TWI893655B - Phosphorus-containing resin and the flame-retardant and heat-resistant composition thereof - Google Patents

Abstract

A phosphorus-containing resin, wherein the phosphorus-containing resin comprises a structure as below: wherein R ^Aand R ^Bare each independently a phenylethene group; Ar ¹and Ar ²are independently a bivalent arylene group. The phosphorus-containing resin of the present invention has high reactivity, and may crosslink with other materials, making the flame-retardant and heat-resistant composition possess excellent flame-retardant and heat-resistant effect, therefore having high industrial value.

Description

Phosphorus-containing resin and flame-resistant and heat-resistant composition containing the same

This work relates to a phosphorus-containing resin and a flame-resistant and heat-resistant composition containing the same.

As the electronics industry continues to evolve, the industry is actively seeking ways to improve the flame retardancy of resin materials to enhance the safety and reliability of telecommunications equipment and reduce the damage caused by fires. Under the commonly used UL 94 standard, the industry generally targets a V0 flame retardancy rating.

Currently, various technologies are available to improve the flame retardancy of resin materials. Traditionally, halogen-containing flame retardants are added to resin materials to enhance their flame retardancy. However, halogen-containing flame retardants are corrosive, release toxic hydrogen halides, and cause environmental pollution. Consequently, several halogen-free regulations have been established internationally to restrict their use.

Therefore, the existing technology has developed a variety of phosphorus-containing flame retardants to solve the many problems derived from halogen-containing flame retardants. Common phosphorus-containing flame retardants on the market include: 2-(6-oxido-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)-1,4-benzenediol, 2,5-dihydroxyphenyldiphenylphosphine-oxide, 9,10-dihydro-9-oxa-10-phosphoranthren-10-oxide, (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviated as DOPO), and 4,4'-[1-(6-oxido-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)ethylidene]bisphenol (abbreviated as DMP).

Phosphorus-containing flame retardants can be categorized as additive and reactive depending on their usage. Additive phosphorus-containing flame retardants are physically blended with resins to create flame retardant compositions. Common resins include epoxy resins, acrylonitrile-butadiene-styrene copolymers, polycarbonate, polyamide, polyethylene terephthalate, and polybutylene terephthalate. Depending on the specific product requirements, additives such as binders, polymerization inhibitors, thickeners, defoaming agents, and fillers may also be added to the flame retardant composition to adjust its properties.

While additive phosphorus-containing flame retardants offer the advantage of low processing costs through physical blending, their physical bonding with other materials makes electronic products extremely susceptible to electron migration, impacting their stability and reliability. Furthermore, additive phosphorus-containing flame retardants require a high dosage to achieve their flame retardant effect. Excessive phosphorus content can impair the flowability and uniformity of the flame retardant composition during subsequent processing, dilute the content of other additives in the flame retardant composition, and reduce their intended performance. Furthermore, excessive phosphorus content can pose a significant burden on the human body and the environment, hindering the flame retardant's continued application.

Unlike physical blending, reactive phosphorus-containing flame retardants react and bond with other materials through chemical bonding. This allows them to maintain stable and long-lasting flame retardancy while also improving the stability and reliability of electronic products. However, existing reactive phosphorus-containing flame retardants still require a certain dosage to achieve V0 flame retardancy, resulting in high phosphorus content in the flame retardant composition and subsequent applications.

Whether additive or reactive, existing phosphorus-containing flame retardants generally suffer from poor heat resistance, hindering their application and the flame retardant compositions containing them in subsequent substrate processing, and even affecting the overall performance of electronic products.

In view of the above-mentioned shortcomings of phosphorus-containing flame retardants, a new phosphorus-containing flame retardant is still to be developed to comprehensively improve the reactivity, flame resistance, and heat resistance of existing phosphorus-containing flame retardants.

One of the goals of this invention is to enhance the reactivity of phosphorus-containing flame retardants with other materials, providing stable and long-lasting flame and heat resistance.

Another purpose of this invention is to further enhance the flame retardancy and heat resistance of phosphorus-containing flame retardants and flame retardant and heat-resistant compositions containing the phosphorus-containing flame retardants while minimizing the amount of the phosphorus-containing flame retardants used.

To achieve the aforementioned objectives, the present invention provides a phosphorus-containing resin comprising the structure shown below: (Formula I) wherein R ¹ , R ² , R ³ , and R ⁴ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms; R ⁵ is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and Ar ³ ; ^RA and ^RB are each independently or Ar ¹ and Ar ² are each independently selected from the group consisting of: 、 、 、 and ; Ar ³ is selected from the group consisting of: 、 、 、 、 、 and R ⁶ , R ⁷ , R ⁹ , R ^6' , R ⁷ ' , R ^9' , and ^Ra are each independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms; R ⁸ and R ^8' are each independently selected from the group consisting of -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, and -O-; l' is an integer from 0 to 5, m, m', and ma are each independently an integer from 0 to 4, n and n' are integers from 0 to 3, p and p' are 0 or 1, the sum of m and n does not exceed 4, and the sum of m' and n' does not exceed 5; * represents a bonding position.

The phosphorus-containing resin of this invention, due to its terminal functional group being a styryl group, has excellent reactivity and can cross-link with other resin materials to form flame-resistant and heat-resistant compositions, providing stable and long-lasting flame retardancy. It can also be used to prepare flame-resistant and heat-resistant compositions with low phosphorus content and excellent flame and heat resistance. This makes the phosphorus-containing resin of this invention particularly suitable as a phosphorus-containing flame retardant, combining the industrial value of high reactivity, high flame resistance, and high heat resistance.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R 6 ^' , R ^7' , R ^9' , and ^Ra can each be an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. R ¹ , R 2, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ^{6 '} , R 7 ^' , R ^9' , and ^Ra can be the same or different structures. In some embodiments, the alkyl group having 1 to 6 carbon atoms can be an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms; and the alkyl group having 1 to 4 carbon atoms can be an alkyl group having 1, 2, 3, or 4 carbon atoms, such as, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl. Alkoxy groups having 1 to 6 carbon atoms may be alkoxy groups having 1, 2, 3, 4, 5, or 6 carbon atoms. Alkoxy groups having 1 to 4 carbon atoms may be alkoxy groups having 1, 2, 3, or 4 carbon atoms, such as, but not limited to, methoxy, ethoxy, and propoxy. Cycloalkyl groups having 3 to 6 carbon atoms may be cycloalkyl groups having 3, 4, 5, or 6 carbon atoms, such as, but not limited to, cyclopropyl. Furthermore, R ¹ , R ² , R ³ , and R ⁴ may each be a hydrogen atom, and R ⁵ may be Ar ³ .

In some embodiments, ^RA and ^RB may each be or , ^RA and ^RB may be the same or different structures.

In some embodiments, l' may be an integer from 0 to 5, m, m', and ma may each independently be an integer from 0 to 4, n and n' may be integers from 0 to 3, p and p' may be 0 or 1, the sum of m and n may not exceed 4, and the sum of m' and n' may not exceed 5. Specifically, l' is 0, 1, 2, 3, 4, or 5; m, m', and ma may each independently be 0, 1, 2, 3, or 4; n and n' may each independently be 0, 1, 2, or 3; the sum of m and n is 0, 1, 2, 3, or 4, and the sum of m' and n' is 0, 1, 2, 3, 4, or 5.

In some embodiments of the present invention, Ar ¹ and Ar ² can each be 、 、 、 、 、 or Ar ¹ and Ar ² may have the same or different structures. R ⁶ , R ⁷ , and R ⁹ may each be an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. R ⁸ may be -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, or -O-. m, n, and p may each independently be 0 or 1.

In some embodiments of the present invention, Ar ³ may be 、 、 、 、 、 、 、 or , R ^6' , R ^7' , and R ^9' may each be an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; R ^8' may be -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, or -O-; and l', m', n', and p' may each independently be 0 or 1.

In one embodiment, R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the phosphorus-containing resin represented by formula (I) are hydrogen atoms, Ar ¹ and Ar ² are , n, m are 0, ^RA and ^RB are For example, the phosphorus-containing resin represented by formula (I) comprises the structure represented by the following formula (Ia): (Ia).

In one embodiment, R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the phosphorus-containing resin represented by formula (I) are hydrogen atoms, Ar ¹ and Ar ² are , n, m are 0, ^RA and ^RB are For example, the phosphorus-containing resin represented by formula (I) comprises the structure represented by the following formula (Ib): (Ib).

In one embodiment, R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the phosphorus-containing resin represented by formula (I) are hydrogen atoms, Ar ¹ and Ar ² are , n, m, ma are 0, ^RA is , ^RB is For example, the phosphorus-containing resin represented by formula (I) comprises the structure represented by the following formula (Ic): (Ic).

In one embodiment, the phosphorus-containing resin may include a phosphorus-containing resin of formula (Ia), formula (Ib), formula (Ic), or a combination thereof.

According to the present invention, the phosphorus content of the phosphorus-containing resin may be less than 5 weight percent (wt%). Preferably, the phosphorus content of the phosphorus-containing resin may be greater than 1 wt% and less than 5 wt%. The phosphorus content of the phosphorus-containing resin may be any of the following values, for example: 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, ..., 4.9 wt%, 4.91 wt%, 4.92 wt%, 4.93 wt%, 4.94 wt%, 4.95 wt%, 4.96 wt%, 4.97 wt%, 4.98 wt%, 4.99 wt%, but the above specific values may serve as endpoints of other numerical ranges.

According to the present invention, the integral value of the characteristic peak located between 4.95 ppm and 6.00 ppm in the hydrogen-1 nuclear magnetic resonance ( ¹ H-NMR) spectrum of the phosphorus-containing resin accounts for 10% to 20% of the integral value of the characteristic peaks of all hydrogen atoms. Specifically, the integral value of the characteristic peak located between 4.95 ppm and 6.00 ppm in the ¹ H-NMR spectrum of the phosphorus-containing resin can be any of the following values, for example: 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% of the integral value of the characteristic peaks of all hydrogen atoms, but is not limited to these values, and the above-mentioned specific values can serve as endpoints of other numerical ranges.

According to the present invention, the number average molecular weight (Mn) of the phosphorus-containing resin can be between 425 g/mol and 470 g/mol; the weight average molecular weight (Mw) of the phosphorus-containing resin can be between 425 g/mol and 470 g/mol. The ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) represents the polydispersity index (PDI). The PDI of the phosphorus-containing resin can be less than or equal to 1.10. Specifically, the PDI of the phosphorus-containing resin can be between 0.99 and 1.10, indicating that the phosphorus-containing resin of the present invention produces minimal byproducts.

According to the present invention, the Fourier transform infrared (FT-IR) spectrum of the phosphorus-containing resin has an absorption peak at 1600 cm ^-1 to 1700 cm ^-1 corresponding to the C=C of olefins.

According to the present invention, the FT-IR spectrum of the phosphorus-containing resin has an absorption peak at 1240 cm ^-1 to 1250 cm ^-1 corresponding to aromatic CO.

According to the present invention, the FT-IR spectrum of the phosphorus-containing resin has an absorption peak corresponding to saturated CO at 1000 cm ^-1 to 1100 cm ^-1 . Specifically, the FT-IR spectrum of the phosphorus-containing resin has an absorption peak corresponding to saturated CO at 1010 cm ^-1 to 1050 cm ^-1 .

According to this work, the FT-IR spectrum of the phosphorus-containing resin has an absorption peak at 1180 cm ^-1 to 1195 cm ^-1 corresponding to PO-Ph.

The present invention also provides a flame-resistant and heat-resistant composition comprising a main resin and a phosphorus-containing resin as represented by the aforementioned formula (I).

According to this invention, the amount of the phosphorus-containing resin is 5 wt% to 50 wt% based on the total weight of the flame-resistant and heat-resistant composition. Specifically, the dosage of the phosphorus-containing resin can be 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, but is not limited thereto; the above specific values may serve as endpoints of other value ranges.

According to the present invention, the main resin includes: a polyphenylene ether resin, a maleimide resin, or a combination thereof. In one embodiment, the polyphenylene ether resin may include, but is not limited to, a polyphenylene oxide resin, a bishydroxyl polyphenylene oxide resin (such as SA90, available from Sabic), a methacrylate polyphenylene oxide resin (such as SA9000, available from Sabic), a vinyl polyphenylene oxide resin (such as OPE-2st, available from Mitsubishi Gas Chemical Co., Ltd.), or a combination thereof. The polyphenylene ether resin is preferably a vinyl polyphenylene oxide resin. For example, the vinyl polyphenylene ether resin may include, but is not limited to, vinyl benzyl polyphenylene oxide resin, vinyl benzyl modified bisphenol A polyphenylene oxide resin, vinyl chain extension polyphenylene oxide resin, or combinations thereof. These polyphenylene ether resins can be mixed with phosphorus-containing resins to form low-dielectric, flame-resistant, and heat-resistant compositions. In another embodiment, the maleimide-based resin is a compound having one or more maleimide functional groups (monofunctional maleimide compound, difunctional maleimide compound, polyfunctional maleimide compound), a monomer, a mixture, or a polymer (including an oligomer). The maleimide-based resin can be suitable for making prepregs, resin films, laminates, printed circuit boards, or combinations thereof. For example, the maleimide resin may include 4,4'-diphenylmethanebismaleimide (CAS No.: 13676-54-5), phenylmethane maleimide oligomer (or polyphenylmethane maleimide, CAS No.: 105391-33-1), bismaleimidetoluene, diethylbismaleimidetoluene, m-phenylene bismaleimide, and diethyl bismaleimidetoluene. bismaleimide), bisphenol A diphenyl ether bismaleimide (also known as 2,2'-bis-[4-(4-maleimidephenoxy)phenyl]propane, CAS No. 79922-55-7), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, CAS No. No.: 105391-33-1), 4-methyl-1,3-phenylbismaleimide (CAS No.: 6422-83-9), 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzenemaleimide, 2,6-dimethylbenzenemaleimide, N-phenylmaleimide (CAS No.: 941-69-5), or a combination thereof, but not limited thereto. The maleimide resin may also include a maleimide resin having a biphenyl structure, a maleimide resin having an aliphatic long chain structure, or a combination thereof, but is not limited thereto. In addition, the maleimide resin may also include a prepolymer of the aforementioned maleimide resin and other compounds. For example, the other compound may be a diallyl compound, a polyfunctional amine (including a diamine), an acidic phenol compound, or a combination thereof, but is not limited thereto. The maleimide resin may also be mixed with a phosphorus-containing resin to form a highly flame-resistant and heat-resistant composition. The styrene group at the end of the phosphorus-containing resin can react and cross-link with the main resin to form a flame-resistant and heat-resistant composition with different properties, thereby obtaining good reactivity. Preferably, the nitrogen element in the maleimide resin can reduce the oxygen density of the flame-resistant and heat-resistant composition during combustion and decomposition, so that the flame-resistant and heat-resistant composition can exhibit synergistic flame-resistant and heat-resistant effects under the condition of low phosphorus content.

Optionally, the flame-resistant and heat-resistant composition may also contain ingredients other than the above-mentioned main resin. Specifically, the components may include: styryl-dicyclopentadienyl phenyl ether, cyanate ester resin, active ester, divinyl benzyl ether, 1,2-bis(vinylphenyl)ethane, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, diallylbisphenol A, styrene, acrylate, polyolefin, epoxy resin, phenol resin, resin), styrene maleic anhydride resin, amine curing agent, polyamide, polyimide or a combination thereof, but not limited thereto. For example, the flame resistant and heat resistant composition may further include modified forms of the above components.

According to this invention, the phosphorus content in the flame-resistant and heat-resistant composition is 0.5 wt% to 1.5 wt%. Specifically, the phosphorus content in the flame-resistant and heat-resistant composition can be 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, and 1.5 wt%, but these values are not limited to these values and may serve as endpoints of other numerical ranges.

According to this invention, the terminal styrene groups of the phosphorus-containing resin in the flame-resistant and heat-resistant composition facilitate addition reactions with the main resin to form covalent bonds. This helps to improve the uniformity of the bond distribution and thus enhance thermal stability, allowing the flame-resistant and heat-resistant composition to achieve a higher glass transition temperature (Tg). Specifically, the glass transition temperature of the flame-resistant and heat-resistant composition can be greater than or equal to 190°C or greater than or equal to 200°C. Preferably, the glass transition temperature of the flame-resistant and heat-resistant composition can be between 190°C and 300°C. The glass transition temperature of the flame-resistant and heat-resistant composition can be any of the following values, for example: 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, and 300°C, but is not limited to these values. The aforementioned specific values can serve as endpoints of other numerical ranges. Accordingly, the flame-resistant and heat-resistant composition of this invention exhibits excellent heat resistance, meeting the subsequent processing requirements of soft or rigid boards.

According to the phosphorus-containing resin and flame-resistant and heat-resistant composition provided by this invention, the inventors discovered that the phosphorus-containing resin of this invention (hereinafter referred to as DMPDS) can be formed by replacing the terminal hydroxyl group of 6-(1,1-bis(4-hydroxyphenyl)ethyl)dibenzo[c,e][1,2]oxaphosphinine-6-oxide (6-(1,1-bis(4-hydroxyphenyl)ethyl)dibenzo[c,e][1,2]oxaphosphinine-6-oxide, abbreviated as DMP, CAS number: 1205686-58-3) with a styryl group. This makes the phosphorus-containing resin of this invention extremely reactive, not only self-crosslinking and curing, but also addition polymerization with a variety of resin materials to form a flame-resistant and heat-resistant composition with both flame-resistant and heat-resistant effects.

More specifically, adding the phosphorus-containing resin of this invention to a main resin can produce chemical bonds between the phosphorus-containing resin and the main resin, thereby obtaining a flame-resistant and heat-resistant composition with excellent flame retardancy and heat resistance through a cross-linking reaction. The flame-resistant and heat-resistant composition also has the characteristic of a low phosphorus content.

This invention provides a phosphorus-containing resin represented by formula (I): (Formula I)

In some embodiments, R ¹ , R ² , R ³ , and R ⁴ are independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms. R ¹ , R ² , R ³ , and R ⁴ may have different structures. However, in some embodiments, two or three of R ¹ , R ² , R ³ , and R ⁴ have the same structure, or R ¹ , R ² , R ³ , and R ⁴ all have the same structure. R ¹ , R ² , R ³ and R ⁴ may be independently selected from the group consisting of a hydrogen atom, a substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted alkoxy group having 1 to 6 carbon atoms, an unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted cycloalkyl group having 3 to 6 carbon atoms, and an unsubstituted cycloalkyl group having 3 to 6 carbon atoms. For example, ^R1 , ^R2 , ^R3 , and ^R4 can be substituted or unsubstituted alkyl groups having 6, 5, 4, 3, 2, 1, or any range therebetween; ^R1 , ^R2 , ^R3 , and ^R4 can be substituted or unsubstituted alkoxy groups having 6, 5, 4, 3, 2, 1, or any range therebetween; or ^R1 , ^R2 , ^R3 , and ^R4 can be substituted or unsubstituted cycloalkyl groups having 6, 5, 4, 3, or any range therebetween. In some embodiments of the present invention, ^R1 , ^R2 , ^R3 , and ^R4 can be independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, and tert-butyl. In other embodiments, R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms.

In some embodiments, R ⁵ is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms. For example, R ⁵ can be a substituted or unsubstituted alkyl group having 6, 5, 4, 3, 2, 1, or any range therebetween; R ⁵ can be a substituted or unsubstituted alkoxy group having 6, 5, 4, 3, 2, 1, or any range therebetween; or R ⁵ can be a substituted or unsubstituted cycloalkyl group having 6, 5, 4, 3, or any range therebetween. In some embodiments of the present invention, R ⁵ can be selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, and tert-butyl. In addition, R ⁵ can also be Ar ³ , ^which can be selected from the group consisting of: 、 、 、 、 、 and .

In some embodiments, R ^6' , R ^7' , and R ^9' are independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms. R ^6' , R ^7' , and R ^9' may have different structures. However, in some embodiments, two of R ^6' , R ^7' , and R ^9' have the same structure, or R ^6' , R ^7' , and R ^9' all have the same structure. For example, R ^6' , R ^7' , and R ^9' can be substituted or unsubstituted alkyl groups having 6, 5, 4, 3, 2, 1, or any range therebetween; R ^6' , R ^7' , and R ^9' can be substituted or unsubstituted alkoxy groups having 6, 5, 4, 3, 2, 1, or any range therebetween; or R ^6' , R ^7' , and R ^9' can be substituted or unsubstituted cycloalkyl groups having 6, 5, 4, 3, or any range therebetween. In some embodiments of the present invention, R ^6' , R ^7' , and R ^9' can be independently selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, and tert-butyl.

Normally, ^RA and ^RB are independent of each other. or , wherein ^RA and ^RB may have different structures from each other, but in some embodiments, ^RA and ^RB have the same structure.

In some embodiments, ^Ra can be selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms. For example, ^Ra can be a substituted or unsubstituted alkyl group having 6, 5, 4, 3, 2, 1, or any range therebetween; ^Ra can each be a substituted or unsubstituted alkoxy group having 6, 5, 4, 3, 2, 1, or any range therebetween; or, ^Ra can be a substituted or unsubstituted cycloalkyl group having 6, 5, 4, 3, or any range therebetween. In some embodiments of the present invention, ^Ra can be selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, and tert-butyl. In one embodiment, ^Ra and R ^B can each be or .

Typically, ^Ar1 and ^Ar2 can be independently selected from the group consisting of: 、 、 、 and .

^Ar1 and ^Ar2 may have the same or different structures. ^R6 , ^R7 , and ^R9 may be independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms. ^R6 , ^R7 , and ^R9 may have different structures. However, in some embodiments, two of ^R6 , ^R7 , and ^R9 have the same structure, or ^R6 , ^R7 , and ^R9 all have the same structure. ^R6 , ^R7 , and ^R9 can each independently be a substituted or unsubstituted alkyl group having 6, 5, 4, 3, ² , 1, or any range therebetween; R6, ^R7 , and ^R9 can each independently be a substituted or unsubstituted alkoxy group having 6, 5, 4, 3, 2, 1, or any range therebetween; or ^R6 , ^R7 , and ^R9 can each independently be a substituted or unsubstituted cycloalkyl group having 6, 5, 4, 3, or any range therebetween. In some embodiments of the present invention, ^R6 , ^R7 , and ^R9 can each independently be selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, and tert-butyl.

R ⁸ and R ^8' can be selected from the group consisting of -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, and -O-, or can be a covalent bond. It is understood that when p in -(R ⁸ ) _p - is 0 or _p' in -(R ^8' ) p' - is 0, it means that -(R ⁸ ) _p - or -(R ^8' ) _p' can be a covalent bond, which is a bond connecting two groups and no other substituents are present.

l' may be an integer from 0 to 5, m, m', and ma may each independently be an integer from 0 to 4, n and n' may be integers from 0 to 3, p and p' may be 0 or 1, the sum of m and n may not exceed 4, and the sum of m' and n' may not exceed 5. Specifically, l' may be 0, 1, 2, 3, 4, or 5; m, m', and ma may each independently be 0, 1, 2, 3, or 4; n and n' may each independently be 0, 1, 2, or 3; the sum of m and n may be 0, 1, 2, 3, or 4, and the sum of m' and n' may be 0, 1, 2, 3, 4, or 5.

Reagent Description:

CMS-P: Contains 45 wt% to 55 wt% of 4-chloromethyl styrene (CAS No. 1592-20-7), 45 wt% to 55 wt% of 3-chloromethyl styrene (CAS No. 39833-65-3), and 0 wt% to 2 wt% of impurities (e.g., dichlorostyrene).

CMS-14: Contains 95 wt% 4-chloromethylstyrene, 5 wt% 3-chloromethylstyrene, and 0 wt% to 2 wt% of impurities (e.g., dichlorostyrene).

The following are several comparative examples and embodiments to illustrate the implementation of this invention. Those skilled in the art can easily understand the advantages and effects that can be achieved by this invention through the contents of this manual.

Comparative Example 1 DOPO (CAS No.: 35948-25-5)

Comparative Example 1 was purchased directly from Taiwan San Huang Co., Ltd., or from Japan San Guang Co., Ltd., with the trade name: HCA.

The DOPO of Control Example 1 was used as the test sample. 1 mg of the test sample was applied to a potassium bromide tablet with a diameter of 13 mm and a thickness of 1 mm using a thin film method. The coated potassium bromide tablet was placed in a tablet holder and placed in a Fourier transform infrared spectrometer (FT-IR) instrument (model: Spotlight 200i; instrument manufacturer: PerkinElmer) to measure the absorption spectrum of the coated potassium bromide tablet in the range of 400 cm ^- 1 to 4000 cm ^-1. The spectral intensity was measured using the transmission method. The resolution of the Fourier transform infrared spectrometer was 1 cm ^- 1. The spectrum is integrated 16 times. The spectrum intensity is the absorbance at each wavelength (arbitrary unit). It is calculated as the integral area of the line connecting the starting and ending points of the peak within the specified range, where P represents phosphorus, H represents hydrogen, O represents oxygen, Ph represents benzene, and C represents carbon.

FT-IR analysis of Control Example 1 revealed the following observations: a distinct PO-Ph absorption peak at 1193 cm ^-1 , a distinct P-Ph absorption peak at 1442 cm ^-1 , a distinct PH absorption peak at 2436 cm ^-1 , and a distinct P=O absorption peak at 1425 cm ^-1 .

Comparative Example 2 DMP

In a 3000 ml three-neck reaction flask, 216.2 g (1 mol) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO, CAS No. 35948-25-5), 470.5 g (5 mol) of phenol, 136.2 g (1 mol) of 4'-hydroxyacetophenone, and 8.65 g (4 wt% of DOPO weight) of p -toluenesulfonic acid were mixed. The reaction mixture was stirred at room temperature for 6 hours at 130°C to obtain a mixture. After cooling to room temperature, a preliminary product was isolated from the mixture. The product was washed with ethanol, filtered, and dried to obtain a white powder. The white powder was DMP from Comparative Example 2, and its structure is shown above.

The yield of Comparative Example 2 was 85%, and its melting point was 306°C. Elemental analysis of Comparative Example 2 revealed that carbon, hydrogen, and oxygen accounted for 72.48%, 4.65%, and 14.90%, respectively. The theoretical carbon, hydrogen, and oxygen contents were 72.89%, 4.65%, and 14.94%, respectively.

After the same FT-IR analysis method as described above, referring to Figure 1, a clear PO-Ph absorption peak was observed at 1191 cm ^-1 , and a clear Ph-OH absorption peak was observed at 3300 cm ^-1 to 3370 cm ^-1. No pH absorption peak was observed at 2436 cm ^-1 , no aromatic CO absorption peak was observed at 1247 cm ^-1 , and no saturated CO absorption peak was observed at 1014 cm ^-1 .

Comparative Example 3 DMPMS

428 g of DMP (as described in Comparative Example 2) was dissolved in 1 kg of dimethyl sulfoxide (DMSO, CAS No. 67-68-5). 176 g of 50 volume percent (vol%) sodium hydroxide (CAS No. 1310-73-2) was added and stirred thoroughly. 76 g (approximately 0.5 equivalents) of CMS-P and 0.2 g of p-hydroxyanisole (hydroquinone monomethyl ether, 4-methoxyphenol, MEHQ, CAS No. 150-76-5) were added dropwise at 65°C until the reaction was complete. After cooling, Comparative Example 3 was obtained, with the main product being DMPMS shown above.

15 mg of Control Example 3 was taken as the sample to be tested and dissolved in 750 μL of deuterated dimethylsulfoxide. The resulting solution was placed in the sample feeder of a nuclear magnetic resonance instrument (model: Bruker AVANCE 500 NMR). After shimming, analysis was performed using a 5 mm probe (model: BBFO Smart probe). The resonance frequency was 500 MHz, the pulse width was 10 μs, the pulse delay time was 2 s, the number of integrations was 32, and the signal of the reference substance was set to 0 ppm. The total integrated intensity was the integrated intensity after deducting the DMSO solvent (@2.5 ppm), the total integrated intensity of the hydrogen signal in Example 3 is 40.15, and the integrated intensity of the hydrogen signal on the terminal C=C (@ 4.95 ppm to 6.00 ppm) is 4.512, which means that the integrated intensity of the hydrogen signal on the terminal C=C accounts for 11.2% of the total integrated intensity.

Example 1 DMPDS-1 DMPDS-2 DMPDS-3

428 g of DMP (as described in Comparative Example 2) was dissolved in 1 kg of DMSO. 176 g of 50% (by volume) sodium hydroxide was added and stirred thoroughly. 340 g of CMS-P and 0.2 g of MEHQ were added dropwise at 65°C until the reaction was complete. After cooling, Example 1 was obtained. The main products were DMPDS-1, DMPDS-2, and DMPDS-3 shown above. After the same FT-IR analysis method as described above, referring to Figure 2, a clear PO-Ph absorption peak was observed at 1184 cm ^{- 1} , an aromatic CO absorption peak was observed at 1246 cm-1, a saturated CO absorption peak was observed at 1014 cm ^-1 , and clear C=C styryl absorption peaks were observed at 1607 cm ^-1 and 1683 cm ^-1. No pH absorption peak was observed at 2436 cm- ¹ , and no Ph-OH absorption peak was observed between 3360 cm ^-1 and 3370 cm ^-1 .

Analyzed using the same ^1H -NMR measurement method as above, ^{the 1H} -NMR measurement results are shown in Figure 4 and Table 1. The total integrated intensity of the hydrogen signal for Example 1 was 48.7031, and the integrated intensity of the hydrogen signal at the terminal C=C (@ 4.95 ppm to 6.00 ppm) was 8.7333. In other words, the integrated intensity of the hydrogen signal at the terminal C=C accounted for 17.9% of the total integrated intensity. Table 1: ^1H -NMR measurement results for Example 1. Chemical shift (ppm) integral area About 1.88 to 1.9 2.9259 About 2.39 2.9923 About 4.5 to 4.6 0.3515 About 4.7 0.1347 About 5.0 4.1318 Around 5.29 to 5.35 2.2841 About 5.8 to 5.9 2.3174 About 6.7 0.2972 About 6.8 4.2985 About 6.9 1.9825 About 7.0 1.0697 About 7.1 to 7.71 1.0586 5.0003 4.3144 9.3922 4.0221 1.1299 1.0000

Example 2 DMPDS-2

428 g of DMP was dissolved in 1 kg of DMSO, and 176 g of 50% sodium hydroxide was added and stirred thoroughly. 340 g of CMS-14 and 0.2 g of MEHQ were then added dropwise at 65°C until the reaction was complete. The mixture was cooled to yield Example 2. Since the reactant is CMS-14, its chloro and vinyl groups are primarily para-positioned, the structure of the main product of Example 2 is shown above as DMPDS-2. After the same FT-IR analysis method as described above, referring to Figure 3, a clear PO-Ph absorption peak was observed at 1184 cm ^{- 1} , an aromatic CO absorption peak was observed at 1247 cm-1, a saturated CO absorption peak was observed at 1014 cm ^-1 , and clear C=C styryl absorption peaks were observed at 1607 cm ^-1 and 1683 cm ^-1. No pH absorption peak was observed at 2436 cm- ¹ , and no Ph-OH absorption peak was observed between 3360 cm ^-1 and 3370 cm ^-1 .

Using the same ^1H -NMR measurement method as above, as shown in Figure 5 and Table 2, the total integrated intensity of the hydrogen signal for Example 2 was 85.1257, and the hydrogen signal at the terminal C=C (@ 4.95 ppm to 6.00 ppm) was 11.7955. This means that the integrated intensity of the hydrogen signal at the terminal C=C accounted for 13.9% of the total integrated intensity. Table 2: ^1H -NMR measurement results for Example 2. Chemical shift (ppm) Absorption area About 1.83 to 1.87 3.7989 About 2.1 11.8973 About 2.34 6.5921 About 4.52 1 About 4.65 0.23 About 4.96 to 4.97 5.06 Around May 26 to May 29 3.0966 About 5.4 0.0759 About 5.76 0.1774 About 5.78 0.4381 About 5.8 2.9475 About 6.67 to 6.82 6.1858 About 6.9 2.5956 Around 7:00 to 7:04 2.8831 Around July 15 to July 21 9.2559 About 7.3 to 7.73 6.7877 1.7371 0.4159 12.9439 4.2325 1.4183 1.3561

Test Example 1 ：Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES)

2.5 grams of each of the samples from Control Example 2, Example 1, and Example 2 were dissolved in 2.5 grams of DMSO. Sample pretreatment procedures were followed according to EPA 3050B (v.1996). After digestion, the phosphorus content was analyzed using an inductively coupled plasma atomic emission spectrometer (PERKIN ELMER Optima 8300 ICP-AES). The results are listed in Table 3 below. Table 3: Phosphorus Content of the Phosphorus-Containing Resins from Control Example 2, Example 1, and Example 2. Comparative Example 2 Example 1 Example 2 Phosphorus content (wt%) 8.3 4.9 4.4

As can be seen from Table 3, the phosphorus content of Comparative Example 2 is greater than 5 wt%, while the phosphorus content of Examples 1 and 2 is less than 5 wt%.

Test Example 2 : Gel osmosis stratification (GPC)

The samples from Comparative Example 2, Example 1, and Example 2 were diluted to 200 ppm with tetrahydrofuran (THF) and placed in an autosampler (Waters 717 Plus Autosampler). The samples were then pumped through four series-connected GPC columns (one TSK gel G3000H _XL , one TSK gel G2000H _XL , and two TSK gel G1000H _XL columns) at a flow rate of 1.0 mL/min via a Waters 515 pump. The samples were then separated using an absorbance detector (Waters 2487 Dual λ Absorbance Detector), integrating the absorption peak area at a wavelength of 254 nm. The GPC measurement results for Comparative Example 2, Example 1, and Example 2 are shown in Table 4. Table 4: GPC measurement results of the phosphorus-containing resins of Comparative Example 2, Example 1, and Example 2. Comparative Example 2 Example 1 Example 2 Number average molecular weight (Mn) (g/mol) 354 412 415 Weight average molecular weight (Mw) (g/mol) 408 414 418 Mw/Mn 1.15 1.01 1.01

Mw/Mn represents the polydispersity index. As shown in Table 4, the PDI of the phosphorus-containing resins of Examples 1 and 2 is lower than that of Control 2, indicating that the phosphorus-containing resins of Examples 1 and 2 are less dispersible than that of Control 2 and produce fewer byproducts.

《 Preparation of flame-resistant and heat-resistant compositions with high safety 》

Embodiment 1A

30.8 g of 2,2'-diallylbisphenol A (DABPA, CAS No. 1745-89-7) and 35.8 g of polyamine maleimide (4,4'-propane-2,2-diyldiphenol-aniline (1:1), CAS No. 67784-74-1, trade name BES1-5950, available from Regina) were placed in a beaker and heated to 130°C using an electromagnetic stirrer. 28.5 g of Example 1 was then added and stirred until the mixture became clear, producing a flame-resistant and heat-resistant composition containing 30 wt% of a phosphorus-containing resin, namely Example 1A.

Embodiment 2A

30.8 g of DABPA and 35.8 g of polyamine maleimide were placed in a beaker and heated to 130°C using an electromagnetic stirrer. 22.2 g of Example 1 was then added and stirred until the mixture became clear, producing a flame-resistant and heat-resistant composition containing 25 wt% of a phosphorus-containing resin, namely Example 2A.

Embodiment 3A

30.8 g of DABPA and 35.8 g of polyamine maleimide were placed in a beaker and heated to 130°C using an electromagnetic stirrer. 16.65 g of Example 1 was then added and stirred until the mixture became clear, producing a flame-resistant and heat-resistant composition containing 20 wt% of a phosphorus-containing resin, namely Example 3A.

Embodiment 4A

30.8 g of DABPA and 35.8 g of polyamine maleimide were placed in a beaker and heated to 130°C using an electromagnetic stirrer. 11.9 g of Example 1 was then added and stirred until the mixture became clear, producing a flame-resistant and heat-resistant composition containing 15 wt% of a phosphorus-containing resin, namely Example 4A.

Embodiment 5A

30.8 g of DABPA and 35.8 g of polyamine maleimide were placed in a beaker and heated to 130°C using an electromagnetic stirrer. 7.4 g of Example 1 was then added and stirred until the mixture became clear, producing a flame-resistant and heat-resistant composition containing 10 wt% of a phosphorus-containing resin, namely Example 5A.

Embodiment 6A

30.8 g of DABPA and 35.8 g of polyamine maleimide were placed in a beaker and heated to 130°C using an electromagnetic stirrer. 11.9 g of Example 2 was then added and stirred until the mixture became clear, producing a flame-resistant and heat-resistant composition containing 15 wt% of a phosphorus-containing resin, namely Example 6A.

Comparative example 1A

30.8 g of DABPA and 35.8 g of polyamine maleimide were placed in a beaker and heated to 130°C using an electromagnetic stirrer. 11.9 g of Comparative Example 2 was added and stirred until the mixture became clear, thereby producing a resin composition containing 15 wt% DMP, namely Comparative Example 1A.

Comparative example 2A

30.8 g of DABPA and 35.8 g of polyamine maleimide were placed in a beaker and heated to 130°C using an electromagnetic stirrer. 11.9 g of Comparative Example 3 was added and stirred until the mixture became clear, thereby producing a resin composition containing 15 wt% DMPMS, namely Comparative Example 2A.

Comparative example 3A

30.8 g of DABPA and 35.8 g of polyamine maleimide were placed in a beaker without any phosphorus-containing resin. The mixture was heated to 130°C using an electromagnetic stirrer to prepare the resin composition of Comparative Example 3A.

Test Example 2 : Determination of phosphorus content

A potassium dihydrogen phosphate solution was used to generate a standard curve for UV-visible light absorption at 420 nm. Sulfuric acid and potassium persulfate were added to the flame-resistant and heat-resistant compositions of Examples 1A to 6A and the resin compositions of Comparative Examples 1A to 3A, respectively. After digestion at 100°C for 60 minutes, the digested sample solutions were treated with a molybdenum vanadium salt reagent to form vanadium-molybdenum phosphate. The UV-visible light absorption of each sample at 420 nm was measured, and the phosphorus content was ultimately determined from the standard curve in units of wt%.

Test Example 3 : UL 94 Vertical combustion test

The flame retardancy of each flame-resistant and heat-resistant composition was measured according to the UL 94 vertical flame test. To compare the flame retardancy of each flame-resistant and heat-resistant composition, glass fiber cloth 2116 was impregnated with Examples 1A to 6A and Comparative Examples 1A to 3A, respectively. After baking at 150°C for 7 minutes, prepregs were prepared. Each prepreg was then cut into 13 x 13 cm square test pieces, covered with copper foil on both sides, and vacuum-pressed at 220°C for 2 hours. Shearing was used to cut the pieces into 13 x 1.3 cm square pieces. After removing the outer copper foil layer, the prepregs were subjected to the UL 94 vertical flame test.

According to the UL 94 flame retardancy test standard, a V0 rating indicates that after two 10-second flame tests, combustion ceased within 10 seconds with no flaming dripping. A V1 rating indicates that after two 10-second flame tests under the test conditions, combustion ceased within 60 seconds with no flaming dripping. In this test, five specimens from each set of samples were subjected to the UL 94 flame retardancy test five times, with each test using a new specimen to re-test the flame retardancy results.

Table 5 below lists the duration (in seconds) that each specimen continued to burn after the first 10-second flame test and after the flame was removed, as well as the duration (in seconds) that the specimen continued to burn after the second 10-second flame test and after the flame was removed, in the UL 94 vertical flame test. As shown in Table 5, after the first specimen of Example 1A was subjected to the UL 94 vertical flame test, the specimen did not continue to burn after the first 10-second flame test and after the flame was removed, nor did it continue to burn after the second 10-second flame test and after the flame was removed. Conversely, after the first specimen of Comparative Example 1A was subjected to the UL 94 vertical flame test, the specimen continued to burn for 13.8 seconds after the first 10-second flame test and after the flame was removed, and continued to burn for 2.6 seconds after the second 10-second flame test and after the flame was removed.

Test Example 4 : Glass transition temperature (Tg)

The flame-resistant and heat-resistant compositions of Examples 1A to 6A and the resin compositions of Comparative Examples 1A to 3A were used as samples and measured using a differential scanning calorimeter (DSC) in accordance with IPC-TM-650-2.4.25, with a scanning rate of 20°C/min. Table 5: UL 94 vertical flammability test results, glass transition temperature, and phosphorus content for Examples 1A to 6A and Comparative Examples 1A to 3A. UL 94 test Tg (°C) Phosphorus content (wt%) 1 2 3 4 5 Example 1A 0/0 0/0 0/0 0/0 0/0 202 1.41 Example 2A 4.0/0 2.8/0 5.2/0 2.2/0 5.6/0 209 1.18 Example 3A 4.0/0 8.5/0 7.0/0 7.0/0 6.1/0 223 0.94 Example 4A 6.3/0 8.8/0 6.9/0 7.0/0 6.1/0 238 0.71 Example 5A 8.9/0 9.9/0 8.3/0 8.1/0 8.6/0 256 0.47 Example 6A 5.7/0 7.1/0 7.5/0 5.8/0 7.7/0 247 0.71 Comparative example 1A 13.8/2.6 16.1/1.5 13.3/3.4 5.7/0 12.9/2.7 187 1.08 Comparative Example 2A 11.5/2.3 12.6/3.8 8.9/1.1 9.6/1.9 10.2/2.5 182 0.86 Comparative Example 3A 18.2/1.6 16.6/1.7 16.1/2.5 17.4/0.9 17.9/3.8 270 0

As shown in Table 5, the phosphorus-containing resins of Examples 1 and 2 exhibit excellent reactivity and are capable of crosslinking with maleimide-based resins to produce flame-resistant and heat-resistant compositions comprising maleimide-based resins. As shown in Table 5, Examples 1A to 6A all completed the five UL 94 vertical flame tests within 10 seconds without any burning dripping. Their flame retardancy ratings were all V0, demonstrating that the flame-resistant and heat-resistant compositions of Examples 1A to 6A possess excellent flame resistance. In contrast, in Comparative Examples 1A to 3A, the resin composition of Comparative Example 3A, because it does not contain any phosphorus-containing resin, has a flame retardancy rating of only V1 in all five tests. The resin composition of Comparative Example 1A (prepared from Comparative Example 2) has a flame retardancy rating of V1 in four of the five tests. The resin composition of Comparative Example 2A (prepared from Comparative Example 3) has a flame retardancy rating of V1 in three of the five tests. This shows that even with the addition of 15 wt% DMP or DMPMS, the flame retardancy of the resin compositions of Comparative Examples 1A and 2A is still significantly inferior to that of the flame-resistant and heat-resistant compositions of Examples 1A to 6A. On the other hand, the glass transition temperatures of Examples 1A to 6A range from 200°C to 260°C, indicating that they have excellent heat resistance. Compared to Comparative Examples 1A and 2A, their glass transition temperatures are only 182°C and 187°C, respectively, both of which are much lower than the flame-resistant and heat-resistant compositions of Examples 1A to 6A.

Looking at Table 5 again, Examples 4A and 6A, as well as Comparative Examples 1A and 2A, all incorporate 15 wt% of a phosphorus-containing resin. However, the phosphorus content of the flame-resistant and heat-resistant compositions of Examples 4A and 6A is only 0.71 wt%, while that of Comparative Example 1A is 1.08 wt%, and that of Comparative Example 2A is 0.86 wt%, all higher than that of Examples 4A and 6A. This demonstrates that the flame-resistant and heat-resistant compositions synthesized from the phosphorus-containing resin of this invention can indeed provide superior flame and heat resistance at relatively low phosphorus contents.

"Low dielectric Flame-resistant and heat-resistant composition 》

Embodiment 1B

25 grams of methacrylate polyphenylene oxide resin (PPO, SA9000, purchased from Sabic) and 10 grams of triallyl-isocyanurate (TAIC, CAS No. 1025-15-6) were placed in a beaker and heated to 90°C using an electromagnetic stirrer. 8.75 grams of Example 2 were then added and stirred thoroughly. The mixture was then heated to 100°C for five minutes. The gelation time at 171°C was 400 seconds, resulting in a flame-resistant and heat-resistant composition containing 20 wt% of a phosphorus-containing resin, Example 1B.

Embodiment 2B

25 g of PPO and 10 g of TAIC were placed in a beaker and heated to 90°C using an electromagnetic stirrer. 6.2 g of Example 2 was added and stirred thoroughly. The mixture was then heated to 100°C for five minutes. The gelation time at 171°C was 450 seconds, resulting in a flame-resistant and heat-resistant composition containing 15 wt% of a phosphorus-containing resin, Example 2B.

Embodiment 3B

25 g of PPO and 10 g of TAIC were placed in a beaker and heated to 90°C using an electromagnetic stirrer. 8.75 g of Example 2 was added and stirred thoroughly. The mixture was then cooled to 50°C and 0.05 g of benzoyl peroxide (CAS No. 94-36-0) was added to produce a flame-resistant and heat-resistant composition containing 20 wt% of the phosphorus-containing resin, Example 3B.

Embodiment 4B

25 g of PPO and 10 g of TAIC were placed in a beaker and heated to 90°C using an electromagnetic stirrer. 6.2 g of Example 2 was added and stirred thoroughly. The mixture was then cooled to 50°C and 0.05 g of benzoyl peroxide was added to prepare a flame-resistant and heat-resistant composition containing 15 wt% of the phosphorus-containing resin, Example 4B.

Comparative example 1B

25 g of PPO and 10 g of TAIC were placed in a beaker and heated to 90°C using an electromagnetic stirrer. 6.2 g of Comparative Example 2 was added and stirred thoroughly. The mixture was then cooled to 50°C and 0.05 g of benzoyl peroxide was added to prepare a resin composition containing 15 wt% of the phosphorus-containing resin, as in Comparative Example 1B.

Comparative example 2B

25 g of PPO and 10 g of TAIC were placed in a beaker and heated to 90°C using an electromagnetic stirrer. 6.2 g of Comparative Example 3 was added and stirred thoroughly. The mixture was then cooled to 50°C and 0.05 g of benzoyl peroxide was added to prepare a resin composition containing 15 wt% of the phosphorus-containing resin, as described in Comparative Example 2B.

Examples 1B to 4B, Comparative Example 1B, and Comparative Example 2B were subjected to the UL 94 vertical flame test according to the method described above, and their phosphorus content and glass transition temperature were measured. The results are reported in Table 6 below. Specifically, to compare the flame retardancy of the flame-resistant and heat-resistant compositions, glass fiber cloth 2116 was impregnated with the flame-resistant and heat-resistant compositions of Examples 1B to 4B and Comparative Examples 1B to 2B, respectively, and then baked at 150°C for 7 minutes to form prepregs. Each prepreg was then cut into 13 x 13 cm square test pieces, covered with copper foil on both sides, and vacuum hot-pressed at 220°C for 2 hours. The sheets were cut into 13 x 1.3 cm squares using a shearing machine. After removing the outer copper foil, they were subjected to a vertical flame test according to UL 94. Table 6: UL 94 vertical flame test, glass transition temperature, and phosphorus content test results for Examples 1B to 4B and Comparative Examples 1B to 2B. UL 94 test Tg (°C) Phosphorus content (wt%) 1 2 3 4 5 Example 1B 6.0/0 6.4/0 7.9/0 4.3/0 5.2/0 207 0.94 Example 2B 5.9/0 5.8/0 1.3/0 8.4/0 2.4/1.2 198 0.71 Example 3B 2.1/0 3.7/0 3.1/0 2.3/0 5.9/0 219 0.94 Example 4B 2.5/0 2.1/0 2.9/0 2.2/0 2.8/0 206 0.71 Comparative Example 1B 14.8/2.2 16.5/1.8 7.5/0 12.3/1.0 6.9/0 155 1.08 Comparative example 2B 8.5/0 8.9/0 10.6/0.8 11.4/1.1 11.8/2.2 174 0.85

The phosphorus-containing resin of this invention exhibits excellent reactivity, allowing it to crosslink with polyphenylene ether resins to produce flame-resistant and heat-resistant compositions containing polyphenylene ether resins. As shown in Table 6, Examples 1B to 4B all stopped within 10 seconds of the five UL 94 vertical flame tests, with no burning dripping observed. All five flame retardancy ratings were V0, demonstrating that the flame-resistant and heat-resistant compositions of Examples 1B to 4B possess excellent flame resistance. In contrast, Comparative Examples 1B and 2B achieved a V1 rating in three of the five flame retardancy tests, indicating that the flame resistance of the resin compositions of Comparative Examples 1B and 2B is significantly inferior to that of the flame-resistant and heat-resistant compositions of Examples 1B to 4B. On the other hand, the glass transition temperatures of Examples 1B to 4B range from 190°C to 220°C, which are significantly higher than those of Comparative Examples 1B and 2B. This indicates that the flame-resistant and heat-resistant compositions of Examples 1B to 4B also have excellent heat resistance.

In summary, the phosphorus-containing resin of this invention possesses excellent reactivity, allowing it to crosslink and form bonds with a variety of resin materials. The flame-resistant and heat-resistant compositions produced therefrom not only possess excellent flame and heat resistance but also possess a low phosphorus content, making this phosphorus-containing resin of this invention highly industrially applicable and commercially valuable.

without

Figure 1 is a Fourier transform infrared spectrum of Comparative Example 2. Figure 2 is a Fourier transform infrared spectrum of Example 1. Figure 3 is a Fourier transform infrared spectrum of Example 2. Figure 4 is a hydrogen-1 nuclear magnetic resonance spectrum of Example 1. Figure 5 is a hydrogen-1 nuclear magnetic resonance spectrum of Example 2.

without.

without.

Claims (16)

A phosphorus-containing resin, wherein the phosphorus-containing resin comprises a structure as shown in formula (I): Formula (I) wherein R ¹ , R ² , R ³ , and R ⁴ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms; R ⁵ is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and Ar ³ ; ^RA and ^RB are each independently or Ar ¹ and Ar ² are each independently selected from the group consisting of: 、 、 ,and ; Ar ³ is selected from the group consisting of: 、 、 、 、 、 and R ⁶ , R ⁷ , R ⁹ , R ^6' , R ⁷ ' , R ^9' , and ^Ra are each independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms; R ⁸ and R ^8' are each independently selected from the group consisting of -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, and -O-; l' is an integer from 0 to 5, m, m', and ma are each independently an integer from 0 to 4, n and n' are integers from 0 to 3, p and p' are 0 or 1, the sum of m and n does not exceed 4, and the sum of m' and n' does not exceed 5; * represents a bonding position. The phosphorus-containing resin as described in claim 1, wherein ^RA and ^RB are independently or . The phosphorus-containing resin of claim 1, wherein Ar ¹ and Ar ² are independently selected from the group consisting of: 、 、 、 ,and R ⁶ , R ⁷ , and R ⁹ are each independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms; R ⁸ is selected from the group consisting of -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, and -O-; and m, n, and p are each independently 0 or 1. The phosphorus-containing resin of claim 1, wherein Ar ³ is selected from the group consisting of: 、 、 、 、 、 、 、 and R ^6' , R ^7' , and R ^9' are each independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms; R ^8' is selected from the group consisting of -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, and -O-; and l', m', n', and p' are each independently 0 or 1. The phosphorus-containing resin as described in claim 1, wherein R ⁵ is -CH ₃ or -C ₆ H ₅ . The phosphorus-containing resin as described in claim 1, wherein the integral value of the characteristic peak located at 4.95 ppm to 6.00 ppm in the hydrogen-1 nuclear magnetic resonance spectrum of the phosphorus-containing resin accounts for 10% to 20% of the integral value of the characteristic peaks of all hydrogen atoms. The phosphorus-containing resin of claim 1, wherein the phosphorus content of the phosphorus-containing resin is less than 5 wt% relative to the weight of the entire phosphorus-containing resin. The phosphorus-containing resin as described in claim 7, wherein the phosphorus content of the phosphorus-containing resin is greater than 1 wt% and less than 5 wt%. The phosphorus-containing resin of claim 1, wherein the phosphorus-containing resin has an absorption peak corresponding to C=C of olefin at 1600 cm ^-1 to 1700 cm ^-1 in a Fourier transform infrared spectrum. The phosphorus-containing resin according to claim 1, wherein the phosphorus-containing resin has an absorption peak corresponding to aromatic CO at 1240 cm ^-1 to 1250 cm ^-1 in its FT-IR spectrum. The phosphorus-containing resin of claim 1, wherein the phosphorus-containing resin has an absorption peak corresponding to PO-Ph at 1180 cm ^-1 to 1195 cm ^-1 in its FT-IR spectrum. A flame-resistant and heat-resistant composition comprising the phosphorus-containing resin according to any one of claims 1 to 11 and a main resin. The flame-resistant and heat-resistant composition as described in claim 12, wherein the content of the phosphorus-containing resin is 5 wt% to 50 wt% based on the total weight of the entire flame-resistant and heat-resistant composition. The flame-resistant and heat-resistant composition as described in claim 12, wherein the phosphorus content is 0.5 wt% to 1.5 wt% based on the total weight of the entire flame-resistant and heat-resistant composition. The flame-resistant and heat-resistant composition as described in claim 12, wherein the glass transition temperature of the flame-resistant and heat-resistant composition is 190°C to 300°C. The flame-resistant and heat-resistant composition as described in claim 12, wherein the main resin comprises: polyphenylene ether resin, maleimide resin or a combination thereof.