening polymerization were carried out at 200 ° C and 300 ° C for one hour. After the completion, the film was released into water and the remaining polymers were prepared in the same manner.

Analytical method

Differential Scanning Calorimeter (DSC), model: Perkin-Elmer DSC 7, nitrogen flow rate of 20 mL/min.

Thermogravimetric Analysis (TGA), model: Thermo Cahn Versa Therm, nitrogen and air flow rate of 20 mL/min.

Dynamic Mechanical Analyzer (DMA), model: Perkin-Elmer Pyris Diamond, made the hardened cured product into a test piece of 20 mm in length, 10 mm in width and 2 mm in thickness, with a heating rate of 5 ° C/min and a frequency of 1 Hz. To determine the storage modulus (Storage Modulus E') and the Tan δ curve.

Thermal Mechanical Analysis (TMA), model: Perkin-Elmer Pyris Diamond, at a ramp rate of 5 °C/min.

Superconducting nuclear magnetic resonance spectrometer (600 MHz Nuclear Magnetic Resonance, NMR), model: Varian Unity Inova-600, DMSO-d ₆ chemical shift was δ = 2.49 ppm.

Fourier Transfer Infrared Spectrometer (FTIR), model: Perkin-Elmer Spectrum RX I, scanning wavenumber range 400~4000cm ^-1 , scanning times at least 32 times. Tensile testing machine, model: EZ-SX, sample size 20mm long, 5mm wide test piece, tensile speed 5mm/min test at room temperature, calculate tensile strength (MPa) and start Modulus (GPa).

UL-94 VTM vertical thin test, the sample is cut to size 8" x 2", one end is crimped onto the iron rod, and the cotton is placed directly underneath, and the fire is applied to the sample. Maintain 3 seconds, detect the flame self-extinguishing time t1, and observe whether the sample dripped, and fall in the case of cotton. After cooling, repeat the test on the same sample. The self-extinguishing time of the detection is t2, if t1+t2 If it is less than 10 seconds, and no dripping occurs, it is recorded as the flame retardant grade VTM-0; if t1+t2 is between 10 and 30 seconds and is in the case of dripping, it is recorded as the flame retardant grade VTM-1.

For the horizontal orientation contact angle measurement, the film samples were cut to a size of 2 cm each in length and width, and as for the instrument platform, droplets of about 5 μL in size were dropped at room temperature, and each sample was tested three times.

Thermal properties of materials

Figure 7 is a dynamic mechanical analysis (DMA) diagram of the material (VII-Ian) series (where VII-Ia-0 is pure PI). The glass transition temperature (T _g ) of the sample is known from the temperature corresponding to the peak of the damping (tan δ). When the content of the compound (Va) increases, the glass transition temperature (T _g ) of each series has a significant upward trend; The most abundant sample (VII-Ia-3) increased the glass transition temperature (Tg) by about 50 ° C compared to the pure PI sample (VII-Ia-0).

On the other hand, in Figure 7, it can also be observed that the damping (tan δ) value is significantly reduced with the increase of the compound (Va) content, indicating that the crosslink density of the material is increased, thereby making the film more rigid, and The formation of the cross-linked structure gives a very significant increase in the glass transition temperature (T _g ) of the material, and even excellent properties of 349 ° C (VII-Ia-3) can be obtained.

The dimensional stability of the material was investigated by thermomechanical analysis (TMA) and the results are shown in Figure 8. It can be seen from the figure that the measured glass transition temperature (T _g ) gradually increases with the increase of the compound (Va), which has the same tendency as the dynamic mechanical analysis (DMA) result.

Measuring its thermal expansion coefficient (CTE) from 50 ° C to 200 ° C shows that as the compound (V-a) increases, the coefficient of thermal expansion will also gradually decrease, indicating that the overall molecule is due to the increase in crosslink density. The movement is extremely limited, thereby improving the dimensional stability of the material, and the polymer (VII-I-a-3) can obtain an excellent property of a thermal expansion coefficient of 24 ppm/°C.

All thermal properties analysis is summarized in Table 1.

Material thermal stability

Thermal stability analysis (TGA) was used to investigate the thermal stability of the material. Figure 9 shows the results of analysis of each sample in a nitrogen atmosphere. When the content of the compound (Va) in the material increases, the 5% weight loss temperature (T _{d 5%} ) The significant decrease is mainly due to the fact that the compound (Va) structure contains a PC bond with a lower bond energy, making it easy to break the bond at a temperature of about 400 ° C, thus causing a decrease in the thermal stability of the polymer. Nevertheless, in the VII-Ia-3 sample, good thermal stability of 5% weight loss temperature (T _{d 5%} ) greater than 440 ° C can be maintained. On the other hand, when the temperature reaches 800 ° C, residual coke from the sample can be obtained. The Char yield was observed to have not changed much, and the sample was able to retain a very good thermal stability.

The sample was subjected to UL-94 flame retardant test, the obtained film was VTM-0 flame retardant grade, and the control material VII-Ia-0, the film containing the compound (Va) was prepared, and t ₁ +t ₂ was measured to be about 7 seconds. It is reduced to a high flame retardancy of less than 2 seconds. Mainly because the compound (Va) is a phosphorus-containing structure, it is introduced into a polymer material to form a coke layer with oxygen when it is burned, thereby improving the flame retarding effect. The data measured for each film are summarized in Table 2.

Mechanical properties and hydrophobicity of materials

The sample was tested by a tensile machine to investigate its mechanical properties. The resulting stress-strain relationship is shown in Figure 10. The data show that the ring-opening cross-linking of the introduced compound (V-a) leads to the molecular chain spacing being expanded, reducing the intermolecular attraction and reducing the regularity of the molecular chain arrangement, thus reducing the Tensile strength.

On the other hand, as the content of the compound (Va) increases, the crosslink density increases, and the polymer structure forms a more rigid network structure, resulting in a decrease in the elongation at break of each series of films, but The initial modulus is increased. The data is summarized in Table 3.

In order to investigate the hydrophobicity of the sample, the contact angle of each series of sample films was carried out (Contact Angle) test, the obtained observation chart is shown in Figure 11, because the compound (Va) has an ethyl structure with hydrophobic properties, and the Mannich bridge structure generated after ring-opening polymerization also has the advantage of helping to improve Methylene groups of hydrophobic properties, therefore, with the increase in the content of the compound (Va), a tendency for the contact angle to rise significantly is observed.

The following patent claims are intended to define the scope of the invention. It should be understood that the obvious modifications that can be made by the skilled person based on the disclosure of the present invention are also within the scope of the present invention.

Claims (19)

An oxonitrobenzocyclohexane resin of a compound of formula (VI), Wherein R ₁ and R ₂ are independently C ₁ -C ₆ alkyl; R ₃ is selected from hydrogen, C ₁ -C ₆ alkyl, phenyl, C ₁ -C ₆ alkoxy, phenylalkyl, benzene a group consisting of an oxy group, a C ₁ -C ₆ haloalkyl group, a C ₃ -C ₇ cycloalkyl group, a -CF ₃ group and a halogen atom; B is H or ; R ₄ is a C ₁ -C ₆ alkylene group. The oxynitrobenzoxylcyclohexane resin of claim 1, wherein when B is H, the compound of formula (VI) is formula (VIi) The oxobenzobenzocyclohexane resin of claim 2, wherein when R ₁ and R ₂ are ethyl and R ₃ is methyl, the compound of formula (VIi) is formula (VIia) The oxynitrobenzo-cyclohexane resin of claim 1, wherein B is , the compound of formula (VI) is of formula (VI-ii) The oxobenzobenzocyclohexane resin of claim 4, wherein when R ₁ and R ₂ are ethyl, R ₃ is methyl, and R ₄ is methyl, the compound of formula (VI-ii) is (V) A process for the preparation of an oxoazobenzocyclohexane resin of the compound of the formula (VI) of claim 1, which comprises the steps of: (a) asymmetric bisamine compound (I) and 2-hydroxybenzaldehyde a compound of a functional group undergoes a condensation reaction, (b) reducing the product obtained in the step (a) with a reducing agent; (c) mixing the product obtained in the step (b) with paraformaldehyde and heating to carry out a reaction to obtain an oxonitrobenzobenzene ring of the compound of the formula (VI) Hexane resin. The method of claim 6, wherein the compound containing a 2-hydroxybenzaldehyde functional group is 2-hydroxybenzaldehyde. The method of claim 6, wherein the compound containing a 2-hydroxybenzaldehyde functional group is 5,5'-methyl bis(2-hydroxybenzaldehyde). The method of claim 6, wherein the step (b) is carried out by using NaBH ₄ as a reducing agent or a palladium carbon catalyst (Pd/C) in a high pressure hydrogen atmosphere. The method of claim 6, wherein the step (c) is carried out by heating to a temperature of from about 50 ° C to about 70 ° C. The method of claim 6, wherein the reaction time of step (c) is from about 10 to about 14 hours. a crosslinked polyimine material of the formula (VII-I), Wherein R ₁ to R _{4 are} as defined in claim 1; and Ar ₁ is selected from the group consisting of: m is selected from an integer from 1 to 100; Ar ₂ is selected from the group consisting of the following groups: , And x and y are independently selected from an integer of from 30 to 300. The crosslinked polyimine material of claim 12, wherein when R ₃ is methyl and R ₄ is methyl, the crosslinked polyimine material of formula (VII-Ia) is The crosslinked polyimine material of claim 13, wherein when R ₁ and R ₂ are ethyl, Ar ₁ is And Ar ₂ is , the crosslinked polyimine material of the formula (VII-Ian) A use of the oxynitrobenzoxylcyclohexane resin of the formula (V-I-ii) of claim 4 for the preparation of a crosslinked polyimine material of the formula (VII-I) of claim 12. A process for the preparation of a crosslinked polyimine material of the formula (VII-I) according to claim 12, which comprises the steps of: (a) oxonitrobenzobenzene of the formula (VI-ii) according to claim 4 a cyclohexane resin is mixed with the bisamine monomer of formula (A) and the dianhydride monomer of formula (B), To form a polyamic acid viscous solution; and (b) to cure the viscous solution at elevated temperature, the crosslinked polyimine material has been obtained; wherein Ar ₁ and Ar ₂ are as defined in claim 12. The method of claim 16, wherein the step (a) is carried out at a low temperature of about 0 °C. The method of claim 16, wherein the reaction ratio of the oxynitride benzocyclohexane resin of the formula (VI-ii) to the bisamine monomer of the formula (A) is based on a total of 10 0:10 to 6:4. The method of claim 18, wherein the ratio of the bisamine monomer of the formula (A) to the dianhydride monomer of the formula (B) is 1:1.