TW201041896A - Asymmetric phosohorus-containing diamines, their polyimides, and method of manufacturing the same - Google Patents

Abstract

A phosphorus-containing diamine having the following formula (I) is disclosed, wherein R1-R6 are independently selected from the group consisting of hydrogen, C1-C10 alkyl, C1-C10 alkyoxy, C1-C10 halo-alkyl, C3-C10 cyclic alkyl, -CF3, -OCF3 and halogen and R7 is selected from the group consisting of C1-C10 alkyl, phenyl, C3-C10 cyclic alkyl, -CF3, and halogen with the proviso that when R7 is methyl or phenyl, R5 and R6 are not hydrogen simultaneously. A method of preparing the phosphorus-containing diamine having the formula (I) is also disclosed. In addition, a phosphorus-containing polyimide having the following formula (PI) is disclosed, wherein R1-R7 are as defined above, Ar'' is selected from the group consisting of, and, and n is 30 to 300. A method of preparing the phosphorus-containing polyimide having the formula (PI) is also disclosed.

Description

201041896 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a phosphorus-based compound and a method of producing the same

law. L-method, especially regarding an imine and its manufacturer [Prior Art]

Since ancient times, fires have been a compound containing nucleus that harms humans to form a composition with high heat resistance. Although the traditional fire-resistant and flame-retardant materials have considerable effects, they produce pure and toxic substances, such as Dioxin, which may cause abnormal metabolism and cause nervousness, sleep disorders, headache, eye diseases, arteriosclerosis, and liver. Diseases such as tumors have been found to cause cancer through animal experiments. In recent years, organophosphorus compounds have been developed to improve the flame retardant properties of high molecular polymers. Compared with halogen-containing flame retardants, organophosphorus compounds do not produce smoke (ie, toxic gases) and are otherwise processable. Good, low addition and low smoke generation, especially when the organophosphorus reactive group is introduced into the main structure of the polymer, the polymer will have more flame retardant effect. Phosphorus-containing compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide

DOPO) is a compound having an active nitrogen atom reactive with electron-deficient compounds, which is compatible with electron-deficient compounds such as benzidine (one), oxirane [2], and horses. Acid (maleic 139871.doc 201041896 acid) [3], bismaleimide [4], diaminobenzophenone [5-6], and p-_ A 0^ (terephthaldicarboxaldehyde:^) reaction, its derivatives are well received by the academic community and the industry. DOPO-derived compounds can be used as raw materials for southern molecular materials such as epoxy resin, polyimine and poly-nitramine. (polyimide, PI) has the advantages of high thermal stability, excellent f-resistance and good mechanical properties. Since the primary bond of the polyimine is a solid structure of the aryl steroid, the poly-imine has a high glass transition. The extremely high melting point of the temperature plate, but because of the poor solubility of polyimine in organic solvents, the lack of processability limits the industrial application of polyimine. However, it has been mentioned in the published literature that the introduction of asymmetry Structure in polyimine [8_] can reduce the number of knives Regularity and crystallinity can effectively improve the solubility of polyimine. It can also increase the glass transition temperature of polymers. According to the invention, the invention utilizes the characteristics of the reaction of organic phosphides with ketones to develop a one-step synthesis. A series of phosphorus-based bisamine compounds with asymmetric structure are used as raw materials for poly-imine in polymer materials, and soluble polyamines with asymmetric structure are synthesized by solution polymerization. References: [! Wang, CS; Lin, c. H. Polymer 1999; 40; 747. U] Lln, C·H>; WanS, CS Polymer 2001, 42, 1869.

[3] Wang, CS; Lin, CH; Wu, CYJ Appl. P〇iym. Sci. 2000, 78, 228. 13987l.d〇, 201041896 [4] Lin, CH; Wang, CSJ Polym. Sci. Part A : Polym. Chem. 2000, 38, 2260.

[5] Liu, Y.L.; Tsai, S. H. Polymer 2002, 43, 5757.

[6] Wu, C. S.; Liu, Y. L.; Chiu, Y.S. Polymer 2002, 43, 1773.

[7] Liu, Y.L.; Wu, C. S.; Hsu, K.Y.; Chang, T. C. J. Polym. Sci. Part A: Polym Chem. 2002, 40, 2329.

[8] Chung, C.L.; Hsiao, S.H., Polymer 2008, 49, 2476. o [9] Wang, C.Y.; Li, G.; Jiang, J.M., Polymer 2009, 50, 1709.

[10] Chern, Y.T.; Tsai, J.U., Macromolecules 2008, 41, 9556.

[11] Chun, I.S.; Kim, S.Y., Macromolecules 2000, 33, 3190.

[12] Yagci, H.; Mathias, L., Polymer 1998, 39, 3779. [Invention] It is an object of the present invention to provide a phosphorus-based bisamine having an asymmetric structure and a method for producing the same, the phosphorus system Diamines can be used as a raw material for polyimine or further used to enhance the flame resistance of materials. Another object of the present invention is to provide a phosphorus-based polyimine which has a preferred solubility and a glass transition temperature, and a process for producing the same. The present invention provides a phosphorus-based bisamine having the structure represented by the chemical formula (I): 139871.doc 201041896

Ri

Among them, Ri~R6 are independent, and the && ^ is selected from the group consisting of ruthenium atoms, C]~Ci 〇 基, Ci~C1(), oxime, C丨~Ci 炫 炫 装, c3~c10 ring a group consisting of an alkyl group, _cf3, _〇cf3 and a halogen atom, and the ulnar system 7 is selected from the group consisting of a Cl~C1Q alkyl group, a phenyl group, a C3~C10 cycloalkyl group, a -CF3 group, and a halogen atom. The group, with the proviso that when R? is a methyl group or a phenyl group, 'R5U is the same hydrogen atom. When the compound of the above formula (1) is a hydrogen atom, R5 is a methyl group, and R7 is an indenyl group, one of the compounds of the formula (I) is a structure represented by the formula ((4).

When R1 to R5 of the compound of the above formula (1) are a hydrogen atom, the core is a fluorenyl group, and the core is a methyl group, a specific example of the compound of the formula (I) is a structure represented by the chemical formula (ib).

NH2 When R1 to R5 of the compound of the above formula (1) are a hydrogen atom, & is isobutyl, and r is a fluorenyl group, a specific example of the compound of the formula (1) is a structure of 13987l.doc 201041896 represented by the formula (Ic).

In the above formula (I), R丨~R_4 is a hydrogen atom, and R5 to R6 are an ethyl group, which is a methyl group. One specific example of the compound of the formula (I) is a structure represented by the chemical formula (Id).

〇 When R! to R4 of the compound of the above formula (1) are a hydrogen atom, r5 to r6 are a fluorine atom 'R·; a methyl group. One specific example of the compound of the formula (1) is a structure represented by the chemical formula (Ie).

When RrR4 of the compound of the above formula (I) is a hydrogen atom, R5 to R·6 are a trifluoromethyl group, and R7 is a methyl group, a specific example of the compound of the formula (1) is a structure represented by the chemical formula (If).

139871.doc 201041896 When R]~ of the compound of the above formula (I) is a hydrogen atom, R_6 is a trianthyl group, and R.7 is a methyl group. One of the compounds of the formula (I) is a chemical formula (Ig). The structure of the show.

The invention also provides a process for preparing a compound of the above formula (I), which comprises reacting an organophosphorus compound of the formula (II), a compound of the formula (III), a compound of the formula (IV) and an acid catalyst to form the formula (I) Compound:

(II)

(IV) wherein RcR·/ is as defined above. According to the above method, wherein when R and R4 are a hydrogen atom, a compound of the formula (Ia), (lb), (Ic), (Id) '(Ie), (If) or (ig) may be included : (1) reacting a compound of the formula (111) with a formula (Π)9,l〇-dioxa-9-oxa-10-filler-i〇_oxide (DOPO) and a selected I group; Ii) adding a compound of the formula (IV) wherein Rs~R0 is fluorenyl and reacting with an acid catalyst to form a compound of the formula (la); or adding a compound of the formula (IV) wherein R5 is a hydrogen atom, a sulfhydryl group and an acid catalyst The reaction is carried out to form a compound of the formula (lb); or the addition & is a hydrogen atom, and I is an isobutyl group 139871.doc -10· 201041896

The compound of the formula (IV) and the acid catalyst are reacted to form a compound of the formula (Ic); or a compound of the formula (IV) wherein R5 to R6 are an ethyl group and an acid catalyst are reacted to form a compound of the formula (Id); Or a compound of the formula (IV) wherein R5 to R6 are a fluorine atom and an acid catalyst are reacted to form a compound of the formula (Ie); or a compound of the formula (IV) wherein R5~6 is a trifluoromethyl group and an acid catalyst are added. The reaction is carried out to form a compound of the formula (If); or a compound of the formula (IV) wherein R5 is a hydrogen atom and R6 is a trifluoromethyl group and an acid catalyst are reacted to form a compound of the formula (Ig). The acid catalyst used in the above method is selected from the group consisting of protic acid and Lewis acid. The acid catalyst used in the above method is selected from the group consisting of acetic acid, p-Toluene sulfonic acid, oxalic acid, methanesulfonic acid, and mommag reagent. ), sulfuric acid, orthanilic acid, 3-pyridinesulfonic acid, sulfanilic acid, hydrogen chloride (HC1), A group consisting of hydrogen bromide (HBr), hydrogen iodide (HI), hydrogen fluoride (HF), trifluoroacetic acid (cf3cooh), nitric acid (hno3), and phosphoric acid (H3P04). The amount of the acid catalyst used in the above method is from 0.1 wt% to 30 wt% of the content of the organic phosphide raw material of the formula (II). The solvent used in the above method is a compound of the formula (IV). The present invention further provides a phosphorus-based polyimine having the following chemical formula (PI), 139871.doc -11 - 201041896

Wherein, as defined by the previous formula (1), the ArM is selected from the group consisting of

Group, η is an integer from 30 to 300. When the RrU of the above formula (ΡΙ) is a hydrogen atom and R5 to R7 are a mercapto group, the structural formula of one of the compounds may be

When the compound of the above formula (PI) is a hydrogen atom and R6 and R7 are a methyl group, the structural formula of one of the compounds may be

(B-PI) 139871.doc -12- 201041896 S Ri~Rs of the above formula (PI) is a hydrogen atom, r6 is an isobutyl group, and is a fluorenyl group. The structural formula of one of the compounds may be

RR~4 of the compound of the above formula (PI) is a hydrogen atom, R5~R^ethyl, and R7 is a fluorenyl group. The structural formula of one of the compounds may be

When the RrR4 of the compound of the above formula (PI) is a hydrogen atom, H6 is a sulfonium 'R_7 is a methyl group'. One of the compounds may have a structural formula of the specific embodiment.

(E-PI) When RrR4 of the above formula (PI) is a hydrogen atom and Rrh is a trimethylmethyl 'R? is a methyl group, one of the compounds may have a structural formula of 139871.doc •13· 201041896

(F-PI) When R1 to R5 of the above formula (PI) are a hydrogen atom and trifluoromethyl R7 is a fluorenyl group, the structural formula of one embodiment of the compound may be

(G-ΡΙ). The present invention also provides a method for preparing a phosphorus-based polyimine according to the above formula (a), which comprises reacting a compound of the formula (1) and a bis-anhydride compound of the formula (V) in a solvent to form a water-repellent method. PI) phosphorus polyimine,

(I) (V) wherein ' Ri~R7 is as defined in the previous formula (1), Ar, is selected from

201041896 group. The solvent used in the above method is selected from the group consisting of xylene, n-methyloxanone (Guess) and m-toluene ((4) resol), preferably using a xylene ww (tetra) mixture or a separate use _ Toluene. [Embodiment] The following embodiments will further the present invention. m ^ ^ < Description ' is only used to limit

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 EXAMPLES The above-described embodiments of the invention will be described in the following specific examples. Example 1 Synthesis of a compound of formula (la) with specific DOPO, 2,6-dimethylaniline, 4'-aminoacetophenone and acid catalyst Synthesis of r]~r4 Each is a wind atom 'R>5~R6 is a methyl group' R7 is a methyl group of the compound of the formula (Ia), and the synthesis procedure is as follows: The organic cyclic phosphorus compound DOPO 25_94 g (0.12 mol) , 4,-methylacetophenone (4'-aminoacetophenone) 16.22 g (0.12 mol), 2,6-dimethylaniline (2,6-dimethylaniline) 43.63 g (0.36 mol) and p-A 1.0376 g of p-Toluene sulfonic acid (4 wt% of DOPO) was placed in a 250 ml three-necked reactor and heated to 130 ° C for 24 hours. 139871.doc -15- 201041896 After the reaction was completed, the stirring was stopped, the reactor was cooled to room temperature, washed with methanol, and dried by filtration to obtain a compound of the formula (la). The β NMR analysis of the compound of formula (la) is shown in Figure 1, with a yield of 75% and a melting point of 280 °C. The high-resolution MASS (C28H31N202P) has a predicted value of 454.4999 and a measured value of 454.1898. Example 2 Synthesis of a compound of formula (lb) with a specific DOPO, o-toluidine, 4'-aminoacetophenone and an acid catalyst to synthesize each hydrogen atom, R6 and R? is a compound of the formula (lb) of a methyl group, and the synthesis procedure is as follows: The organic cyclic phosphorus compound DOPO 10.81 g (〇.〇5 mol), 4'-methylbenzophenone (4'-aminoacetophenone) 6.7585 g (〇.〇5 mol), o-toluidine 21.43 g (0.2 mol) and p-mercaptobenzoic acid (p-

Toluene sulfonic acid) 0.4324 g (4 wt% of DOPO) was placed in a 250 ml two-neck reactor' and heated to 130 ° C for 12 hours. After the completion of the reaction, the stirring was stopped. The reactor was cooled to room temperature, precipitated with ethanol, and dried overnight to obtain a compound of the formula (lb). The 1H NMR analysis is shown in Fig. 2, the yield was 45%, and the melting point was 244 °C. . The high-resolution MASS (C27H25N202P) has an estimated value of 440.4734 and a measured value of 440.1687. Example 3 Synthesis of a compound of formula (Ic) synthesized by special DOPO, 2-tert-butylaniline, 4'-aminoacetophenone and acid catalyst R 丨 ~ 尺 5 each is a hydrogen atom, Re is an isobutyl group and R7 is a methyl group of the compound of the formula (Ic), 139871.doc 201041896 The synthesis steps are as follows: The organic cyclic phosphorus compound DOPO 10.81 g (0.05 Mo Ear), 4'-aminoacetophenone 6.7585 g (0.05 mol), 2-tert-butylaniline (29.85 g (0-2 mol)) and p-methyl 0.4324 g of p-Toluene sulfonic acid (4 wt% of DOPO) was placed in a 250 ml three-neck reactor and heated to 130 ° C for 12 hours. After the reaction was completed, the stirring was stopped, the reactor was cooled to room temperature, poured out with methanol, and precipitated by filtration, and dried by filtration to give a compound of the formula (Ic), yield 65%, melting point 240 °C. The high-resolution MASS (C3()H31N2O2P) has a predicted value of 482.5531 and a measured value of 482.2190. Example 4 Synthesis of a compound of formula (Id) with a specific 00?0,2,6-diethylaniline (2,6-(1丨61:11}/1&11 mountain 116), 4'-曱4'-aminoacetophenone and acid catalysts are synthesized as a hydrogen atom, R5 to R6 are ethyl and R7 is a methyl group of the compound of formula (Id), and the synthesis steps are as follows: The organic cyclic phosphorus compound DOPO 10.81 g (0.05 mol), 4'-aminoacetophenone (6.75 g (0.05 mol), 2,6-diethylaniline (2,6-) Diethylaniline) 29.85 g (0.2 mol) and 0.4324 g of p-Toluene sulfonic acid (4 wt% of DOPO) were placed in a 250 ml three-neck reactor and heated to 130 ° C for continuous reaction. After 12 hours, the reaction was stopped, the reactor was cooled to room temperature, washed with methanol, and dried by filtration to give a compound of formula (Id). C. High-resolution MASS (C3〇H31N202P) 139871.doc 201041896 The estimated value is 482.5531, and the measured value is 482.2198. Example 5 Synthesis of a compound of formula (Ie) with a specific 00?0, 2,6-two Aniline (2,6-(^111〇1>〇811 11^), 4'-aminoacetophenone (4'-aminoacetophenone) and acid catalyst synthesis scale: ^ each is a nitrogen atom, R5~R_6 The compound of the formula (Ie) which is a fluorine group and a methyl group of R7 is synthesized as follows: 10.81 g (0.05 mol) of organic cyclic phosphorus compound DOPO, 4,-mercaptophenone amine (4'-8.111)丨11〇3〇61;〇卩11611〇1^)6.7585 grams (0.05 moles), 2,6-difluoroaniline (2,6-difluoroaniline) 25.83 grams (0.2 moles) and p-nonylbenzene Acid (p-Toluene sulfonic acid) 0.4324 g (4 wt% of DOPO) was placed in a 250 ml three-neck reactor' and heated to 130 ° C for 12 hours. The reaction was stopped and the reactor was cooled to room temperature. It was washed with methanol, filtered, and dried to give a compound of formula (Ie) with a yield of 75% and a sleek point of 235 C. The southern analytical MASS (C26H2iF2N2〇2P) was estimated to be 462.4277 and the measured value was 462.1376. Synthesis of a compound of the formula (If) with a specific DOPO, 2,6-ditrifluoroaniline (2,6-ditri flu oromethyl aniline), 4'-nonylbenzophenone (4, aminoacetophenone) and acid touch The synthesis catalyst has a hydrogen atom, R5~I is a trifluoromethyl group and R? is a methyl group having a compound of the formula (If), and the synthesis steps are as follows: The organic cyclic phosphorus compound DOPO 1〇_81 Gram (0.05 mol), 4,-methyl 139871.doc -18- 201041896 Benzeneamine (4'-aminoacetophenone) 6.7585 g (0.05 mol), 2,6-bis(trifluoromethyl)aniline (2 , 6-bis(trifluoromethyl)aniline) 45.83 g (0.2 mol) and 0.4324 g of p-Toluene sulfonic acid (4 wt% of DOPO) were placed in a 250 ml three-neck reactor, and The temperature was raised to 13 (TC continued to react for 12 hours. After the completion of the reaction, the stirring was stopped, the reactor was cooled to room temperature, washed with methanol, and dried to give a compound of the formula (If), yield 70%, melting point 245 °C. The high-resolution MASS (C28H21F6N202P) has a predicted value of 562.4427 and a measured value of 562.1245. Example 7 Synthesis of a compound of formula (Ig) The synthesis of RrRs by specific DOPO, 2_aminotrifluoromethylbenzene, 4'-aminoacetophenone and acid catalyst was A hydrogen atom, a compound of the formula (Ig) wherein r6 is a trifluoromethyl group and R.7 is a methyl group, and the synthesis procedure is as follows: 10.81 g (0.05 mol) of an organic cyclic phosphorus compound DOPO, 4,-methyl Benzophenone (4'-3111丨11〇3〇61〇卩11611〇116) 6.7585 g (0.05 mol), o-trifluorodecyl aniline (2-3111111〇1; 1^111〇1*〇11161 ;117 ization 61126116) 32.23 g (0.2 mol) and p-Toluene sulfonic acid 0.4324 g (4 wt% of DOPO) placed in a 250 ml three-neck reactor and warmed to i3 ( Rc continued to react for 12 hours. After the reaction was completed, the mixing was stopped, the reactor was cooled to room temperature, washed with methanol, and dried by filtration to obtain a compound of the formula (Ig), yield 75% 'melting point 215 ° C. High resolution The estimated value of MASS (C27H22F3N202P) is 494.4448, and the measured value is 494.137. 139871.doc -19- 201041896 Example 8 Polymer A-PI(a) with formula (A-PI) RrR4 phosphorous synthesized using each a hydrogen atom, r5~r7 is methyl having the formula (Ia) of the

The synthetic procedure for synthesizing the phosphorus-based polyimine A-PI(a) with the compound of ArM is as follows: First, 0.6818 g (1.5 mmol) of the diamine monomer of the formula (ia) and 0.4653 g are weighed. (1.5 mmol) 4,4'-Oxydiphthalic anhydride (ODPA), dissolved in 3.4413 g of NMP to give a solution solids content of about 25%, followed by 8 ML of Xylene was added to a 100 ml three-necked reactor, stirred with water, and the reaction temperature was raised to reflux. After maintaining the reaction for 12 hours, the polyimine solution was directly coated with a coater. The glass substrate is controlled to have a film thickness of about 25 μm. The mixture was heat-treated at 80 ° C for 12 hours in a hot air circulating oven to remove most of the solvent, and then heated to ioo ° c for 1 hour and then warmed to 200 ° C & 30 (rc treatment for 1 hour. Measured by DMA) The glass transition temperature was 327. 〇 (see Figure 4). Example 9 Synthesis of polymer A-PI(b) with formula (A-PI) Using R!~R4 each as a hydrogen atom, R5~R7 are fluorenyl a phosphorus-containing compound of formula (Ia), and Ar"

The synthetic steps of the synthesis of the phosphorus-based polyimine A-PI (b) are as follows: First, 0.681 8 g (1.5 mmol) of the diamine monomer and 0.4833 g (1.5 mmol) are weighed. ,3,4,4'-tetracarboxydiphenyl ketone anhydride (4,4'-139871.doc -20- 201041896 carbonyldiphthalic anhydride, BTDA), dissolved in 3.4954g N-decyl n ketone (NMP) The solution has a solid content of about 250/. Then, add 8 ml of xylene (xylene) to a 1-inch three-necked reactor, remove the water and stir to raise the reaction temperature to reflux. After maintaining the reaction for 2 hours, directly apply the poly-imine solution. It was coated on a glass substrate by a coater, and the film thickness was controlled to be about 25 μm. The mixture was heated in a hot air circulating oven for 8 hours at rc for 12 hours. After removing most of the solvent, the temperature was raised to 100 ° C for 1 hour, and then heated to 200 C and 300 C for 1 hour. The glass transfer was measured by DMA. The temperature Θ is 354 ° C (see Fig. 4). Example 10 The synthesis of the compound A-PI (c) having the formula (A_PI) is carried out using 1 ^ ~ 4 each of which is a hydrogen atom, and r5 to r7 are a fluorenyl group ( The synthetic steps of the phosphorus-containing compound of Ia) and the compound of the compound of Ar'' for the synthesis of the phosphorus-based polyimine A-PI(c) are as follows: First, 0.6818 g (1.5 mmol) of the formula (ia) is weighed. The diamine monomer is dissolved in 0.32.7 g (1.5 mol) of pyrommenic dianhydride (PMDA) and dissolved in 3. 274 g of NMP to make the solution solid content about 25%. Adding 8 ml of diphenylbenzene (Xyiene) to a 1-inch three-necked reactor, stirring with water, raising the reaction temperature to reflux, and maintaining the reaction for 12 hours, then directly coating the polyimine solution. The machine is coated on a glass substrate and controlled to a film thickness of about 25 μη. Heated in a hot air circulating oven at 80 C for 12 hours to remove most of the solution. After the treatment, the temperature was raised to 100 ° C for 1 hour and the temperature was further increased to 2 ° C and 300. (: Each treatment was carried out for 1 hour. The glass transition temperature was measured by DMA to be 4 Torr. (See FIG. 4). 13987l.doc -21 - 201041896 Example 11 Synthesis of polymer A-PI(d) with formula (Α·ΡΙ) The use of formula (la) in which each of Ri-FU is a hydrogen atom 'R5~R7 is a fluorenyl group Phosphorus compounds, with ArM

The synthetic steps of the synthesis of the phosphorus-based polyimine A-PI(d) are as follows: First, 0.68 18 g (1_5 mmol) of the diamine monomer of the formula (Ia) and 0.4413 g (1.5 mmol) are weighed. Ear) 3,3,4,4,4-biphenyltetracarboxylic anhydride (BPDA), dissolved in 3.3694 g of NMP to give a solution solids content of about 25 〇/〇, the receiver and 8 ml of xylene (xylene) were added to a 1-inch three-necked reactor, stirring with water, raising the reaction temperature to reflux, maintaining the reaction for 2 hours, then directly polymerizing the mixture. The imine solution was coated on a glass substrate by a coater, and the film thickness was controlled to be about 25 μm. 8 〇 in a hot air circulation oven. 〇 Heat treatment for 2 hours to remove most of the solvent, then raise the temperature to 〇〇. 〇 丨 丨 hours, then heat up to

Each treatment was carried out at 200 ° C and 300 ° C for 1 hour. The glass transition temperature was measured by DMA to be 371 ° C (see Fig. 4). X Solubility Test Table 1 shows the solubility test of polyimine Α· PI(a) to A-PI(d), parentheses

The data in the case is for the symmetry U polyimine 0 in the G97l () l54i of the Republic of China (Ri~y is hydrogen 'ai·" is XX, < 139871.doc -22· 201041896 shows that the introduction of asymmetric structure can greatly increase the solubility of polyimine, which can effectively improve its processability. Table 1 · Solubility test of asymmetric polyimine

After the gamma of f·, if it is not fully dissolved, then proceed to the temperature step. Ο dissolve. NMP: N-methylrrolidone. Let the liver, the heat in the brackets of the data for the Republic of China application No. 97101541, "Similarity of the symmetry group" according to the solubility data. [Simplified description of the drawing] Fig. 1 is a 1H NMR spectrum of the compound la. Fig. 2 is a 1H NMR spectrum of the compound lb. The figure shows the 1H NMR spectrum of the compound Id. Fig. 4 is a DMA analysis diagram of the polymer A-PI(ad). The following patent application scope is used to define the reasonable protection scope of the present invention. However, it should be understood that the skilled person is based on The obvious improvements that can be achieved by the disclosure of the present invention should also fall within the reasonable scope of protection of the present invention. 139871.doc •23·

Claims (1)

201041896 VII. Patent application scope: l- A phosphorus-based bisamine of general formula (I), R7 ^ (I) Wherein RcR is independently selected from the group consisting of a hydrogen atom, 1 ^1 G thiol, α~(:10 alkoxy, CrC^ohaloalkyl, c3~Ci〇cycloalkyl, ·%, -OCF3, and a halogen atom The group consisting of R? is selected from the group consisting of C1~CW alkyl, stupyl, C3~c10 cycloalkyl, _cf3 and a functional atom, with the following conditions: when R7 is methyl or phenyl When it is a hydrogen atom. ▼ 2. As claimed in the formula (1) Phosphorus bisamine, wherein r]~R4 are each a chlorine atom, (4) when two are methyl groups, 'r7 is a methyl group, and the phosphorus bisamine of the formula (1) (la), or, 201041896 (C) When R5 is a hydrogen atom and R6 is an isobutyl group, R7 is a fluorenyl group, and the phosphorus-based bisamine of the formula (1) is a formula (Ic); (d) when R5 to R6 are ethyl, R7 is a methyl group, and the phosphorus-based bisamine of the formula (I) is of the formula (Id); (e) when R5 to R6 are a fluorine atom, R7 is a fluorenyl group, and the phosphorus-based bisamine of the formula (I) is of the formula (Ie); (f) when R5 to R6 are a trifluoromethyl group, R7 is a methyl group, and the phosphorus-based bisamine of the formula (I) is a formula (If); (g) When R5 is a hydrogen atom and 116 is a trifluoromethyl group, R7 is a fluorenyl group, and the formula is 139871.doc 201041896 (i) The phosphorus-based bisamine is of the formula (Ig). (Ig) 33 3. A method for preparing a phosphorus-based bisamine of the formula (I) according to claim 1, which comprises the organophosphorus compound (II), the compound of the formula (III), the compound of the formula (IV) and the acid contact The medium is reacted to form a phosphorus-based bisamine of formula (I); 4. The method of claim 3, wherein 1^~4 is a hydrogen atom, which comprises, Ο (1) a formula (11) 9,10-dihydro-9-oxa-10-infanta-10-oxide (d〇p〇) reacting with a compound of the formula (ΙΠ) wherein R7 is a fluorenyl group; (ii) reacting a compound of the formula (IV) wherein Rs to R6 is a methyl group and an acid catalyst to form a compound of the formula (la); or adding a compound of the formula (IV) wherein Rs is a hydrogen atom and r6 is a methyl group. The catalyst is reacted to form a compound of the formula (lb); or a compound of the formula (iv) wherein R is a hydrogen atom and the compound of the formula (iv) wherein r6 is an isobutyl group and an acid catalyst are reacted to form a compound of the formula (Ic) or R_5 is added. a compound of the formula (IV) wherein R0 is ethyl and an acid catalyst are reacted to form a compound of the formula (Id); or a compound of the formula (IV) wherein r5 to r6 are a fluorine atom and an acid catalyst are reacted to form a formula ( Ie) 139871.doc 201041896 a compound; or a compound of the formula (IV) wherein R5~6 is a trifluoromethyl group and an acid catalyst are reacted to form a compound of the formula (if); or 115 is added as a hydrogen atom, and the ruler 6 is The trifluoromethyl compound of formula (IV) and the acid catalyst are reacted to form a compound of formula (Ig). 5. The method of claim 3 or 4, wherein the acid catalyst is selected from the group consisting of protic acid and Lewis acid. 6. The method of claim 3 or 4, wherein the acid catalyst is selected from the group consisting of acetic acid, oxalic acid (H2C2O4), pt〇luene sulfonic acid, and methanesulfonic acid. Calmagite, Sulfuric acid, Orthanilic acid, 3-pyridinesuifonic acid, Sulfanilic acid A group consisting of hydrogenated hydrogen (Hci), hydrogen bromide (HBr), hydrogen iodide (HI), hydrogen fluoride (HF), trifluoroacetic acid (CF3COOH), nitric acid (hno3), and phosphoric acid (H3P〇4). 7_ The method of claim 3 or 4 wherein the acid catalyst is used in an amount of from about wt j wt% to about 3 〇 wt% of the raw material content of the formula (π). 8. The method of claim 3 or 4 wherein the method further comprises using a compound of formula (IV) as a solvent. 9. A phosphorus-based polyimine of the formula (PI), 139871.doc 201041896 where Group, η is an integer of 30 to 300. 10. The phosphorus-based polyimine of the formula (9), wherein Ri to R4 are a hydrogen atom, ', (4) when RS to R7 are a fluorenyl group, the phosphorus (PI) polyethylenimine is Formula (A_ pi); or (8) When 1 is a hydrogen atom and ~(iv) is a methyl group, the formula (ρι) is a formula (B-PI); (c) (B-PI) 5 is a hydrogen atom. When R6 is an isobutyl group and the ruler 7 is a methyl group, the formula (PI) is a poly(imine) of the formula (C-PI), or 139871.doc 201041896 (C-PI) (d) when a 7 M & π 6 horse ethyl and R 7 are methyl amines of formula (D_PI); or earth nitrite, the formula (PI) phosphorus system poly N—(E-PI) (1) When R5 to R6 are a difluoromethyl group and I is a methyl group, the (ρι) phosphorus-based polyimine is of the formula (F-PI); 13987Ldoc -6- 201041896 (g) When Rs is hydrogen (pi) 嶙 聚 聚 Atoll' R6 is difluoromethyl and R7 is methyl, the imine is of formula (G-PI); 11. It is defined by ~"(〇-PI)»月求项9. 9 (PI) phosphorus-based polyimine, in which 1^~4 is hydrogen as methyl, and Ar, is selected from ^^, 12. A method of preparing a (pi)m imine according to the formula 9 The reaction of the compound of the formula (1) and the bis-anhydride compound of the formula (v) in a solvent to form a (PI)-filled polyimine, (I) (V) where R^R7 is as defined in claim i, Ar, is selected from 139871.doc 201041896 :03⁄4: and: 〇Γ°~〇 成成群. 13. The method of claim 12, wherein the solvent is selected from the group consisting of xylene, fluorenyl-mercaprolidone, and m-cresol. 14. The method of claim 13 wherein the solvent is dinonylbenzene and anthracene-fluorenylpyrrolidone. 15. The method of claim 13 wherein the solvent is m-cresol. 139871.doc