TWI650344B - Phosphoric phenyl ether oligo polymer having crosslinkable group, preparation method thereof, curing composition and cured product - Google Patents

Abstract

A phosphorus-based phenylene ether oligomer having a crosslinkable group, represented by formula (1), wherein Z, R ¹ , R ² , Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , m and n are as defined in the specification and the scope of the patent application. Formula (1) The present invention also provides a method for preparing a phosphorus-based phenylene ether oligomer having a crosslinkable group, and a curing composition comprising the phosphorus-based phenylene ether oligomer having a crosslinkable group, And a cured product formed by the curing reaction of the curing composition. The cured product has better flame retardancy.

Description

Phosphoric phenyl ether oligo polymer having crosslinkable group, preparation method thereof, curing composition and cured product

This invention relates to a phenyl ether oligopolymer, and more particularly to a phosphorus phenyl ether oligopolymer having a phosphorus group.

U.S. Patent No. 9051465 B1 discloses a curable composition comprising a functionalized phenylene ether oligomer represented by formula (A), a flame retardant, an acrylate-based polymerizable monomer, and an initiator. Formula (A) Z is , , , , single button or X ¹ and X ² are each hydrogen or a C ₁ to C ₁₂ alkyl group; t and u are each from 1 to 500.

In the patent, the flame retardant is formed by the flame retardant by the flame retardant, however, the cured product has a potential problem of poor mechanical properties, and the flame retardant belongs to The small molecular type has a problem that it easily migrates or volatilizes from the cured product, resulting in poor flame retardancy or mechanical properties of the cured product.

In order to improve the above problem of migration or volatilization of the flame retardant, Polymer Degradation and Stability 2014, 99, 105-110 discloses a method of grafting a phosphorus-based flame retardant to a phenyl ether oligopolymer. However, the phosphorus-based phenylene ether oligopolymer obtained by this method cannot be self-hardened or cannot be crosslinked with an epoxy resin.

Accordingly, a first object of the present invention is to provide a phosphorus-based phenylene ether oligomer having a crosslinkable group having a preferred glass transition temperature and flame retardancy.

Thus, the phosphorus-based phenylene ether oligomer having a crosslinkable group of the present invention is represented by the formula (1): Formula (1) Z is a single bond or X ¹ and X ² are each hydrogen or a C ₁ to C ₁₂ alkyl group; R ¹ and R ² are each hydrogen, , ,or ; R ³ is a C ₁ to C ₁₂ alkyl group, a substituted phenyl group, or an unsubstituted phenyl group; each of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ Methyl or And at least one of Y ¹ to Y ⁸ is When Y ² is plural, the Y ² may be the same or different. When Y ³ is plural, the Y ³ may be the same or different. When Y ⁶ is plural, the Y ⁶ may be The same or different, when Y ⁷ is plural, the Y ⁷ may be the same or different; T ¹ , T ² , T ³ , T ⁴ , T ⁵ , T ⁶ , T ⁷ and T ⁸ each represent hydrogen or C ₁ to C ₆ alkyl; m and n are each 5 to 15.

A second object of the present invention is to provide a process for preparing a phosphorus-based phenylene ether oligomer having a crosslinkable group.

Accordingly, the present invention provides a method for preparing a phosphorus-based phenylene ether oligo polymer having a crosslinkable group, comprising the steps of: causing a phenyl ether material represented by the formula (2), a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide compound represented by the formula (2) and the formula (3), Formula (3) undergoes a nucleophilic substitution reaction to form a phosphorus-based phenylene ether oligomer represented by formula (1-1), Formula (1-1) In the formula (2), Z is a single bond or X ¹ and X ² are each hydrogen or a C ₁ to C ₁₂ alkyl group; Y ¹¹ , Y ²¹ , Y ³¹ , Y ⁴¹ , Y ⁵¹ , Y ⁶¹ , Y ⁷¹ and Y ⁸¹ are each a methyl group or a halomethyl group. And at least one of Y ¹¹ , Y ²¹ , Y ³¹ , Y ⁴¹ , Y ⁵¹ , Y ⁶¹ , Y ⁷¹ and Y ⁸¹ is a halomethyl group, and when Y ²¹ is plural, the Y ²¹ may be the same or Differently, when Y ³¹ is plural, the Y ³¹ may be the same or different. When Y ⁶¹ is plural, the Y ⁶¹ may be the same or different, and when Y ⁷¹ is plural, the Y ⁷¹ It may be the same or different; m and n are each 5 to 15; in the formula (3), T ¹ , T ² , T ³ , T ⁴ , T ⁵ , T ⁶ , T ⁷ and T ⁸ each represent hydrogen or C ₁ An alkyl group to C ₆ ; in the formula (1-1), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are each a methyl group or And at least one of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ is When Y ² is plural, the Y ² may be the same or different. When Y ³ is plural, the Y ³ may be the same or different. When Y ⁶ is plural, the Y ⁶ may be The same or different, when Y ⁷ is plural, the Y ⁷ may be the same or different.

A third object of the present invention is to provide a curing composition.

Thus, the curing composition of the present invention comprises the above-mentioned phosphorus-based phenylene ether oligomer having a crosslinkable group.

A fourth object of the present invention is to provide a cured product having better flame retardancy.

Thus, the cured product of the present invention is formed by curing reaction of the above-mentioned curing composition.

The effect of the present invention is to pass through a phosphorus group in the phosphorus-based phenylene ether oligomer having a crosslinkable group represented by the formula (1) ( And the design of the crosslinkable group, so that the cured product formed of the phosphorus-based phenylene ether oligomer having a crosslinkable group represented by the formula (1) has better flame retardancy.

The contents of the present invention will be described in detail below.

<Phosphophenylene oligopolymer having a crosslinkable group represented by the formula (1)>

Preferably, Z is R ¹ and R ² are hydrogen.

Preferably, Z is , R ¹ and R ² are .

Preferably, Z is , R ¹ and R ² are .

Preferably, Z is , R ¹ and R ² are .

<Method for preparing phosphorus-based phenylene ether oligomer having crosslinkable group>

In the present invention, the nucleophilic substitution reaction can be carried out in the presence of an alkaline catalyst. The basic catalyst may be used alone or in combination, and the basic catalyst is, for example but not limited to, potassium carbonate (K ₂ CO ₃ ), sodium carbonate (Na ₂ CO ₃ ), potassium hydroxide (KOH), hydrogen. Sodium oxide (NaOH), sodium carbonate (Na ₂ CO ₃ ), sodium hydrogencarbonate (NaHCO ₃ ), 4-dimethylamino pyridine, N-bromosuccinimide , abbreviated as NBS), or pyridine or the like.

The method for preparing a phosphorus-based phenylene ether oligo polymer having a crosslinkable group according to the present invention further comprises reacting the phosphorus-based phenylene ether oligopolymer represented by the formula (1-1) with a reaction reagent to form a formula (1-2) a phosphorus-based phenylene ether oligo polymer; the reaction reagent is selected from a material having an unsaturated group or acetic anhydride, wherein the unsaturated group is selected from ,or ; Formula (1-2) R ¹¹ and R ²¹ are each , ,or R ³ is a C ₁ to C ₁₂ alkyl group, a substituted phenyl group, or an unsubstituted phenyl group.

The unsaturated group-containing material may be used singly or in combination of plural kinds, and the material having an unsaturated group such as, but not limited to, methacrylic anhydride, methacrylic acid, or (4-chloromethyl) Styrene (4-chloromethylstyrene) and the like. In the present invention, the reaction can be carried out in the presence of an alkaline catalyst. The basic catalyst may be used alone or in combination, and the basic catalyst is, for example but not limited to, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, 4-dimethyl group. 4-dimethylamino pyridine, sodium dimethyl acetamide, or pyridine.

<Curing composition>

The curing composition of the present invention further contains a starter. The initiator is for example but not limited to a peroxide.

<cured product>

The cured product is formed by a curing reaction of the curing composition as described above. The curing reaction has an operating time ranging from 1 hour to 6 hours. The curing reaction has an operating temperature in the range of 160 ° C to 220 ° C.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

Synthesis Example 1

10 g (13.07 mmole) of poly 2,6-dimethylphenyl ether bisphenol (label: SABIC; model: SA90), 0.4652 g (13.07 x 0.2 mmole) of N-bromosuccinimide (N -bromosuccinimide (abbreviated as NBS), 0.2 g of azobisisobutyronitrile [2,2'-azobis (2-methylpropionitrile), referred to as AIBN], and 80 ml of chlorobenzene in a 100 ml three-necked flask, stirred Nitrogen gas was introduced, and the temperature was raised to 130 ° C for 4 hours. After the reaction was completed, methanol was added to produce a precipitate. Next, filtration was carried out to obtain a filter cake. The filter cake was then washed several times with methanol to give a dark grey product. The dark gray product was subjected to a drying treatment in a vacuum oven at 80 ° C to form a partially brominated poly 2,6 dimethyl phenyl ether bisphenol represented by the formula (2-1), and the yield was about 85%. The chemical structure of the partially brominated poly(2,6-dimethylphenylene ether bisphenol) represented by the formula (2-1) is The part of the formula (2-1), Y ¹¹ , Y ²¹ , Y ³¹ , Y ⁴¹ , Y ⁵¹ , Y ⁶¹ , Y ⁷¹ and Y ⁸¹ is a bromomethyl group, and the remainder is a methyl group. From the ¹ H-NMR spectrum, it was found that there was a characteristic absorption peak of -CH ₂ -Br at 4.3 ppm.

Synthesis Example 2

10 g of the partially brominated poly(2,6-dimethylphenylether bisphenol) represented by the formula (2-1) of Synthesis Example 1, 100 g of 9,10-dihydro-9-oxa-10-phosphine 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO for short) was placed in a 100 ml three-necked flask, stirred and purged with nitrogen, and the temperature was raised to 140 °C. The reaction was carried out for 24 hours. After the reaction was completed, methanol was added to produce a precipitate. Next, filtration was carried out to obtain a filter cake. The filter cake was then washed several times with methanol to give a brown product. The brown product was subjected to a drying treatment in a vacuum oven at 80 ° C to form a phosphorus-based phenylene ether oligomer represented by the formula (1-1-1), and the yield was about 80%. The chemical structure of the phosphorus-based phenylene ether oligomer represented by the formula (1-1-1) is Formula (1-1-1) wherein Y ¹ , Y ² , Y ³ and Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are The remainder is methyl. From the ¹ H-NMR spectrum, it was found that the characteristic absorption peak of -CH ₂ -Br disappeared at 4.3 ppm, and the characteristic absorption peak of -CH ₂ -P- appeared at 3.3 ppm.

Synthesis Example 3

10 g (11.52 mmole) of the phosphorus-based phenylene ether oligomer represented by the formula (1-1-1) of Synthesis Example 2, 0.098 g of 4-dimethylaminopyridine, and 6.47 g (11.52 × 3) The mmole) methacrylic anhydride was placed in a 100 ml three-necked flask, stirred and purged with nitrogen, and allowed to react at room temperature for 24 hours. After the reaction was completed, methanol was added to produce a precipitate. Next, filtration was carried out to obtain a filter cake. The filter cake was then washed several times with methanol to give a brown product. The brown product was subjected to a drying treatment in a vacuum oven at 80 ° C to form a methacrylate-terminated phosphorus phenyl ether oligomer represented by the formula (1-2-1), and the yield was about 86%. The chemical structure of the methacrylate-terminated phosphorus-based phenylene ether oligomer represented by the formula (1-2-1) is Formula (1-2-1). Referring to Fig. 1, it can be seen from Fig. 1 that there is no characteristic absorption peak of -CH ₂ -Br at 4.3 ppm, and a characteristic absorption peak of -CH ₂ -P- at 3.3 ppm, and -C= at 5.7 ppm. Characteristic absorption peak of CH ₂ . In the infrared spectrum, there is a characteristic absorption peak of C=O at 1720 cm ^-1 and a characteristic absorption peak of C=C at 1650 cm ^-1 .

Synthesis Example 4

10 g (11.52 mmole) of the phosphorus-based phenylene ether oligomer represented by the formula (1-1-1) of Synthesis Example 2, 5.984 g (11.52 × 3 mmole) of 4-chloromethylstyrene, and 6.47 g. Potassium carbonate (11.52 x 2.2 mmole) was placed in a 100 ml three-necked flask, stirred and purged with nitrogen, and the temperature was raised to 85 ° C for 12 hours. After the reaction was completed, methanol was added to produce a precipitate. Next, filtration was carried out to obtain a filter cake. The filter cake was then washed several times with methanol to give a brown product. The brown product was subjected to a drying treatment in a vacuum oven at 80 ° C to form a methyl styrene-terminated phosphorus-based phenyl ether oligomer represented by the formula (1-2-2) in a yield of about 80%. The chemical structure of the methylstyrene-terminated phosphorus-based phenylene ether oligomer represented by the formula (1-2-2) is Formula (1-2-2). Referring to Figure 2, as can be seen from Figure 2, there is at 4.8ppm. The characteristic absorption peaks have a characteristic absorption peak of -C=CH ₂ at 5.3 ppm and 5.9 ppm, and a characteristic absorption peak of -CH ₂ -P- at 3.4 ppm.

Synthesis Example 5

10 g (11.52 mmole) of the phosphorus-based phenylene ether oligomer represented by the formula (1-1-1) of Synthesis Example 2, 5.852 g (11.52 × 2.2 mmole) of acetic anhydride, and 0.01 g of acetic acid, 50 ml The sodium dimethyl acetamide was placed in a 100 ml three-necked flask, stirred and purged with nitrogen, and the temperature was raised to 85 ° C for 12 hours. After the reaction was completed, methanol was added to produce a precipitate. Next, filtration was carried out to obtain a filter cake. The filter cake was then washed several times with methanol to give a brown product. The brown product was subjected to a drying treatment in a vacuum oven at 80 ° C to form an acetate-terminated phosphophenyl ether oligomer represented by the formula (1-2-3), and the yield was about 80%. The chemical structure of the acetate-terminated phosphorus-based phenylene ether oligomer represented by the formula (1-2-3) is Formula (1-2-3). From the ¹ H-NMR spectrum, it was found that there was a characteristic absorption peak of -CH ₂ -P- at 3.4 ppm.

Example 1 Composition for curing and cured product

10 g of the methacrylate-terminated phosphorus-based phenylene ether oligomer represented by the formula (1-2-1) of Synthesis Example 3, and 1.3512 g of epoxy resin (label: DIC; model: HP-) 7200), 6.75 mg of 4-dimethylaminopyridine (used in an amount of 0.5 wt% of the epoxy resin) and 0.2 g of tert-butyl hydroperoxide (the amount used is (1) -2-1) 2% by weight of the methacrylate-terminated phosphorus-based phenylene ether oligo polymer shown was dissolved in 17.0 g of xylene to form a cured composition. The curing composition was applied onto a glass by a glass coater, and then the temperature was raised to 80 ° C to carry out a curing reaction for 12 hours, and then the temperature was further raised to 180 ° C to carry out a curing reaction for 2 hours, and then, The temperature was raised to 200 ° C for 2 hours, and finally, the temperature was raised to 220 ° C for 2 hours. After the curing reaction is completed, a brown cured product is formed on the glass.

Example 2 Composition for curing and cured product

10 g of a methylstyrene-terminated phosphorus-based phenylene ether oligomer represented by the formula (1-2-2) of Synthesis Example 4 and 0.2 g of peroxidized third butanol were used (the amount used was (1). -2-2) 2 wt% of the methyl styrene-terminated phosphorus phenyl ether oligo polymer shown was dissolved in 15 g of xylene to form a cured composition. The curing composition was applied onto a glass by a glass coater, and then the temperature was raised to 80 ° C to carry out a curing reaction for 12 hours, and then the temperature was further raised to 180 ° C to carry out a curing reaction for 2 hours, and then, The temperature was raised to 200 ° C for 2 hours, and finally, the temperature was raised to 220 ° C for 2 hours. After the curing reaction is completed, a brown cured product is formed on the glass.

Example 3 Composition for curing and cured product

10 g of the acetate-terminated phosphorus-based phenyl ether oligomer represented by the formula (1-2-3) of Synthesis Example 5, and 1.3362 g of epoxy resin (label: DIC; model: HP-7200) 6.69 mg of 4-dimethylaminopyridine (used in an amount of 0.5 wt% of the epoxy resin) and 0.2 g of peroxidized third butanol (used in the formula (1-2-3)) 2% by weight of the acetate-terminated phosphorus-based phenylene ether oligo polymer and 16.8 g of xylene were mixed to form a curing composition. The curing composition was applied onto a glass by a glass coater, and then the temperature was raised to 80 ° C to carry out a curing reaction for 12 hours, and then the temperature was further raised to 180 ° C to carry out a curing reaction for 2 hours, and then, The temperature was raised to 200 ° C for 2 hours, and finally, the temperature was raised to 220 ° C for 2 hours. After the curing reaction is completed, a brown cured product is formed on the glass.

Comparative Example 1 Curing composition and cured product

10 grams of thiol acrylate-terminated polyphenylene ether resin (label: SABIC; model: SA9000 or MX9000), 1.3888 grams of epoxy resin (label: DIC; model: HP-7200), 6.69 mg 4-dimethylaminopyridine (used in an amount of 0.5% by weight of the epoxy resin) and 0.2 g of peroxidized third butanol (2wt of the amount of the thiol acrylate-terminated polyphenylene ether resin used) %) was dissolved in 17.0 g of xylene to form a curing composition. The curing composition was applied onto a glass by a glass coater, and then the temperature was raised to 80 ° C to carry out a curing reaction for 12 hours, and then the temperature was further raised to 180 ° C to carry out a curing reaction for 2 hours, and then, The temperature was raised to 200 ° C for 2 hours, and finally, the temperature was raised to 220 ° C for 2 hours. After the curing reaction is completed, a yellow solidified material is formed on the glass.

Comparative Example 2 Curing composition and cured product

10 g of methyl styrene-terminated polyphenylene ether resin (brand: Japan Mitsubishi Gas Chemical Company, Inc.; model: OPE-2St) and 0.2 g of peroxidized third butanol (used in amount) 2% by weight of the amount of the styrene-terminated polyphenylene ether resin was dissolved in 15 g of xylene to form a curing composition. The curing composition was applied onto a glass by a glass coater, and then the temperature was raised to 80 ° C to carry out a curing reaction for 12 hours, and then the temperature was further raised to 180 ° C to carry out a curing reaction for 2 hours, and then, The temperature was raised to 200 ° C for 2 hours, and finally, the temperature was raised to 220 ° C for 2 hours. After the curing reaction is completed, a yellow solidified material is formed on the glass.

Evaluation project

The glass transition temperature (unit: ° C) was measured by DMA: The cured products of Examples 1 to 3 and Comparative Examples 1 to 2 were each grown into a sample having a length of 5 cm, a width of 1 cm, and a thickness of about 100 μm. The samples were placed in a tension fixture of a dynamic mechanical analyzer (brand: Perkin Elmer; model: Pyris Diamond) for measurement. The measurement conditions were as follows: the heating rate was 5 ° C / min and the temperature was raised from 40 ° C to 370 ° C, the frequency was 1 Hz, and the amplitude was 25 μm.

The glass transition temperature (unit: ° C) was measured by TMA: The cured products of Examples 1 to 3 and Comparative Examples 1 to 2 were each made into a sample having a length of 3 cm, a width of 0.5 cm, and a thickness of about 100 μm. The samples were measured using a thermomechanical analyzer (label: SII TMA; model: SS6100). The measurement conditions were as follows: the heating rate was 5 ° C / min and the temperature was raised from 40 ° C to 350 ° C.

Thermal stability measurement: 3 to 5 mg of the cured products of Examples 1 to 3 and Comparative Examples 1 to 2 were placed in a platinum plate of a thermogravimetric analysis (label: Perkin-Elmer; model: Pyris 1). Nitrogen gas was introduced, and the temperature was raised from 40 ° C to 800 ° C at a heating rate of 20 ° C / min. The thermal cracking temperature and the temperature loss of 5% were measured, and the weight of the residue was measured at 800 ° C and calculated. The coke residual rate (Char yield).

Flame Retardancy Measurement: To facilitate the description of the test procedure, the cured product of Example 1 was explained, and the cured materials of Examples 2 to 3 and the cured products of Comparative Examples 1 to 2 were also tested in accordance with this manner. The cured product of Example 1 was formed into a film of 8 in. × 2 in. The film of about 5 in. length was wound around a cylindrical support having a diameter of 0.5 in., and the remaining portion was stretched into a conical shape. Then, it is exposed to the flame for 3 seconds, then the flame is removed and the burning time t1 (unit: second) is recorded, and then, after cooling, the second burning is performed, and the contact flame time is 3 seconds, then, Remove the flame and record the burning time t2 (unit: second). During the above burning process, cotton was disposed about 12 in. below the film, and it was observed whether there was a drip. The above experiment was repeated and five sets of experimental data were obtained. Each set of t1 and t2 is added, and the average of the sum of t1 and t2 is calculated. UL-94 VTM-0 rating: The average is between 10 and 30 seconds, and the sum of t1 and t2 for each group must not exceed 50 seconds, and no dripping is observed. UL-94 VTM-1 rating: The average is between 10 and 30 seconds and no dripping is observed.

Dielectric constant (unit: U) and dielectric loss (unit: mU) Measurement: The cured products of Examples 1 to 3 and Comparative Examples 1 to 2 were respectively grown to 1 cm in width, 1 cm in width, and approximately in thickness. 400 μm sample. The samples were measured using a dielectric analyzer (label: Agilgent; model: E4991A). The measurement condition: the frequency is 1 MHz.

Table 1  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Evaluation Project</td><td> Example </td><td> Comparative Example < /td></tr><tr><td> 1 </td><td> 2 </td><td> 3 </td><td> 1 </td><td> 2 </td> </tr><tr><td> Glass transition temperature (°C) </td><td> DMA measurement</td><td> 235 </td><td> 253 </td><td> 226 </td><td> 226 </td><td> 246 </td></tr><tr><td> TMA measurement</td><td> 207 </td><td> 223 < </ br><td> 5% temperature (Td5%) </td><td> 421 </td><td> 372 </td><td> 420 </td><td> 437 </td><td> 365 </ Td></tr><tr><td> coke residual rate (%) at 800 °C </td><td> 28 </td><td> 37 </td><td> 26 </td>< Td> 25 </td><td> 25 </td></tr><tr><td> flame retardancy</td><td> UL-94 </td><td> VTM-0 </ Td><td> VTM-0 </td><td> VTM-0 </td><td> VTM-1 </td><td> VTM-1 </td></tr><tr>< Td> Dielectric constant at 1MHz (U) </td><td> 2.96 </td><td> 2.70 </td><td> 2.80 </td><td> 2.85 </td><td> 2.64 </td></tr><tr><td> Dielectric loss (mU) at 1MHz </td><td> 5.8 </td><td> 5.8 </td ><td> 6.70 </td><td> 3.2 </td><td> 5.6 </td></tr></TBODY></TABLE>

In summary, the present invention transmits a phosphorus group in a phenylene ether oligopolymer having a crosslinkable group represented by the formula (1) ( And the design of the crosslinkable group, so that the cured product formed from the phenylene ether oligopolymer represented by the formula (1) has better flame retardancy and still maintains a high glass transition temperature, low dielectric The characteristics of the constant and the low dielectric loss are such that the object of the present invention can be achieved.

However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the simple equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still Within the scope of the invention patent.

Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is a ¹ H-NMR light spectrum illustrating the formula (1-2-1) of Synthesis Example 3 of the present invention. The chemical structure of the mercaptoacrylate-terminated phosphorus-based phenylene ether oligo polymer shown; and FIG. 2 is a ¹ H-NMR spectrum showing the formula (1-2-2) of Synthesis Example 4 of the present invention. The chemical structure of the methyl styrene-terminated phosphorus-based phenyl ether oligomer.

Claims (7)

A phosphorus-based phenylene ether oligomer having a crosslinkable group, represented by formula (1): Z is a single bond or X ¹ and X ² are each hydrogen or a C ₁ to C ₁₂ alkyl group; each of R ¹ and R ² is , ,or ; R ³ is a C ₁ to C ₁₂ alkyl group, a substituted phenyl group, or an unsubstituted phenyl group; each of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ Methyl or And at least one of Y ¹ to Y ⁸ is When Y ² is plural, the Y ² may be the same or different. When Y ³ is plural, the Y ³ may be the same or different. When Y ⁶ is plural, the Y ⁶ may be The same or different, when Y ⁷ is plural, the Y ⁷ may be the same or different; T ¹ , T ² , T ³ , T ⁴ , T ⁵ , T ⁶ , T ⁷ and T ⁸ each represent hydrogen or C ₁ to C ₆ alkyl; m and n are each 5 to 15. A phosphorus-based phenylene ether oligomer having a crosslinkable group according to claim 1, wherein Z is , R ¹ and R ² are . A phosphorus-based phenylene ether oligomer having a crosslinkable group according to claim 1, wherein Z is , R ¹ and R ² are . A phosphorus-based phenylene ether oligomer having a crosslinkable group according to claim 1, wherein Z is , R ¹ and R ² are . A method for preparing a phosphorus-based phenylene ether oligo polymer having a crosslinkable group, comprising the steps of: using a phenyl ether material represented by the formula (2), And 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide compound represented by formula (3), Performing a nucleophilic substitution reaction to form a phosphorus-based phenylene ether oligomer represented by formula (1-1); In the formula (2), Z is a single bond or X ¹ and X ² are each hydrogen or a C ₁ to C ₁₂ alkyl group; Y ¹¹ , Y ²¹ , Y ³¹ , Y ⁴¹ , Y ⁵¹ , Y ⁶¹ , Y ⁷¹ and Y ⁸¹ are each a halomethyl group or a methyl group. And at least one of Y ¹¹ , Y ²¹ , Y ³¹ , Y ⁴¹ , Y ⁵¹ , Y ⁶¹ , Y ⁷¹ and Y ⁸¹ is a halomethyl group, and when Y ²¹ is plural, the Y ²¹ may be the same or Differently, when Y ³¹ is plural, the Y ³¹ may be the same or different. When Y ⁶¹ is plural, the Y ⁶¹ may be the same or different, and when Y ⁷¹ is plural, the Y ⁷¹ May be the same or different; m and n are each 5 to 15; in the formula (3), T ¹ , T ² , T ³ , T ⁴ , T ⁵ , T ⁶ , T ⁷ and T ⁸ each represent hydrogen or C ₁ An alkyl group to C ₆ ; in the formula (1-1), each of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ is a methyl group or And at least one of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ is When Y ² is plural, the Y ² may be the same or different. When Y ³ is plural, the Y ³ may be the same or different. When Y ⁶ is plural, the Y ⁶ may be When Y ⁷ is plural, the Y ⁷ may be the same or different; the phosphorus-based phenyl ether oligomer represented by the formula (1-1) is reacted with a reaction reagent to form a formula ( 1-2) a phosphorus-based phenylene ether oligo polymer; the reaction reagent is selected from a material having an unsaturated group or acetic anhydride, wherein the unsaturated group is selected from or ; R ¹¹ and R ²¹ are each , ,or R ³ is a C ₁ to C ₁₂ alkyl group, a substituted phenyl group, or an unsubstituted phenyl group. A curing composition comprising the phosphorus-based phenylene ether oligomer having a crosslinkable group according to any one of claims 1 to 4. A cured product formed by a curing reaction of the curing composition according to claim 6.