TW201502134A - Novel phosphinated compounds, phosphinated curable polyimides, and the preparation thereof - Google Patents

Abstract

A series of novel phosphinated compounds and novel phosphinated curable polyimides. Their preparation methods are also disclosed.

Description

Novel phosphorus compound, phosphorus crosslinkable polyimine and manufacturing method thereof

The present invention relates to a series of phosphorus-based compounds and a series of phosphorus-based cross-linkable polyimines and a process for the preparation thereof.

Aromatic polyimine is widely used in electronic materials and composite materials because of its excellent properties such as high glass transition temperature, good thermal stability, and good mechanical properties [1-9]. However, good thermal stability is often accompanied by disadvantages such as poor organic solubility, which limits its processability. Therefore, many methods have been proposed to improve its organic solubility, including: (1) introduction of heat stable but flexible segments, such as ether, methylene, sulfonic acid, hexafluoroisopropylidene [10-12] (2) introduction of asymmetric segments or macro-substituents [13-19]; (3) copolymerization [24-29].

Although organic soluble polyimine retains processability, it has reduced thermal stability compared to insoluble polyimine. The literature indicates that many thermoset polyimines are introduced into crosslinkable segments at the end, such as phenylmaleic [30], phenylethynyl [31,32], maleic (maleic) [ 33], nadic [34, 35], allylic [36], benzocyclobutene [37], carboxylic acid [38]. However, thermoset polyimine having crosslinkable functional groups in the repeating unit is rarely discussed.

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The present invention relates to a series of phosphorus-based compounds and a series of phosphorus-based cross-linkable polyimines and a process for the preparation thereof.

Phosphorus compound

The present invention discloses a phosphorus-based compound having the following general formula (I):

Where X is -OH or A is -O- or Q is selected from -NO ₂ or -NH ₂ , with a group consisting of; R ₁ , R ₂ , R ₃ and R ₅ are each independently selected from a hydrogen atom, a phenyl group, a phenoxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₁ group _; a group consisting of ~C ₆ haloalkyl, C ₃ -C ₇ cycloalkyl, -CF ₃ , -OCF ₃ and a halogen atom; R ₄ is a C ₂ -C ₆ alkenyl group; R is selected from C ₁ -C ₆ alkyl, phenyl, C ₁ -C ₆ alkoxy, phenylalkyl, phenoxy, C ₁ -C ₆ haloalkyl, C ₃ -C ₇ cycloalkyl, -CF ₃ and a halogen atom And a, b, c, d, and m are integers each of 1 to 4.

When X of the compound of the above formula (I) is -OH, the compound is a compound of the formula (II-1)

When the compound of the above formula (I) has X And when Q is -NO ₂ , the compound is a compound of formula (III-1)

When the compound of the above formula (I) has X And when Q is -NH ₂ , the compound is a compound of formula (IV-1)

When R ₁ , R ₂ , R ₃ and R _{5 of} the above formula (I) are each a hydrogen atom, R ₄ is an allyl group, and X is -OH, the compound is a compound of the formula (II)

When R ₁ , R ₂ , R ₃ and R _{5 of} the compound of the above formula (I) are each a hydrogen atom, R ₄ is an allyl group, and X is , A is -O-, and when Q is -NO ₂ , the compound is a compound of formula (III)

When R ₁ , R ₂ , R ₃ and R _{5 of} the compound of the above formula (I) are each a hydrogen atom, R ₄ is an allyl group, and X is , A is -O-, and when Q is -NH ₂ , the compound is a compound of formula (IV)

Method for preparing phosphorus compound

The present invention provides a process for preparing a compound of the above formula (II-1), which comprises reacting a phosphorus compound of the formula (1) with a compound of the formula (2) and a compound of the formula (3) under acid catalysis to obtain the formula (II-1). Compound

Wherein R ₁ , R ₂ , R ₄ , R, a, b, c, d and m are as defined above.

According to the above method, wherein R ₁ , R ₂ and R _{3 are} each a hydrogen atom, R ₄ is an allyl group, and R is a methyl group, which comprises a phosphorus compound of the formula (1) and a compound of the formula (2) and a formula ( 3) The compound is reacted under acid catalysis to give a compound of formula (II).

In the above method, for example, the phosphorus compound of the formula (1) is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10- Phosphatanthrene 10-oxide, DOPO), the compound of formula (2) is 4-hydroxyacetophenone, and the compound of formula (3) is 2-allylphenol.

The acid used in the above methods is well known in the art, such as p-toluenesulfonic acid (p-TSA).

The reaction temperature and time used in the above method are those known in the art, for example, the reaction temperature is between 45 ° C and 75 ° C, preferably between 50 ° C and 70 ° C, and most preferably between 55 ° C and 65 ° C. The reaction time may be between 9 hours and 15 hours, preferably between 10 hours and 14 hours, and most preferably between 11 hours and 13 hours.

The present invention provides a process for preparing a compound of the above formula (III-1) which comprises reacting a compound of the formula (II-1) with a compound of the formula (4) under a base catalysis to obtain a compound of the formula (III-1).

Where B is halogen or Y is a halogen, and R ₁ to R ₅ , R, a, b, c, d, and m are as defined above.

According to the above method, wherein R ₁ , R ₂ , R ₃ and R _{5 are} each a hydrogen atom, R ₄ is an allyl group, R is a methyl group, A is -O-, and B is F, which includes formula (II) -1) The compound is reacted with a compound of the formula (4) under base catalysis to give a compound of the formula (III).

The base used in the above methods is well known in the art, such as potassium carbonate.

The reaction temperature and time used in the above method are those known in the art, such as a reaction temperature of between 90 ° C and 130 ° C, preferably between 100 ° C and 120 ° C, most preferably from 105 ° C to 115 ° C. The reaction time may be between 9 hours and 15 hours, preferably between 10 hours and 14 hours, and most preferably between 11 hours and 13 hours.

The present invention provides a process for the preparation of a compound of the above formula (IV-1) which comprises reducing a compound of the formula (III-1) to give a compound of the formula (IV-1).

According to the above method, wherein R ₁ , R ₂ , R ₃ and R _{5 are} each a hydrogen atom, R ₄ is an allyl group, R is a methyl group, and A is -O-, which comprises reducing a compound of the formula (III) The compound of formula (IV) is obtained.

The method of reduction in the above process is known to those skilled in the art, such as reduction with Fe/HCl.

Phosphorus crosslinkable polyimine

In another aspect, the present invention discloses a phosphorus-based crosslinkable polyimine having the following formula (V-1), Where A is -O- or R ₁ , R ₂ , R ₃ and R ₅ are each independently selected from a hydrogen atom, a phenyl group, a phenoxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ haloalkyl group. a group consisting of C ₃ -C ₇ cycloalkyl, -CF ₃ , -OCF ₃ and a halogen atom; R ₄ is a C ₂ -C ₆ alkenyl group; R is a C ₁ -C ₆ alkyl group, benzene a group consisting of a C ₁ -C ₆ alkoxy group, a phenylalkyl group, a phenoxy group, a C ₁ -C ₆ haloalkyl group, a C ₃ -C ₇ cycloalkyl group, a -CF ₃ group and a halogen atom; b, c, d and m are each an integer from 1 to 4; n is an integer from 30 to 300; and Ar' is selected from The group formed.

When the phosphorus-based crosslinkable polyimine of the above formula (V-1) is -O-, R ₁ , R ₂ , R ₃ and R ₅ are each a hydrogen atom, R ₄ is an allyl group, and R is an A group. At the base time, it is a phosphorus-based cross-linkable polyimine of formula (V)

When the above formula (V-1) phosphorus-based crosslinkable polyimine is A One embodiment of the phosphorus-based crosslinkable polyimine is of the formula (Va)

Method for preparing phosphorus-based cross-linkable polyimine

The present invention provides a process for preparing a phosphorus-based crosslinkable polyimine of the formula (V-1) which comprises subjecting a compound of the formula (IV-1) to a dianhydride of the formula (5) to obtain a formula (V- 1) Phosphorus-based cross-linkable polyimine,

Where Ar' is selected from The group formed.

According to the above method, wherein A is -O-, R ₁ , R ₂ , R ₃ and R ₅ are each a hydrogen atom, R ₄ is an allyl group, and when R is a methyl group, it comprises a compound of the formula (IV) The dianhydride of the formula (5) is subjected to condensation to obtain a phosphorus-based crosslinkable polyimine of the formula (V).

According to the above method, wherein Ar' is And comprising condensing a compound of the formula (IV-1) as described above with a dianhydride of the formula (5) to obtain a phosphorus-based crosslinkable polyimine of the formula (Va).

Figure 1 is a ¹ H NMR spectrum of compound (II)

Figure 2 is a ¹ H NMR spectrum of compound (IV)

Figure 3 is a dynamic mechanical analysis of (V-a) and (VI-a)

Figure 4 shows the TMA analysis of (V-a) and (VI-a)

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

The implementation of the above related inventions will be illustrated by the following specific examples.

Example 1 Synthesis of Compound (II)

Weigh 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide, DOPO 10.81 g (0.05 mole), 4-hydroxyacetophenone 6.81 g (0.05 mole), 2-allylphenol 6.71 g (0.15 mole), p-toluenesulfonic acid (p-TSA) 0.432 g (by DOPO) Based on a calculation of 4 wt%), it was placed in a 100 ml three-neck reactor. The reaction temperature was controlled at 60 ° C, and a nitrogen gas reaction was carried out for 12 hours. After completion of the reaction, the reactor was cooled to room temperature, and the product was naturally precipitated, poured into ethyl acetate and filtered, and then filtered to afford white product. The product was recrystallized from methanol to give white crystals (II). After suction filtration, it was placed in a vacuum oven and dried at 100 ° C, and the yield was about 70%. Melting point (DSC) 227 ° C. ¹ H-NMR (DMSO- d ₆ ), δ=1.58 (3H, H ¹⁴ ), 3.09 (2H, H ²⁰ ), 4.91 (2H, H ²² ), 5.78 (1H, H ^{21 )} ), 6.57 (3H, H ^17,25 ), 6.96 (1H, H ¹⁶ ), 7.07-7.12 (4H, H ¹⁰ , ²³ , ²⁴ ), 7.14-7.20 (2H, H ⁴ , ⁸ ), ^{7.32 - 7.36} ( 2H, H ³ , ⁹ ), 7.66 (1H, H ² ), 7.95 (1H, H ⁷ ), 8.07 (1H, H ¹ ), 9.33-9.41 (2H, OH).

Synthesis of Compound (III)

Weigh bisphenol monomer (II) 4.6848 g (0.01 mole), 1,4-fluoronitrobenzene (1,4-fluoronitrobenzene) 3.1042 g (0.022 mole), K ₂ CO ₃ 3.0405 g (0.022 mole), NN - 30 mL of dimethylacetamide (DMAc) was placed in a 100 ml three-neck reactor. The reaction temperature was controlled at 110 ° C, and a nitrogen reaction was carried out for 12 hours. After the completion of the reaction, the reactor was cooled to room temperature, the salt was filtered off, and the filtrate was poured into methanol/water (volume ratio = 1/5) to precipitate, and after suction filtration, a yellow powder product (III) was obtained. 80%. Mp ^{(DSC) 184 ℃. 1 H} -NMR (ppm, DMSO- d 6), δ = 1.85-1.90 (3H, H 14), 3.02-3.12 (2H, H 20), 4.83-4.95 (2H, H 22 ), 5.65 (1H, H ²¹ ), 6.88 (1H, H ¹⁷ ), 6.95 (2H, H ²⁸ ), 7.08 (4H, H ²⁵ , ^28' ), 7.15 (1H, H ¹⁰ ), 7.21 (2H, H) ^8,16 ), 7.32 (1H, H ²³ ), 7.38 (1H, H ⁹ ), 7.47 (3H, H 4, ²⁴ ), 7.52 (1H, H ³ ), 7.76 (1H, H ² ), 8.07 (1H , H ⁷ ), 8.18 (1H, H ¹ ), 8.26-8.30 (4H, H ²⁹ , ^29' ).

Synthesis of Compound (IV)

Weigh 2 g of monomer (III) (7 mmole) dissolved in DMAc 20 mL, place in a 100 ml three-neck reactor, slowly drip 15 mL of 50% ethanol in a separatory funnel, and add 1.96 g (35 mmole) of iron. The powder was heated to reflux temperature under a nitrogen atmosphere, and a mixture of 1.5 mL of 37% HCl and 3 mL of 50% ethanol was slowly added dropwise under reflux. After the completion of the dropwise addition, the reaction was continued for 3 hours, and 1.3 mL of ammonia water was added thereto to maintain a constant temperature reaction for 1 hour. After the reaction, the mixture was filtered while hot, and the filtrate was poured into water to precipitate. After suction filtration, the skin color powder product (IV) was obtained in a yield of about 70%. Melting point (DSC) 103 ° C. ¹ H-NMR (ppm, DMSO-D ₆ ), δ = 1.70 (3H, H ¹⁴ ), 4.23 (2H, H ²⁰ ), 4.99 (6H, H ²⁰ , NH ₂ ), 5.82 (1H, H ²¹ ), 6.37 (1H, H ¹⁷ ), 6.57 (4H, H ²⁹ , ^29' ), 6.65 (4H, H ²⁵ , ²⁸ ), 6.73 (2H, H ^28' ), 6.97 (1H, H ¹⁶ ), 7.08 (1H, H ¹⁰ ), 7.20 (4H, H ^8,23,24 ), 7.33 (1H, H ⁹ ), 7.37 (1H, H ⁴ ), 7.43 (1H, H ³ ), 7.70 (1H , H ² ), 7.95 (1H, H ⁷ ), 8.07 (1H, H ¹ ).

Synthesis of crosslinkable polyimine (v-a)

The diamine monomer (IV) 1.301 g (2 mmole) and m-cresol (8.7 g) were placed in a 100 mL three-necked flask and stirred, after the diamine monomer (IV) was completely dissolved. 4,4'-oxydiphthalic anhydride (ODPA) 0.436 g (2 mmole), two drops of isoquinoline, and the temperature was raised to 200 ° C for high temperature closed loop. After the reaction is completed, it is poured into methanol and washed. After filtering, the filter cake is placed in an oven to be dried, and the product can be cross-linked polyimine (Va). The solid content of the solution is 20 wt% in DMAc, and the solution is uniformly coated by an automatic coater. Spread on a glass substrate. The mixture was heated in a circulating oven at 60 ° C for 12 hours, and most of the solvent was dried, and then heated to 100 ° C, 150 ° C, and 200 ° C for 1 hour.

Preparation of crosslinked polyimine (VI-a)

The heat-curable reaction (VI-a) can be obtained by heating the crosslinkable polyimine (V-a) to 300 ° C for 1 hour to carry out a heat curing reaction.

Polymer properties

3 is a DMA chart of (V-a) and (VI-a), and the Tg of (V-a) is increased from 253 ° C to 307 ° C of (VI-a). The modulus of (V-a) increases significantly from the glassy state to the rubbery state. This is because the allyl group on (V-a) enhances the rigidity after the curing reaction. The increase in stiffness can also be observed by the fact that the tan (δ) height of (VI-a) is smaller than (V-a).

4 is a TMA chart of (V-a) and (VI-a), and the Tg of (V-a) is increased from 225 ° C to 277 ° C of (VI-a). Both charts show the advantages of improving Tg after cross-linking. Figure 4 also shows that the coefficient of thermal expansion (CTE) decreases from 52 ppm/°C of (Va) to 29 ppm/°C of (VI-a) in the interval 50-150 °C, and its CTE is significantly smaller than other polyimine. A lot, this also shows the advantages of improving dimensional stability after cross-linking. The thermal stability of PEIs can be seen from the TGA data in Table 1. The 5 wt% pyrolysis temperature in the nitrogen atmosphere (Va) is 443 ° C and the (VI-a) is 447 ° C; in the air environment (Va) 5 wt% The thermal cracking temperature was 440 ° C and (VI-a) was 443 ° C. The coke residual ratio (V-a) in the nitrogen atmosphere was 54% and (VI-a) was 60%; in the air environment (V-a), the coke residual ratio was 20% and (VI-a) was 41%. Even after the thermal curing reaction, there was a significant improvement in Tg and CTE, but there was no significant difference in the initial cracking temperature between (Va) and (VI-a) in TGA, because the PC bond was the most in both systems. It is fragile, so the effect of cross-linking in the initial thermal cracking reaction is not significant, but the effect of cross-linking significantly improves the coke residual rate.

Table 2 shows the thermal flame retardancy test of the two systems with UL-94VTM. Both systems have t ₁ + t ₂ less than 3 seconds. Therefore both reach the VTM-0 rating. Kapton's t ₁ +t ₂ is greater than 6 seconds. Even though Kapton is also a VTM-0 grade, (Va) and (VI-a) still have shorter burn times, indicating that the phosphorus-containing structure provides good flame retardant properties.

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 (22)

a phosphorus compound of the formula (I), Where X is -OH or A is -O- or Q is selected from -NO ₂ or -NH ₂ , with a group consisting of; R ₁ , R ₂ , R ₃ and R ₅ are each independently selected from a hydrogen atom, a phenyl group, a phenoxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₁ group _; a group consisting of ~C ₆ haloalkyl, C ₃ -C ₇ cycloalkyl, -CF ₃ , -OCF ₃ and a halogen atom; R ₄ is a C ₂ -C ₆ alkenyl group; R is selected from C ₁ -C ₆ alkyl, phenyl, C ₁ -C ₆ alkoxy, phenylalkyl, phenoxy, C ₁ -C ₆ haloalkyl, C ₃ -C ₇ cycloalkyl, -CF ₃ and a halogen atom And a, b, c, d, and m are each an integer from 1 to 4. The compound of the formula (I) of claim 1, wherein when X is -OH, the compound is of the formula (II-1); or A compound of formula (I) according to claim 1, wherein X is (a) when Q is -NO ₂ , the compound of formula (I) is of formula (III-1); or (b) When Q is -NH ₂ , the compound of formula (I) is formula (IV-1) A compound of the formula (I) according to claim 1, wherein R ₁ , R ₂ , R ₃ and R _{5 are} each a hydrogen atom, R ₄ is an allyl group, and (a) when X is -OH, the compound of the formula (I) For formula (II); or (b) when X is , A is -O-, Q is -NO ₂ , and the compound of formula (I) is of formula (III); (c) when X is , A is -O-, Q is -NH ₂ , and the compound of formula (I) is of formula (IV); A process for preparing a compound of the formula (II-1) according to claim 2, which comprises reacting a phosphorus compound of the formula (1) with a compound of the formula (2) and a compound of the formula (3) under acid catalysis to obtain a formula (II-1) Compound Wherein R ₁ , R ₂ , R ₄ , R, a, b, c, d and m are defined in claim 1. The method of claim 5, wherein R ₁ , R ₂ and R _{3 are} each a hydrogen atom, R ₄ is an allyl group, and R is a methyl group, which comprises a phosphorus compound of the formula (1) and a compound of the formula (2) The compound of formula (3) is reacted under acid catalysis to give a compound of formula (II). The method of claim 5, wherein the acid is p-toluenesulfonic acid (p-TSA). The method of claim 5, wherein the reaction temperature is between 45 ° C and 75 ° C. The method of claim 5, wherein the reaction time is between 9 hours and 15 hours. A process for the preparation of a compound of the formula (III-1) according to claim 3, which comprises reacting a compound of the formula (II-1) with a compound of the formula (4) under a base catalysis to obtain a compound of the formula (III-1), (4) where B is halogen or , Y is a halogen; and R ₁ to R ₅ , R, a, b, c, d, and m are defined in claim 1. The method of claim 10, wherein R ₁ , R ₂ , R ₃ and R _{5 are} each a hydrogen atom, R ₄ is an allyl group, R is a methyl group, A is -O-, and B is F, which includes The compound of formula (II-1) is reacted with a compound of formula (4) under base catalysis to give a compound of formula (III). The method of claim 10, wherein the base is potassium carbonate. The method of claim 10, wherein the reaction temperature is between 90 ° C and 130 ° C The method of claim 10, wherein the reaction time is between 9 hours and 15 hours. A process for the preparation of a compound of formula (IV-1) according to claim 3, which comprises reducing a compound of formula (III-1) to give a compound of formula (IV-1). The method of claim 15, wherein R ₁ , R ₂ , R ₃ and R _{5 are} each a hydrogen atom, R ₄ is an allyl group, R is a methyl group, and A is -O-, which comprises a compound of formula (III) Reduction to give a compound of formula (IV). a phosphorus-based cross-linkable polyimine of the formula (V-1), Where A is -O- or R ₁ , R ₂ , R ₃ and R ₅ are each independently selected from a hydrogen atom, a phenyl group, a phenoxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ haloalkyl group. a group consisting of C ₃ -C ₇ cycloalkyl, -CF ₃ , -OCF ₃ and a halogen atom; R ₄ is a C ₂ -C ₆ alkenyl group; R is a C ₁ -C ₆ alkyl group, benzene a group consisting of a C ₁ -C ₆ alkoxy group, a phenylalkyl group, a phenoxy group, a C ₁ -C ₆ haloalkyl group, a C ₃ -C ₇ cycloalkyl group, a -CF ₃ group and a halogen atom; b, c, d and m are each an integer from 1 to 4; n is an integer from 30 to 300; and Ar' is selected from with The group formed. The phosphorus-based crosslinkable polyimine of claim 17, wherein A is -O-, R ₁ , R ₂ , R ₃ and R ₅ are each a hydrogen atom, R ₄ is an allyl group, and R is a methyl group. The phosphorus-based crosslinkable polyimine of the formula (V-1) is of the formula (V) The phosphorus-based cross-linkable polyimine of claim 18, wherein Ar' is , the phosphorus-based crosslinkable polyimine of the formula (V) is of the formula (Va) A process for the preparation of a phosphorus-based crosslinkable polyimine of the formula (V-1) according to claim 17, which comprises diluting a compound of the formula (IV-1) according to claim 3 with a dianhydride of the formula (5) And obtaining a phosphorus-based crosslinkable polyimine of formula (V-1) Where Ar' is selected from with The group formed. The method of claim 20, wherein A is -O-, R ₁ , R ₂ , R ₃ and R ₅ are each a hydrogen atom, R ₄ is an allyl group, and R is a methyl group, which comprises the same as in claim 3 The compound of the formula (IV) is condensed with the dianhydride of the formula (5) to give a phosphorus-based crosslinkable polyimine of the formula (V). The method of claim 21, wherein Ar' is And comprising the condensation of a compound of the formula (IV-1) as claimed in claim 3 with a dianhydride of the formula (5) to give a phosphorus-based crosslinkable polyimine of the formula (Va).