TWI501974B - Novel phosphinated diamines and novel phosphinated polyimides and preparation method thereof - Google Patents

Description

Novel phosphorus-based bisamine compound and novel phosphorus-based polyimine and preparation method thereof

The present invention relates to a phosphorus-based compound and a process for producing the same, and, in particular, to a phosphorus-based bisamine having an asymmetric structure, a polyimine thereof, and a process for producing the same.

Since ancient times, fires have always been one of the biggest accidents that endanger human life and property. Therefore, various buildings or constructions need fire-resistant and flame-retardant materials as building materials to reduce the losses in the event of fire accidents. Conventional fire-retardant materials are mostly added with a halogen-containing compound to form a composition having high heat resistance. Although traditional fire-retardant materials have a considerable effect on fire suppression, they can produce corrosive and toxic substances, such as Dioxin, which may cause abnormal metabolism and cause nervousness, sleep disorders, headache, eye diseases, arteriosclerosis, Diseases such as liver tumors, and more through animal experiments, can lead to cancer.

Recent studies have shown that organophosphorus compounds can enhance the flame retardant properties of high molecular polymers. Compared with halogen-containing flame retardants, organophosphorus compounds do not produce smoke (ie, toxic gases), and have the advantages of good processability, low added amount, and low smoke generation, especially the introduction of organophosphorus reactive groups. The main structure of the polymer will make the polymer more flame retardant.

Reactive 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) in phosphorus-containing derivatives , DOPO) is highly regarded because it can be combined with, for example, benzoquinone ^[1] , ethylene oxide (oxirane) ^[2] , maleic acid ^[3] , bimaleimide (bismaleimide) ^[4] , diaminobenzophenone ^[5-6] and phthalic acid (terephthaldicarboxaldehyde) ^[7] and other electron-deficient compounds for nucleophilic addition reaction. The DOPO-derived compound can be used as a raw material for a polymer material such as an epoxy resin, a polyimide, or a polyamide. Since bisphenol A is cleavable by acid catalysis to phenol and unstable 4-isopropenylphenol ^[7] , DOPO and bisphenol A are reacted under acid catalysis to form monofunctional Phenolic compounds.

Polyimide (PI) has the advantages of high thermal stability, excellent chemical resistance, and good mechanical properties. Polyethylenimine whose main chain is aromatic has been widely used. Because of their strong structure, the polyimine has a high glass transition temperature and a very high melting point, but its disadvantage is that it has poor solubility in organic solvents and cannot be processed by melting. The industrial applicability of amines is still limited. Therefore, the lack of processability limits the industrial application of polyimine. It is known to introduce an asymmetric structure into a polyimine or to introduce a large substituent ^[8] or a soft group ^[9] into a polyethylenimine side chain, thereby reducing the regularity of molecular stacking and Crystallinity to improve the solubility of polyimine in organic solvents.

According to the above, how to improve the solubility of phosphorus-based polyimine in organic solvents while maintaining its good thermal stability is still an important research topic at present.

[1] Wang, C.S. and Lin, C.H.Polymer 1999;40;747.

[2] Lin, C.H. and Wang, C.S. Polymer., 2001, 42, 1869.

[3] Wang, C.S.; Lin, C.H. and Wu, C.Y.J. Appl.Polym.Sci.2000,78,228.

[4] Lin, C.H. and Wang, C.S.J.Polym.Sci.Part A: Polym.Chem.2000, 38, 2260.

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

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

[7] Andrew J.C. and Julia L.L.J.Org.Chem.1997, 62, 1058.

[8] Wang, Kun-Li; Liou, Wun-Tai; Liaw, Der-Jang; Huang, Sheng-Tung, Polymer, 2008, 49, 1538

[9] Lin, C.H.; Lin, C.H.J Polym Sci Part A: Polym.Chem. 2007, 45, 2897.

The present inventors have found that the introduction of a large phosphorus-containing group of an asymmetric structure into a polymethylene imine structure can effectively enhance its organic solubility as compared with the prior art. Further, the phosphorus-containing polyimine according to the present invention has better flame retardancy and thermo-oxygen stability, and at the same time has a high glass transition temperature.

Phosphate bisamine compound

The present invention provides a phosphorus-based bisamine compound of the formula (I):

Wherein Y ₁ and Y _{2 are} each independently H, C ₁ -C ₆ alkyl, phenyl or CF ₃ , or Y ₁ and Y ₂ together with the carbon atom to which they are attached form a C ₅ -C ₁₃ carbocycle; And R ₁ and R _{2 are} each independently H, C ₁ -C ₆ alkyl or C ₃ -C ₆ cycloalkyl, wherein the cycloalkyl is unsubstituted or via one or more C ₁ -C ₆ alkyl groups Replace.

In one embodiment of the present invention, the phosphorus-based bisamine compound of the formula (I) may be a compound of the formula: Wherein Y ₁ , Y ₂ , R ₁ and R ₂ are as defined above.

In one embodiment of the invention, the phosphorus bisamine compound of formula (I) may be a compound of the formula:

Method for producing phosphorus-based bisamine compound

The present invention provides a method for producing a phosphorus-based bisamine compound of the formula (I),

It contains the following steps:

(i) reacting a compound of formula (DOPO) with a compound of formula (BP),

To produce a compound of formula (II);

(ii) reacting a compound of formula (II) with a compound of formula (DN) in the presence of a base,

To produce a compound of formula (III);

(iii) reducing a compound of formula (III) to produce a phosphorus-based bisamine compound of formula (I) wherein Y ₁ , Y ₂ , R ₁ and R ₂ are as defined above, and L represents an aromatic nucleophilic substitution leaving base.

The term "aromatic nucleophilic substitution leaving group" is a technique well known in the art of organic synthesis. In the process of the present invention, an aromatic nucleophilic substituted leaving group refers to a group suitable as a leaving group in an aromatic nucleophilic substitution reaction. Suitable leaving groups include, but are not limited to, F, Cl, Br, I or sulfonates (e.g., tosylate, methanesulfonate, besylate, triflate, and the like).

In the step (i) of the above method of the present invention, a catalyst may be used to increase the reaction rate, and the catalyst may be an acid catalyst. When an acid catalyst is present, the acid catalyst includes, but is not limited to, oxalic acid, acetic acid, p-Toluenesulfonic acid (PTSA), methanesulfonic acid, fluorosulfonic acid (Fluorosulfonic acid). ), Trifluoromethanesulfonic acid, Sulfuric acid, Orthanilic acid, 3-Pyridinesulfonic acid, Sufanilic Acid), hydrogen chloride (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), hydrogen fluoride (HF), trifluoroacetic acid (CF ₃ COOH), nitric acid (HNO ₃ ), and phosphoric acid (H ₃ PO ₄ ). Further, the amount of the acid catalyst is between 0.1% by weight and 10% by weight of the phenolic compound, preferably between 1% by weight and 5% by weight.

In the above step (i) of the present invention, the reaction time may be from 6 to 24 hours, preferably from 12 to 20 hours, and the reaction temperature is from 90 ° C to 200 ° C.

In the step (i) of the above method of the present invention, a solvent may be optionally used for the reaction. When a solvent is present, the solvent includes, but is not limited to, ethoxyethanol, methoxyethanol, 1-methoxy-2-propanol, monomethyl A cosolvent consisting of propylene glycol monomethyl ether (DOW PM), dioxane, or a solvent as described above.

In the above step (ii) of the present invention, the base is a base catalyst used in a general aromatic nucleophilic substitution reaction, including but not limited to potassium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, and hydroxide. lithium.

In step (iii) of the above process of the present invention, the reduction reaction is a conventional nitro reduction reaction including, but not limited to, reduction under Pd/C catalysis under hydrogen.

Phosphorus bisnitrobenzene compound

The present invention further provides a phosphorus-based bisnitrobenzene compound of the formula (III),

Wherein Y ₁ , Y ₂ , R ₁ and R ₂ are as defined above. This compound is used as a synthetic intermediate of the phosphorus-based bisamine compound of the formula (I) as shown above.

Method for producing phosphorus-based bisnitrobenzene compound

The present invention provides a method for producing a phosphorus-based dinitrobenzene compound of the formula (III), which comprises the steps of:

(i) reacting a compound of formula (DOPO) with a compound of formula (BP),

To produce a compound of formula (II);

(ii) reacting a compound of formula (II) with a compound of formula (DN) in the presence of a base,

To produce a compound of formula (III),

Wherein Y ₁ , Y ₂ , R ₁ , R _{2 ,} L and the reaction conditions of steps (i) and (ii) are as defined above.

Phosphorus polyimine

The present invention further provides a phosphorus-based polyimine which is obtained by polymerizing a phosphorus-based bisamine compound of the above formula (I), a dianhydride monomer, and optionally one or more other bisamine monomers.

In the phosphorus-based polyimine of the present invention, the other bisamine monomer is optionally selected, and any bisamine monomer conventionally suitable for use in polyimine can be selected. For example, the bisamine monomer may be selected from m-phenylenediamine, p-phenylenediamine, and 4,4'-oxydianiline. , 3,4'-diphenylphenyl ether (4,4'-oxydianiline), 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1 , 3-bis(4-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)benzene (1,2-bis (1,2-bis) 4-aminophenoxy)benzene), 1,3-bis(3-aminophenoxy)benzene, 2,5-bis(4-aminophenoxy) Toluene (2,5-bis(4-aminophenoxy)toluene), bis[4-(4-aminophenoxy)phenyl]ether, 4,4'-4,4'-bis[4-aminophenoxy]biphenyl, 2,2-bis[4(4-aminophenoxy)phenyl]propane (2,2-bis a group consisting of [4-(4-aminophenoxy)]phenyl)propane) or an analogue thereof. In an embodiment of the present invention, the other bisamine monomer may be represented by the formula H ₂ NZ-NH ₂ , wherein Z may be

In one embodiment of the present invention, the phosphorus polyimine has the formula (V)

Where R is

Wherein Y ₁ , Y ₂ , R ₁ and R ₂ are as defined above; Z is a residue of the other diamine monomer; Ar is independently a tetravalent organic group; x is an integer from 1 to 100; and y is An integer from 0 to 99.

In the phosphorus-based polyimine of the formula (V), Ar is a tetravalent organic group which is not particularly limited, and is preferably selected from the group consisting of: and Wherein A is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH-, -COO- , -(CH ₂ ) _n -, -O(CH ₂ ) _n2 O- or -COO(CH ₂ ) _n3 OCO-, wherein n, n2 and n3 are each independently an integer from 1 to 10, and * represents a bond point .

In a preferred embodiment of the invention, the Ar system is selected from , , , , with The group formed.

The present invention further provides a method for producing a phosphorus-based polyimine comprising a phosphorus-based bisamine compound of the formula (I), a dianhydride monomer, and optionally one or more other bisamine monomers, as described above, Solution polymerization is carried out under a solvent.

In one embodiment of the present invention, the content of the bis-anhydride monomer is equivalent to the total content of the phosphorus-based bisamine compound of the formula (I) and the optionally added other bisamine monomer as shown above; The ratio of the phosphorus bisamine compound to the other bisamine monomer optionally added is optionally between 10:0 and 1:9, preferably between 9:1 and 1:9.

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

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

Figure 3 is a ¹ H NMR spectrum of the compound of the formula (IV-C).

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

Figure 5 is a dynamic mechanical analysis of a compound of formula (V-C).

Figure 6 is a thermomechanical analysis of the formula (V-C(c)) polyimine.

Figure 7 is a dynamic mechanical analysis of polyimine (ODA-BTDA).

Figure 8 is a thermomechanical analysis of polyimine (ODA-BTDA).

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention, and any modifications and variations which may be obtained without departing from the spirit of the invention are range.

Example 1, Synthesis of Compound of Formula (IV-A)

Take 9,9-bis(4-hydroxyphenyl)fluorene 35.041 g (0.1 mol), DOPO 43.234 g (0.2 mol), p-methylbenzenesulfonate Acid (p-Toluene sulfonic acid) and 1.729 g (4 wt% of DOPO) were placed in a 250 ml three-necked flask, and nitrogen gas was introduced thereto, and the temperature was raised to 140 ° C for 12 hours. After the reaction is completed, cool to room temperature and add a small amount. The ethanol was washed into a three-necked flask, and the filter cake was taken by suction filtration, and dried in a vacuum oven at 100 ° C to obtain a white powder of the compound of the formula (II-A) in a yield of 90%.

23.624 g (0.05 mol) of compound of formula (II-A), 11.14 g (0.055 mol) of 2,4-dinitrochlorobenzene, and 7.602 g of potassium carbonate (0.055) 100 ml of dimethyl acetamide (N, N-Dimethylacetamide) in a 250 ml three-necked flask, nitrogen gas, heating to 80 ° C, reaction for 12 hours, cooling to room temperature after the reaction, pumping The filtrate was filtered, and the filtrate was poured into a saturated brine for several times, and the filter cake was taken by suction filtration, and dried in a vacuum oven at 100 ° C to obtain a yellow powder of the compound of the formula (III-A) in a yield of 80%.

6.38 g (0.01 mol) of the compound of the formula (III-A), palladium carbon catalyst (Pd/C) 0.255 g (4 wt% of III-A), and 30 ml of ethanol were heated in a high pressure reactor to a boiling point of ethanol and stirred. It was repeated three times by introducing a nitrogen gas inflating gas, and then it was repeated three times by introducing a hydrogen gas inflating gas. The pressure was maintained at 140 psi until the pressure no longer decreased. After the reaction was completed, Pd/C was filtered off. The filtered droplets were precipitated into 500 ml of deionized water to collect the product. Drying in a vacuum oven at 70 ° C gave a dark red powder of the compound of formula (IV-A) in a yield of 75%. The ¹ H-NMR spectrum of IV-A is shown in Fig. 1 .

Example 2 Synthesis of a compound of the formula (IV-B)

Take 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane (28.439 g (0.1 mol)), DOPO 43.234 g (0.2 mol), p-Toluene sulfonic acid 1.729 g (4 wt% of DOPO), placed in a 250 ml three-necked flask, purged with nitrogen, and warmed to 140 ° C, the reaction 12 hours. After the reaction is completed, the mixture is cooled to room temperature, and a small amount of ethanol is added to the three-necked flask for washing. After suction filtration, the filter cake is taken and dried in a vacuum oven at 100 ° C to obtain a white powder of the compound of the formula (II-B). The yield was 92%.

18.92 g (0.05 mol) of compound of formula (II-B), 11.14 g (0.055 mol) of 2,4-dinitrochlorobenzene, 7.602 g of potassium carbonate (0.055 g (0.055) 100 ml of dimethyl acetamide (N, N-Dimethylacetamide) in a 250 ml three-necked flask, nitrogen gas, heating to 80 ° C, reaction for 12 hours, cooling to room temperature after the reaction, pumping The filtrate was filtered, and the filtrate was poured into a saturated saline solution for several times. The filter cake was taken by suction filtration, and dried in a vacuum oven at 100 ° C to obtain a yellow powder of the compound of the formula (III-B) in a yield of 85%.

5.44 g (0.01 mol) of the compound of the formula (III-B), 0.218 g (4 wt% of III-B) of palladium carbon catalyst (Pd/C), and 30 ml of ethanol were heated in a high pressure reactor to a boiling point of ethanol and stirred. It was repeated three times by introducing a nitrogen gas inflating gas, and then it was repeated three times by introducing a hydrogen gas inflating gas. The pressure was maintained at 140 psi until the pressure no longer decreased. After the reaction was completed, Pd/C was filtered off. The deep red crystal IV-B was obtained by standing at room temperature, and the yield was 65%. The ¹ H-NMR spectrum of IV-B is shown in Fig. 2 .

Example 3, Synthesis of a compound of formula (IV-C)

Take bisphenol A (Bisphenol A) 22.829 g (0.1 mol), DOPO 43.234 g (0.2 mol), p-Toluene sulfonic acid 1.729 g (4 wt% of DOPO), placed In a 250 ml three-necked flask, nitrogen gas was introduced, and the temperature was raised to 130 ° C for 12 hours. After the reaction is completed, it is cooled to room temperature, and a small amount of ethanol is added to the three-necked flask for washing. After filtering with air, the filter cake is taken and dried in a vacuum oven at 100 ° C to obtain a white powder of the compound of the formula (II-C). The yield was 88%. Its structural formula is as follows

Taking 17.518 g (0.05 mol) of compound of formula (II-C), 11.14 g (0.055 mol) of 2,4-dinitrochlorobenzene, 7.602 g of potassium carbonate (0.055 g (0.055) 100 ml of dimethyl acetamide (N, N-Dimethylacetamide) in a 250 ml three-necked flask, nitrogen gas, heating to 80 ° C, reaction for 12 hours, cooling to room temperature after the reaction, pumping The filtrate was filtered, and the filtrate was poured into a saturated brine for several times, and the filter cake was taken by suction filtration, and dried in a vacuum oven at 100 ° C to obtain a yellow powder of the compound of the formula (III-C) in a yield of 82%.

5.16 g (0.01 mol) of the compound of the formula (III-C), 0.26 g of Pd/C (4 wt% of III-C), and 30 ml of ethanol were heated in a high pressure reactor to a boiling point of ethanol and stirred. It was repeated three times by introducing a nitrogen gas inflating gas, and then it was repeated three times by introducing a hydrogen gas inflating gas. The pressure was maintained at 140 psi until the pressure no longer decreased. After the reaction was completed, Pd/C was filtered off. The filtered droplets were precipitated into 500 ml of deionized water to collect the product. Drying in a vacuum oven at 70 ° C gave a dark red powder of the compound of formula (IV-C) in a yield of 72%. The ¹ H-NMR spectrum of IV-C is shown in Fig. 3.

Example 4 Synthesis of a compound of formula (IV-D)

Take 1,1'-bis(4-hydroxyphenyl)cyclohexane (26.835 g (0.1 mol), DOPO 43.234 g (0.2 mol), p-toluenesulfonic acid (p-Toluene sulfonic acid) 1.729 g (4 wt% of DOPO), placed in a 250 ml three-necked flask, purged with nitrogen, heated to 130 ° C, and reacted for 12 hours. After the reaction is completed, it is cooled to room temperature, and a small amount of ethanol is added to the three-necked flask for washing. After suction filtration, the filter cake is taken and dried in a vacuum oven at 100 ° C to obtain a white powder of the compound of the formula (II-D). The rate is 92%.

19.521 g (0.05 mol) of compound of formula (II-D), 11.14 g (0.055 mol) of 2,4-dinitrochlorobenzene, 7.602 g of potassium carbonate (0.055 g (0.055) 100 ml of dimethyl acetamide (N, N-Dimethylacetamide) in a 250 ml three-necked flask, nitrogen gas, heating to 80 ° C, reaction for 12 hours, cooling to room temperature after the reaction, pumping The filtrate was filtered, and the filtrate was poured into a saturated brine for several times, and the filter cake was taken by suction filtration, and dried in a vacuum oven at 100 ° C to obtain a yellow powder with a yield of 86%. Recrystallization from ethanol gave the compound of formula (III-D) in a yield of 59%.

5.56 g (0.01 mol) of the compound of the formula (III-D), 0.222 g (4 wt% of III-D) of Pd/C, and 30 ml of ethanol were heated in a high pressure reactor to a boiling point of ethanol and stirred. It was repeated three times by introducing a nitrogen gas inflating gas, and then it was repeated three times by introducing a hydrogen gas inflating gas. The pressure was maintained at 140 psi until the pressure no longer decreased. After the reaction was completed, Pd/C was filtered off. Upon standing at room temperature, a deep red crystal of the compound of the formula (IV-D) was obtained in a yield of 75%. The ¹ H-NMR spectrum of the formula (IV-D) is shown in Fig. 4 .

Example 5, Synthesis of Poly(imine) of Formula (V-C(c))

1.0 g (2.19 mmol) of the bis-amine compound of the formula (IV-C) and 0.4387 g (2.19 mmol) of 4,4'-Oxydianiline (ODA) were dissolved. M-cresol (m-cresol) 16 ml, maintained with nitrogen for 30 minutes, after complete dissolution, add 4,4'-carbonyldiphthalic anhydride (BTDA) 1.412 g (2.19) *2 millimolar), the solid content is approximately 12% by weight. At the same time, a small amount of isoquinoline is quickly added to help the ring-closing reaction, and then the temperature is rapidly raised to 170 ° C for high-temperature ring closure. After the reaction is completed, it is poured into methanol to precipitate, repeated washing several times, and placed in a vacuum oven at 70 ° C to dry. Skin color fibrous product. Next, a 15 wt% solid solution was prepared with N-methylrrolidone (NMP), and the solution was controlled to a thickness of about 45 μm by an automatic film coater to be uniformly coated on a glass substrate. The temperature was raised to 60 ° C in a circulating oven for 12 hours. After removing most of the solvent, the temperature was raised to 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour. Thermal imidization. Next, the glass substrate is immersed in water to separate the film from the substrate to obtain a film of the formula (V-C(c)) polyimine. As shown in Fig. 5, the dynamic mechanical analyzer showed a storage modulus of 4.70 GPa and a glass transition temperature of 296 °C. As shown in Fig. 6, the thermomechanical analyzer showed a coefficient of thermal expansion of 39 ppm/° C. and a glass transition temperature of 275 ° C.

Example 6, Synthesis of Compound V-A (c)

The reaction conditions were the same as in Example 5 except that the bisamine compound of the formula (IV-C) was changed to the bisamine compound of the formula (IV-A). The dynamic mechanical analyzer showed a storage modulus of 3.84 GPa and a glass transition temperature of 312 °C. The thermomechanical analyzer showed a coefficient of thermal expansion of 36 ppm/° C. and a glass transition temperature of 288 ° C.

Example 7, Synthesis of Compound V-B(c)

The reaction conditions were the same as in Example 5 except that the bisamine compound of the formula (IV-C) was changed to the bisamine compound of the formula (IV-B). The dynamic mechanical analyzer showed a storage modulus of 3.11 GPa and a glass transition temperature of 306 °C. The thermomechanical analyzer showed a coefficient of thermal expansion of 32 ppm/° C. and a glass transition temperature of 282 ° C.

Example 8, Synthesis of Compound V-D(c)

The reaction conditions were the same as in Example 5 except that the bisamine compound of the formula (IV-C) was changed to the bisamine compound of the formula (IV-D). The dynamic mechanical analyzer showed a storage modulus of 6.23 GPa and a glass transition temperature of 305 °C. The thermomechanical analyzer showed a coefficient of thermal expansion of 37 ppm/° C. and a glass transition temperature of 285 ° C.

Comparative Example, Synthesis of Polyimine (ODA-BTDA)

Polyimine (ODA-BTDA) is polymerized from 4,4'-diaminodiphenyl ether (ODA) and 4,4'-carbonyldiphthalic anhydride (BTDA). to make.

Take 4,4'-diaminodiphenyl ether (ODA) 1.0 g (4.99 mmol) and 4,4'-tetracarboxybenzophenone anhydride (BTDA) 1.609 g (4.99 mmol) dissolved in water N,N-Dimethylacetamide was stirred in an ice bath under nitrogen for 12 hours to form a polyamic acid viscous solution, which was then coated on a glass substrate by a coater. Placed in a circulating oven After heating to 60 ° C for 12 hours, most of the solvent was removed, and the temperature was raised by 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour to carry out thermal imidization. Next, the glass substrate was immersed in water to separate the film from the substrate to obtain a film of polyimine.

Figure 7 shows dynamic mechanical analysis data for polyimine (ODA-BTDA) with a storage modulus of 8.91 GPa and a glass transition temperature of 294 °C. Figure 8 shows thermoelastic analysis data of polyimine (ODA-BTDA) with a coefficient of thermal expansion of 53 ppm/°C and a glass transition temperature of 270 °C.

The phosphorus-based polyimine of the present invention has a lower storage modulus and thermal expansion coefficient and a higher glass transition temperature than the polyimine obtained without using the bisamine compound of the present invention. Further, since the present invention introduces a phosphorus-based compound into the polyimine, the flame retardancy and thermo-oxidation stability of the polyimide can be improved.

Solubility test

The table below shows the results of solubility experiments of the example compounds V-A(c), V-B(c), V-C(c) and V-D(c) according to the present invention and the comparative compound ODA-BTDA. This experiment was carried out by adding 5 mg of the test compound to the corresponding solvent in the 0.5 mL table. In the table below, the symbol "+" indicates that the test compound can be dissolved in the corresponding solvent at room temperature; the symbol "+h" indicates that the test compound is soluble in the corresponding solvent under heating; the symbol "+-" indicates the test. The compound is only partially dissolved in the corresponding solvent under heating; the symbol "-" indicates that the test compound is not dissolved in the corresponding solvent under heating. As is apparent from the following table, the compounds V-A(c), V-B(c), V-C(c) and V-D(c) according to the present invention have better solubility in different solvents than the comparative compound ODA-BTDA.

Claims (18)

a phosphorus-based bisamine compound of the formula (I), Wherein Y ₁ and Y _{2 are} each independently H, C ₁ -C ₆ alkyl, phenyl or CF ₃ , or Y ₁ and Y ₂ together with the carbon atom to which they are attached form a C ₅ -C ₁₃ carbocycle; R ₁ and R _{2 are} each independently H, C ₁ -C ₆ alkyl or C ₃ -C ₆ cycloalkyl, wherein the cycloalkyl is unsubstituted or substituted by one or more C ₁ -C ₆ alkyl groups . A compound of claim 1 which is a compound of the formula: A method for producing a phosphorus-based bisamine compound having the formula (I), It comprises the steps of: (i) reacting a compound of formula (DOPO) with a compound of formula (BP), To produce a compound of formula (II); (ii) reacting a compound of formula (II) with a compound of formula (DN) in the presence of a base, To produce a compound of formula (III); (iii) reducing a compound of formula (III) to produce a phosphorus-based bisamine compound of formula (I) wherein Y ₁ , Y ₂ , R ₁ and R ₂ are as defined in claim 1 and L represents aromatic nucleophile Substituting the leaving group. The method of claim 3, wherein the step (i) is carried out in the presence of an acid catalyst. The method of claim 4, wherein the acid catalyst is selected from the group consisting of p-Toluenesulfonic acid (PTSA), Methanesulfonic acid, Sulfuric acid, and oxalic acid. group. The method of claim 3, wherein the base is potassium carbonate. The method of claim 3, wherein the reduction is carried out under Pd/C catalysis under hydrogen. The method of claim 3, wherein the aromatic nucleophilic substitution leaving group is F, Cl, Br, I or a sulfonate. a phosphorus-based bisnitrobenzene compound of the formula (III), Wherein Y ₁ , Y ₂ , R ₁ and R ₂ are as defined in claim 1. A method for producing a phosphorus-based bisnitrobenzene compound having the formula (III), It comprises the steps of: (i) reacting a compound of formula (DOPO) with a compound of formula (BP), To produce a compound of formula (II); (ii) reacting a compound of formula (II) with a compound of formula (DN) in the presence of a base, To produce a compound of formula (III) wherein Y ₁ , Y ₂ , R ₁ and R ₂ are as defined in claim 1 and L represents an aromatic nucleophilic substituted leaving group. A phosphorus-based polyimine, which is a phosphorus-based bisamine compound of the formula (I) of claim 1 The dianhydride monomer and other diamine monomers selected as needed are polymerized. The phosphorus-based polyimine of claim 11, which is a phosphorus-based polyimine of the formula (V) Where R is Wherein Y ₁ , Y ₂ , R ₁ and R ₂ are as defined in claim 1; Z is a residue of the bisamine monomer; each of Ar is independently a tetravalent organic group; and x is an integer from 1 to 100; y is an integer from 0 to 99. The phosphorus-based polyimine of claim 12, wherein the Ar is selected from the group consisting of: and Wherein A is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH-, -COO- , -(CH ₂ ) _n -, -O(CH ₂ ) _n2 O- or -COO(CH ₂ ) _n3 OCO-, wherein n, n2 and n3 are each independently an integer from 1 to 10, and * represents a bond point . The phosphorus-based polyimine of claim 13, wherein the Ar is selected from the group consisting of: The phosphorus-based polyimine of claim 12, wherein Z is A method for producing a phosphorus-based polyimine according to claim 11, which comprises a phosphorus-based bisamine compound of the formula (I), a dianhydride monomer, and optionally other diamine monomers, as in claim 1 Solution polymerization is carried out under a solvent. The method of claim 16, wherein the content of the bis-anhydride monomer is equivalent to the total content of the phosphorus-based bisamine compound of the formula (I) of claim 1 and the optionally added other bisamine monomer. The method of claim 17, wherein the ratio of the phosphorus bisamine compound of the formula (I) of claim 1 to the other bisamine monomer optionally added is optionally between 10:0 and 1:9.