Structure of phosphorous-containing functionalized poly(arylene ether) and compositions prepared therefrom

Abstract

A structure of phosphorous-containing functionalized poly(arylene ether), a preparation method thereof, and a composition prepared therefrom are provided. The curable (cross-linkable) composition includes an unsaturated monomer and a phosphorous-containing functionalized poly(arylene ether) having a polymerizable group and a molecular weight between 500 and 20,000. The composition provides excellent fluidity and fast curing rate. After curing, the composition exhibits excellent low dielectric coefficient and dielectric loss, high heat resistance and flame retardancy. It is suitable for prepregs, laminated sheets for printed circuits or the like.

Claims

1. A preparation method of a phosphorous-containing functionalized poly(arylene ether) represented by chemical structure (I): ##STR00015## wherein each R.sub.1 is independently selected from a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C1-C10 hydroxyalkyl group, a phenyl group, and a C1-C10 alkoxyl group; each R.sub.2 is independently selected from H, a C1-C10 alkyl group, a C2-C10 alkenyl group, C2-C10 alkynyl group, a C1-C10 hydroxyalkyl group, a phenyl group and a C1-C10 alkoxyl group; i and j are integers of 0-2 respectively, and sum of i and j is not equal to 0; m and n are integers of 0-50, and sum of m and n is not smaller than 3; z is 1; W is independently selected from H and C1-C5 alkyl group; s and t are integers of 1-4; Q is ##STR00016## wherein R.sub.6 is a C1-C10 alkyl group or a C6-C18 aromatic group, and a is an integer of 0-4; Y is ##STR00017## and X is ##STR00018## wherein the preparation method comprises: mixing a bisphenol compound and DOPO (9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) to perform condensation reaction to obtain a phosphorus-containing bisphenol compound; oxidatively polymerizing a phenol to form a corresponding poly(arylene ether) under a suitable condition and a catalyst; reacting the poly(arylene ether) and the phosphorus-containing bisphenol compound to form a phosphorus-containing poly(arylene ether) having two terminal hydroxyl groups; and reacting a capping agent with the phosphorus-containing poly(arylene ether) having two terminal hydroxyl groups to form the phosphorous-containing functionalized poly(arylene ether), wherein the capping agent comprises halogenated hydrocarbons and carboxylic anhydrides.

2. A preparation method of a phosphorous-containing functionalized poly(arylene ether) represented by chemical structure (I): ##STR00019## wherein each R.sub.1 is independently selected from a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C1-C10 hydroxyalkyl group, a phenyl group, and a C1-C10 alkoxyl group; each R.sub.2 is independently selected from H, a C1-C10 alkyl group, a C2-C10 alkenyl group, C2-C10 alkynyl group, a C1-C10 hydroxyalkyl group, a phenyl group and a C1-C10 alkoxyl group; i and j are integers of 0-2 respectively, and sum of i and j is not equal to 0; m and n are integers of 0-50, and sum of m and n is not smaller than 3; z is 1; W is independently selected from H and C1-C5 alkyl group; s and t are integers of 1-4; Q is ##STR00020## wherein R.sub.6 is a C1-C10 alkyl group or a C6-C18 aromatic group, and a is an integer of 0-4; Y is ##STR00021## and X is ##STR00022## wherein the preparation method comprises: oxidatively copolymerizing a phenol and a phosphorous-containing bisphenol to form a phosphorus-containing poly(arylene ether) having two terminal hydroxyl groups; and reacting a capping agent with the phosphorus-containing poly(arylene ether) having two terminal hydroxyl groups to form the phosphorous-containing functionalized poly(arylene ether), wherein the capping agent comprises halogenated hydrocarbons and carboxylic anhydrides.

3. The preparation method of claim 2, wherein the phenol having a structure below: ##STR00023## wherein each R.sub.1 is independently selected from a primary or secondary C1-C10 alkyl group, a C2-C10 alkenyl group, C2-C10 alkynyl group, a C1-C10 hydroxyalkyl group, a phenyl group, a C1-C10 alkoxyl group; and each R.sub.2 is independently selected from H, a primary or secondary C1-C10 alkyl group, a C2-C10 alkenyl group, C2-C10 alkynyl group, a C1-C10 hydroxyalkyl group, a phenyl group, a C1-C10 alkoxyl group.

4. The preparation method of claim 2, wherein the phenol is selected from 2,6-dimethylphenol, 2,3,6-trimethylphenol, and a mixture thereof.

5. The preparation method of claim 2, wherein the phosphorous-containing bisphenol having a chemical structure below: ##STR00024## wherein each W is independently selected from H and C1-C5 alkyl group; s and t are integers of 1-4; i and j are integers of 0-2 respectively, and sum of i and j is not equal to 0; X is selected from ##STR00025## wherein R.sub.7 and R.sub.8 are independently selected from H, a C1-C10 alkyl group, and a C6-C18 aromatic group.

Description

DETAILED DESCRIPTION

(1) In order to make the description of this disclosure more detailed and complete, the embodiments of this invention are illustratively described below. However, this is not the only form of practicing or using the embodiments of this invention. The disclosed various embodiments may be combined or substituted by each other and one embodiment may be added with other embodiments in a beneficial situation. In the following description, numerous specific details will be described in detail in order to enable the reader to fully understand the following embodiments. However, embodiments of this invention may be practiced without certain specific details.

(2) The detailed reaction conditions of the phosphorus-containing bisphenol compound are described below.

REFERENCE EXAMPLE 1

(3) 376 g bisphenol, 210 g formaldehyde aqueous solution (mass concentration is 37%), and 24 g NaOH were put into a reactor and then stirred. The temperature was increased to 50 C. and then kept for 3 hours. Next, the temperature was increased to 85 C. and then kept for 3 hours. Afterwards, 480 g n-butanol was added and then refluxed for 12 hours. The temperature was then decreased to 55-60 C. About 324 g n-butanol was removed by reduced pressure distillation to obtain an intermediate. The intermediate was added with 380 g DOPO (9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), and the material temperature was progressively increased from 80 C. to 180 C. in 2 hours. The pressure was decreased at 130 C. to ensure timely discharge the n-butanol. The temperature was kept at 180 C. for 1 hour. The material temperature was decreased to 130 C. About 1000 g toluene was added and then stirred for 0.5 hour. The material was discharged to obtain a DOPO-containing dihydroxyl biphenyl (A1).

REFERENCE EXAMPLE 2

(4) 456 g bisphenol A, 210 g formaldehyde aqueous solution (mass concentration is 37%), and 24 g NaOH were put into a reactor and then stirred. The temperature was increased to 50 C. and then kept for 3 hours. Next, the temperature was increased to 65 C. and then kept for 3 hours. Afterwards, 480 g n-butanol was added and then refluxed for 12 hours. The material temperature was then decreased to 55-60 C. About 324 g n-butanol was removed by reduced pressure distillation to obtain an intermediate. The intermediate was added with 380 g DOPO (9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), and the material temperature was progressively increased from 80 C. to 175 C. in 2 hours. The pressure was decreased at 120 C. to ensure timely discharge the n-butanol. The temperature was kept at 175 C. for 2 hour. The material temperature was decreased to 130 C. About 1000 g toluene was added and then stirred for 0.5 hour. The material was discharged to obtain a DOPO-containing bisphenol A (A2).

REFERENCE EXAMPLE 3

(5) 400 g bisphenol F, 210 g formaldehyde aqueous solution (mass concentration is 37%), and 24 g NaOH were put into a reactor and then stirred. The temperature was increased to 50 C. and then kept for 3 hours. Next, the temperature was increased to 65 C. and then kept for 3 hours. Afterwards, 480 g n-butanol was added and then refluxed for 12 hours. The temperature was then decreased to 55-60 C. About 324 g n-butanol was removed by reduced pressure distillation to obtain an intermediate. The intermediate was added with 380 g DOPO (9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), and the material temperature was progressively increased from 80 C. to 180 C. in 2 hours. The pressure was decreased at 120 C. to ensure timely discharge the n-butanol. The temperature was kept at 180 C. for 2 hour. The material temperature was decreased to 130 C. About 1000 g toluene was added and then stirred for 0.5 hour. The material was discharged to obtain a DOPO-containing bisphenol F (A3).

REFERENCE EXAMPLE 4

(6) 520 g bisphenol S, 210 g formaldehyde aqueous solution (mass concentration is 37%), and 24 g NaOH were put into a reactor and then stirred. The temperature was increased to 50 C. and then kept for 3 hours. Next, the temperature was increased to 85 C. and then kept for 3 hours. Afterwards, 480 g n-butanol was added and then refluxed for 12 hours. The temperature was then decreased to 55-60 C. About 324 g n-butanol was removed by reduced pressure distillation to obtain an intermediate. The intermediate was added with 380 g DOPO (9,10-Dihydro-9-oxa-10-phosphaphenanthene-10-oxide), and the material temperature was progressively increased from 80 C. to 180 C. in 2 hours. The pressure was decreased at 130 C. to ensure timely discharge the n-butanol. The temperature was kept at 180 C. for 1 hour. The material temperature was decreased to 130 C. About 1000 g toluene was added and then stirred for 0.5 hour. The material was discharged to obtain a DOPO-containing bisphenol S (A4).

REFERENCE EXAMPLE 5

(7) 664 g dicyclopentadiene phenol resin, 210 g formaldehyde aqueous solution (mass concentration is 37%), and 24 g NaOH were put into a reactor and then stirred. The temperature was increased to 50 C. and then kept for 3 hours. Next, the temperature was increased to 65 C. and then kept for 3 hours. Afterwards, 480 g n-butanol was added and then refluxed for 12 hours. The temperature was then decreased to 55-60 C. About 324 g n-butanol was removed by reduced pressure distillation to obtain an intermediate. The intermediate was added with 1080 g DOPO (9,10-Dihydro-9-oxa-10-phosphaphenanth ene-10-oxide), and the material temperature was progressively increased from 80 C. to 180 C. in 2 hours. The pressure was decreased at 120 C. to ensure timely discharge the n-butanol. The temperature was kept at 180 C. for 2 hour. The material temperature was decreased to 130 C. About 1000 g toluene was added and then stirred for 0.5 hour. The material was discharged to obtain a DOPO-containing dicyclopentadiene phenol resin (A5).

SYNTHETIC EXAMPLE 1

(8) In this reference example, the preparation of poly (2,6-dimethylphenyl ether) is detailed described. In a 5 L 5-necked round bottom flask equipped with a top stirrer, thermometer, and oxygen dip tube, 2.5 g N,N-di-t-butyl-ethylenediamine (DBEDA), 32 g N,N-dimethyl-butylamine (DBMA), 10 g di-n-butylamine (DBA), 2.8 g methyl trioctyl ammonium chloride, 500 g toluene, and 45 g 50% toluene solution of 2,6-dimethylphenol were added, 8.5 g copper catalyst (a storage solution prepared by adding 14.3 g cuprous oxide to 187.07 g of 48% HBr) was added. Under vigorous stirring, a flow rate of 2 ft.sup.3/min oxygen was passed through the solution and a solution of 2,6-dimethylphenol. The mixture was re-stirred for 3 hours, and a water bath was used to keep the temperature below 35 C. 10 ml of glacial acetic acid was used to treat the solution to quench the catalyst. The polymer was separated from the organic phase through methanol precipitation, and the obtained wet cake was dissolved in toluene and re-precipitated in methanol. The separated solid was dried at 70 C. and under vacuum overnight to obtain poly(2,6-dimethylphenyl ether) (A). The obtained poly(2,6-dimethylphenyl ether) containing hydroxyl groups (OH) was derived through using phosphorous agent, and the content of the terminal hydroxyl group was determined by .sup.31P NMR to be 0.16%. Weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography using standard polystyrene in THE to be 12531 and 26945 respectively, and the polydispersity index (Mw/Mn) was 2.15.

(9) Synthetic examples 2-6 describe the preparation of phosphorus-containing dihydroxylated poly(arylene ether) in the presence of phosphorous-containing bisphenol compound to redistribute poly (2,6-dimethylphenyl ether).

SYNTHETIC EXAMPLE 2

(10) In a reactor with a bottom plug valve, 300 g toluene was added as a solvent. After heating to 90 C., 100 g poly(2,6-dimethylphenyl ether) in the reference synthetic example 1 and 10 g DOPO-containing dihydroxybiphenyl in the reference example 1 were dissolved to be a polyphenol compound. 100 g toluene solution of benzoyl peroxide (BPO) was added in 60 minutes and reacted at 90 C. for 180 minutes. Then, the reaction solution was sufficiently washed by NaHCO.sub.3 aqueous solution, and the aqueous solution was removed. The polymer was separated from the organic phase through methanol precipitation, and the obtained wet cake was dissolved in toluene and re-precipitate in methanol. The separated solid was dried at 70 C. and under vacuum overnight to obtain phosphorous-containing dihydroxylated poly(arylene ether) (C1). The hydroxyl groups (OH) of the obtained material containing phosphorous was derived through using phosphorous agent, and the content of the terminal hydroxyl group was determined by .sup.31P NMR to be 2.09%. Weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography using standard polystyrene in THF to be 2531 and 3215 respectively, and the polydispersity index (Mw/Mn) was 1.27.

SYNTHETIC EXAMPLES 3-6

(11) The synthesis was performed according to the raw material composition of Table 1 and the method of the synthetic example 2 to obtain a different phosphorous-containing dihydroxylated poly(arylene ether) (C2-C5).

(12) TABLE-US-00001 TABLE 1 Synthetic example 2 3 4 5 6 Crude Material C1 C2 C3 C4 C5 poly(2,6-dimethylphenyl ether) 300 300 300 300 300 (B) (g) DOPO-containing dihydroxyl 10 biphenyl (A1) (g) DOPO-containing bisphenol 10 A (A2) (g) DOPO-containing bisphenol 10 F (A3) (g) DOPO-containing bisphenol 10 S (A4) (g) DOPO-containing dicyclo- 10 pentadiene phenol resin (A5) (g) Benzoyl peroxide (BPO) (g) 10 10 10 10 10 Hydroxyl group content (%) 2.09 2.04 1.97 1.98 1.95 Number average molecular 2531 2331 2241 2150 2548 weight (Mw) Weight average molecular 3215 3007 2958 2688 3338 weight (Mn) polydispersity index (Mw/Mn) 1.27 1.29 1.32 1.25 1.31

(13) Synthetic examples 7-11 describe phosphorous-containing dihydroxylated poly(arylene ether) copolymerized by 2,6-dimethyl phenol in the presence of phosphorous-containing bisphenol compounds.

SYNTHETIC EXAMPLE 7

(14) In a 5 L 5-necked round bottom flask equipped with a top stirrer, thermometer, and oxygen dip tube, 900 mL toluene, 20 g DOPO-containing dihydroxyl biphenyl (A1) in the reference example 1, 2.5 mL of 10% toluene solution of methyl trioctyl ammonium chloride, 60 mL of toluene solution of an amine (prepared by a composition of 5 mL di-t-butyl ethylene diamine, 100 mL dimethylbutyl amine, 25 mL dibutyl amine, and 300 mL toluene), 60 g 2,6-dimethylphenol in 50 wt % toluene solution, and 2.5 mL copper bromide solution were added. Under vigorous stirring, oxygen was passed through the solution at a flow rate of 0.4 ft.sup.3/min. When the reaction temperature was kept at 90 C., 600 g 2,6-dimethyl phenol in 50% toluene solution was added through an additional funnel in 100 minutes. In that period, a water bath was used to keep the reaction temperature at about 25 C. After addition, the water bath was removed, and the reaction temperature was increased to 35 C. After 1 hour at that temperature, the oxygen flow was terminated, and the water bath was increased to 60 C. The temperature was kept for 60 minutes. 10 mL acetic acid was used to quench the reaction, and the temperature was cooled to room temperature. The polymer was separated from the organic phase through methanol precipitation, and the obtained wet cake was dissolved in toluene and re-precipitated in methanol. The separated solid was dried at 70 C. overnight to obtain phosphorous-containing dihydroxylated poly(arylene ethee) (D1). The hydroxyl groups (OH) of the obtained material containing phosphorous was derived through using phosphorous agent, and the content of the terminal hydroxyl group was determined by .sup.31P NMR to be 2.03%. Weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography using standard polystyrene in THF to be 2256 and 3722 respectively, and the polydispersity index (Mw/Mn) was 1.65.

SYNTHETIC EXAMPLES 8-11

(15) The synthesis was performed according to the raw material composition of Table 2 and the method of the synthetic example 7 to obtain a different phosphorous-containing dihydroxylated poly(arylene ether) (D2-D5).

(16) TABLE-US-00002 TABLE 2 Synthetic example 7 8 9 10 11 Crude Material D1 D2 D3 D4 D5 poly(2,6-dimethylphenyl ether) (g) 330 330 330 330 330 DOPO-containing dihydroxyl 20 biphenyl (A1) (g) DOPO-containing bisphenol 20 A (A2) (g) DOPO-containing bisphenol 20 F (A3) (g) DOPO-containing bisphenol 20 S (A4) (g) DOPO-containing dicyclo- 20 pentadiene phenol resin (A5) (g) Hydroxyl group content (%) 2.03 1.98 1.92 2.02 1.89 Number average molecular 2256 2376 2178 2673 2793 weight (Mw) Weight average molecular 3722 4158 3680 4330 4945 weight (Mn) Polydispersity index (Mw/Mn) 1.65 1.75 1.69 1.62 1.77

(17) Synthetic examples 12-16 describe that methacrylic anhydride was used as a capping agent to cap the phosphorous-containing dihydroxylated poly(arylene ether) to prepare phosphorous-containing di-functionalized poly(arylene ether).

SYNTHETIC EXAMPLE 12

(18) 100 g phosphorous-containing di-hydroxylated poly(arylene ether) (C1) in synthetic example 2 was dissolved in 300 mL toluene, and 20 g 4-dimethylaminopyridine was added to the obtained solution. The mixture solution was heated to 90 C. under a stirring condition. When the reaction temperature was kept at 90 C. the 60 mL 50% toluene solution of methacrylic anhydride was added through an additional funnel in 30 minutes. The temperature was kept for 10 hours, and then cooled to room temperature. The polymer was separated from the organic phase through methanol precipitation, and the obtained wet cake was dissolved in toluene and re-precipitated in methanol. The separated solid was dried at 70 C. overnight to obtain phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid (E1). The content of hydroxyl group of the phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid was smaller than the detecting limit of 15 ppm.

SYNTHETIC EXAMPLE 13

(19) 100 g phosphorous-containing dihydroxylated poly(arylene ether) (C2) in synthetic example 3 was dissolved in 300 mL toluene, and 20 g 4-dimethylaminopyridine was added to the obtained solution. The mixture solution was heated to 90 C. under a stirring condition. When the reaction temperature was kept at 90 C., the 60 mL 50% toluene solution of methacrylic anhydride was added through an additional funnel in 30 minutes. The temperature was kept for 10 hours, and then cooled to room temperature. The polymer was separated from the organic phase through methanol precipitation, and the obtained wet cake was dissolved in toluene and re-precipitated in methanol. The separated solid was dried at 70 C. overnight to obtain phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid (E2). The content of hydroxyl group of the phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid was smaller than the detecting limit of 15 ppm.

SYNTHETIC EXAMPLE 14

(20) 100 g phosphorous-containing dihydroxylated poly(arylene ether) (C3) in synthetic example 4 was dissolved in 300 mL toluene, and 20 g 4-dimethylaminopyridine was added to the obtained solution. The mixture solution was heated to 90 C. under a stirring condition. When the reaction temperature was kept at 90 C., the 60 mL 50% toluene solution of methacrylic anhydride was added through an additional funnel in 30 minutes. The temperature was kept for 10 hours, and then cooled to room temperature. The polymer was separated from the organic phase through methanol precipitation, and the obtained wet cake was dissolved in toluene and re-precipitated in methanol. The separated solid was dried at 70 C. overnight to obtain phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid (E3). The content of hydroxyl group of the phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid was smaller than the detecting limit of 15 ppm.

SYNTHETIC EXAMPLE 15

(21) 100 g phosphorous-containing dihydroxylated poly(arylene ether) (C4) in synthetic example 5 was dissolved in 300 mL toluene, and 20 g 4-dimethylaminopyridine was added to the obtained solution. The mixture solution was heated to 90 C. under a stirring condition. When the reaction temperature was kept at 90 C., the 60 mL 50% toluene solution of methacrylic anhydride was added through an additional funnel in 30 minutes. The temperature was kept for 10 hours, and then cooled to room temperature. The polymer was separated from the organic phase through methanol precipitation, and the obtained wet cake was dissolved in toluene and re-precipitated in methanol. The separated solid was dried at 70 C. overnight to obtain phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid (E4). The content of hydroxyl group of the phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid was smaller than the detecting limit of 15 ppm.

SYNTHETIC EXAMPLE 16

(22) 100 g phosphorous-containing dihydroxylated poly(arylene ether) (C5) in synthetic example 6 was dissolved in 300 mL, toluene, and 20 g 4-dimethylaminopyridine was added to the obtained solution. The mixture solution was heated to 90 C. under a stirring condition. When the reaction temperature was kept at 90 C., the 60 mL 50% toluene solution of methacrylic anhydride was added through an additional funnel in 30 minutes. The temperature was kept for 10 hours, and then cooled to room temperature. The polymer was separated from the organic phase through methanol precipitation, and the obtained wet cake was dissolved in toluene and re-precipitated in methanol. The separated solid was dried at 70 C. overnight to obtain phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid (E5). The content of hydroxyl group of the phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid was smaller than the detecting limit of 15 ppm.

(23) Synthetic examples 17-21 describe that vinylbenzyl chlodide was used as a capping agent to cap the phosphorous-containing dihydroxylated poly(arylene ether) to prepare phosphorous-containing di-functionalized poly(arylene ether).

SYNTHETIC EXAMPLE 17

(24) 100 g phosphorous-containing di-hydroxylated poly(arylene ether) (C1) prepared in synthetic example 2 and 27 g vinylbenzyl chloride was dissolved in 300 mL N,N-dimethylacetamide. The mixture solution was heated to 50 C. under a stirring condition. When the reaction temperature was kept at 50 C., the 50 mL 20% methanol solution of sodium methoxide was added through an additional funnel in 30 minutes. The temperature was kept for 1 hour, and 10 mL 20% MeOH solution of sodium methoxide was dropwise added. The reaction mixture was heated to 70 C., and stirred for 1 hour at a kept temperature. 2.5 g 30% N,N-dimethylacetamide solution of phosphate was then added. 500 g toluene and 500 g water was added and stirrer. After standing, the pH of the separated water phase was 4.0. The generated salt was removed by filtering. After removing the salt, the acidic solution was dropwise added by 150 g 20% methanol solution of sodium methoxide. 300 g toluene and 300 g pure water were added and stirred. After standing, the pH of the separated water phase was 5.8. The salt obtained by adding alkaline material was removed, and the salt-free solution was dropwise added to 600 g water to precipitate polymer. The wet cake of the separated polymer was dissolved in toluene and re-precipitated in methanol. The separated solid was dried under vacuum at 70 C. overnight to obtain phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group (F1). The content of hydroxyl group of the phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group was smaller than the detecting limit of 15 ppm.

SYNTHETIC EXAMPLE 18

(25) 100 g phosphorous-containing di-hydroxylated poly(arylene ether) (C2) prepared in synthetic example 3 and 27 g vinylbenzyl chloride was dissolved in 300 mL N,N-dimethylacetamide. The mixture solution was heated to 50 C. under a stirring condition. When the reaction temperature was kept at 50 C., the 50 mL 20% methanol solution of sodium methoxide was added through an additional funnel in 30 minutes. The temperature was kept for 1 hour, and 10 mL 20% MeOH solution of sodium methoxide was dropwise added. The reaction mixture was heated to 70 C., and stirred for 1 hour at a kept temperature. 2.5 g 30% N,N-dimethylacetamide solution of phosphate was then added. 500 g toluene and 500 g water was added and stirrer. After standing, the pH of the separated water phase was 4.0. The generated salt was removed by filtering. After removing the salt, the acidic solution was dropwise added by 150 g 20% methanol solution of sodium methoxide. 300 g toluene and 300 g pure water were added and stirred. After standing, the pH of the separated water phase was 5.8. The salt obtained by adding alkaline material was removed, and the salt-free solution was dropwise added to 600 g water to precipitate polymer. The wet cake of the separated polymer was dissolved in toluene and re-precipitated in methanol. The separated solid was dried under vacuum at 70 C. overnight to obtain phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group (F2). The content of hydroxyl group of the phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group was smaller than the detecting limit of 15 ppm.

SYNTHETIC EXAMPLE 19

(26) 100 g phosphorous-containing di-hydroxylated poly(arylene ether) (C3) prepared in synthetic example 4 and 27 g vinylbenzyl chloride was dissolved in 300 mL N,N-dimethylacetamide. The mixture solution was heated to 50 C. under a stirring condition. When the reaction temperature was kept at 50 C., the 50 mL 20% methanol solution of sodium methoxide was added through an additional funnel in 30 minutes. The temperature was kept for 1 hour, and 10 mL 20% MeOH solution of sodium methoxide was dropwise added. The reaction mixture was heated to 70 C., and stirred for 1 hour at a kept temperature. 2.5 g 30% N,N-dimethylacetamide solution of phosphate was then added. 500 g toluene and 500 g water was added and stirrer. After standing, the pH of the separated water phase was 4.0. The generated salt was removed by filtering. After removing the salt, the acidic solution was dropwise added by 150 g 20% methanol solution of sodium methoxide. 300 g toluene and 300 g pure water were added and stirred. After standing, the pH of the separated water phase was 5.8. The salt obtained by adding alkaline material was removed, and the salt-free solution was dropwise added to 600 g water to precipitate polymer. The wet cake of the separated polymer was dissolved in toluene and re-precipitated in methanol. The separated solid was dried under vacuum at 70 C. overnight to obtain phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group (F3). The content of hydroxyl group of the phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group was smaller than the detecting limit of 15 ppm.

SYNTHETIC EXAMPLE 20

(27) 100 g phosphorous-containing di-hydroxylated poly(arylene ether) (C4) prepared in synthetic example 5 and 27 g vinylbenzyl chloride was dissolved in 300 mL N,N-dimethylacetamide. The mixture solution was heated to 50 C. under a stirring condition. When the reaction temperature was kept at 50 C., the 50 mL 20% methanol solution of sodium methoxide was added through an additional funnel in 30 minutes. The temperature was kept for 1 hour, and 10 mL 20% MeOH solution of sodium methoxide was dropwise added. The reaction mixture was heated to 70 C. and stirred for 1 hour at a kept temperature. 2.5 g 30% N,N-dimethylacetamide solution of phosphate was then added. 500 g toluene and 500 g water was added and stirrer. After standing, the pH of the separated water phase was 4.0. The generated salt was removed by filtering. After removing the salt, the acidic solution was dropwise added by 150 g 20% methanol solution of sodium methoxide. 300 g toluene and 300 g pure water were added and stirred. After standing, the pH of the separated water phase was 5.8. The salt obtained by adding alkaline material was removed, and the salt-free solution was dropwise added to 600 g water to precipitate polymer. The wet cake of the separated polymer was dissolved in toluene and re-precipitated in methanol. The separated solid was dried under vacuum at 70 C. overnight to obtain phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group (F4). The content of hydroxyl group of the phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group was smaller than the detecting limit of 15 ppm.

SYNTHETIC EXAMPLE 21

(28) 100 g phosphorous-containing di-hydroxylated poly(arylene ether) (C5) prepared in synthetic example 6 and 27 g vinylbenzyl chloride was dissolved in 300 mL N,N-dimethylacetamide. The mixture solution was heated to 50 C. under a stirring condition. When the reaction temperature was kept at 50 C., the 50 mL 20% methanol solution of sodium methoxide was added through an additional funnel in 30 minutes. The temperature was kept for 1 hour, and 10 mL 20% MeOH solution of sodium methoxide was dropwise added. The reaction mixture was heated to 70 C., and stirred for 1 hour at a kept temperature. 2.5 g 30% N,N-dimethylacetamide solution of phosphate was then added. 500 g toluene and 500 g water was added and stirrer. After standing, the pH of the separated water phase was 4.0. The generated salt was removed by filtering. After removing the salt, the acidic solution was dropwise added by 150 g 20% methanol solution of sodium methoxide 300 g toluene and 300 g pure water were added and stirred. After standing, the pH of the separated water phase was 5.8. The salt obtained by adding alkaline material was removed, and the salt-free solution was dropwise added to 600 g water to precipitate polymer. The wet cake of the separated polymer was dissolved in toluene and re-precipitated in methanol. The separated solid was dried under vacuum at 70 C. overnight to obtain phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group (F5). The content of hydroxyl group of the phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group was smaller than the detecting limit of 15 ppm.

APPLIED EXAMPLE 1

(29) 100 g phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid (E1) in synthetic example 12 was completely dissolved in 100 g toluene to obtain a solution of functionalized poly(arylene ether). 40 g styrene-butadiene copolymer as a crosslinking agent, 3.5 g dicumyl peroxide (DCP) as an initiator, 50 g silica as a filler, and 3 g 3-glycidyltrimethoxysilane were added and then stirred to dissolve them in toluene until a resin composition was formed.

(30) Afterward, the uniform resin composition obtained above was infiltrate an E-fiberglass cloth and heated at 155 C. for 3-10 minutes to completely volatilize the solvent to obtain a prepreg. 8 prepregs were laminated, and two surfaces thereof were cladded by 35 m copper foils. Thermocompression was performed under a temperature of 200 C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided cooper clad laminate.

APPLIED EXAMPLE 2

(31) 80 g phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid (E1) in synthetic example 12 was dissolved in 80 g toluene to obtain a solution of functionalized poly(arylene ether) after dissolved completely. 60 g styrene-butadiene copolymer as a crosslinking agent, 3.5 g dicumyl peroxide (DCP) as an initiator, 50 g silica as a filler, and 3 g 3-glycidyitrimethoxysilane were added and then stirred to dissolve them in toluene until a resin composition was formed.

(32) Afterward, the uniform resin composition obtained above was infiltrate an E-fiberglass cloth and heated at 155 C. for 3-10 minutes to completely volatilize the solvent to obtain a prepreg. 8 prepregs were laminated, and two surfaces thereof were cladded by 35 m copper foils. Thermocompression was performed under a temperature of 200 C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided cooper clad laminate.

APPLIED EXAMPLE 3

(33) 50 g phosphorous-containing di-functionalized poly(arylene ether) capped by methacrylic acid (E1) in synthetic example 12 was dissolved in 50 g toluene to obtain a solution of functionalized poly(arylene ether) after dissolved completely. 80 g maleic anhydride modified butadiene resin as a crosslinking agent, 3.5 g dicumyl peroxide (DCP) as an initiator, 50 g silica as a filler, and 3 g 3-glycidyltrimethoxysilane were added and then stirred to dissolve them in toluene until a resin composition was formed.

(34) Afterward, the uniform resin composition obtained above was infiltrate an E-fiberglass cloth and heated at 155 C. for 3-10 minutes to completely volatilize the solvent to obtain a prepreg. 8 prepregs were laminated, and two surfaces thereof were cladded by 35 m copper foils. Thermocompression was performed under a temperature of 200 C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided cooper clad laminate.

APPLIED EXAMPLE 4

(35) 100 g phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group (F1) in synthetic example 17 was dissolved in 100 g toluene to obtain a solution of functionalized poly(arylene ether) after dissolved completely. 60 g styrene-butadiene copolymer as a crosslinking agent, 3.5 g dicumyl peroxide (DCP) as an initiator, 50 g silica as a filler, and 3 g 3-glycidyltrimethoxysilane were added and then stirred to dissolve them in toluene until a resin composition was formed.

(36) Afterward, the uniform resin composition obtained above was infiltrate an E-fiberglass cloth and heated at 155 C. for 3-10 minutes to completely volatilize the solvent to obtain a prepreg. 8 prepregs ere laminated, and two surfaces thereof were cladded by 35 m copper foils. Thermocompression was performed under a temperature of 200 C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided cooper clad laminate.

APPLIED EXAMPLE 5

(37) 80 g phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group (F1) in synthetic example 17 was dissolved in 80 g toluene to obtain a solution of functionalized poly(arylene ether) after dissolved completely. 80 g styrene-butadiene copolymer as a crosslinking agent, 3.5 g dicumyl peroxide (DCP) as an initiator, 50 g silica as a filler, and 3 g 3-glycidyltrimethoxysilane were added and then stirred to dissolve them in toluene until a resin composition was formed.

(38) Afterward, the uniform resin composition obtained above was infiltrate an E-fiberglass cloth and heated at 155 C. for 3-10 minutes to completely volatilize the solvent to obtain a prepreg. 8 prepregs were laminated, and two surfaces thereof were cladded by 35 m copper foils. Thermocompression was performed under a temperature of 200 C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided cooper clad laminate.

APPLIED EXAMPLE 6

(39) 100 g phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group (F1) in synthetic example 17 was dissolved in 80 g toluene to obtain a solution of functionalized poly(arylene ether) after dissolved completely. 60 g styrene-butadiene-divinylbenzene copolymer as a crosslinking agent, 3.5 g dicumyl peroxide (DCP) as an initiator, 50 g silica as a filler, and 3 g 3-glycidyltrimethoxysilane were added and then stirred to dissolve them in toluene until a resin composition was formed.

(40) Afterward, the uniform resin composition obtained above was infiltrate an E-fiberglass cloth and heated at 155 C. for 3-10 minutes to completely volatilize the solvent to obtain a prepreg. 8 prepregs were laminated, and two surfaces thereof were cladded by 35 m copper foils. Thermocompression was performed under a temperature of 200 C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided cooper clad laminate.

APPLIED COMPARISON EXAMPLE 1

(41) 80 g phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group (F1) in synthetic example 17 was dissolved in 80 g toluene to obtain a solution of functionalized poly(arylene ether) after dissolved completely. 30 g triallyl isocyanurate (DVB) as a crosslinking agent, 3.5 g dicumyl peroxide (DCP) as an initiator, 50 g silica as a filler, and 3 g 3-glycidyltrimethoxysilane were added and then stirred to dissolve them in toluene until a resin composition was formed.

(42) Afterward, the uniform resin composition obtained above was infiltrate an E-fiberglass cloth and heated at 155 C. for 3-10 minutes to completely volatilize the solvent to obtain a prepreg. 8 prepregs were laminated, and two surfaces thereof were cladded by 35 m copper foils. Thermocompression was performed under a temperature of 200 C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided cooper clad laminate.

APPLIED COMPARISON EXAMPLE 2

(43) 80 g phosphorous-containing di-functionalized poly(arylene ether) capped by vinylbenzyl group (F1) in synthetic example 17 was dissolved in 80 g toluene to obtain a solution of functionalized poly(arylene ether) after dissolved completely. 35 g divnyl benzene (DVB) as a crosslinking agent, 3.5 g dicumyl peroxide (DCP) as an initiator, 50 g silica as a filler, and 3 g 3-glycidyltrimethoxysilane were added and then stirred to dissolve them in toluene until a resin composition was formed.

(44) Afterward, the uniform resin composition obtained above was infiltrate an E-fiberglass cloth and heated at 155 C. for 3-10 minutes to completely volatilize the solvent to obtain a prepreg. 8 prepregs were laminated, and two surfaces thereof were cladded by 35 m copper foils. Thermocompression was performed under a temperature of 200 C. and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided cooper clad laminate.

(45) TABLE-US-00003 TABLE 3 Applied comparison Material and Applied example example properties 1 2 3 4 5 1 2 Compatibility good good good good good good good Volatility no no no no no yes yes Fluidity good good good good good good good Peel strength 1.30 1.42 1.28 145 1.41 0.81 0.55 (n/mm) Tg (DMA) 231 225 226 240 235 220 200 ( C.) Dielectric 3.68 3.65 3.25 3.71 3.31 3.49 3.61 constant (10 GHz) Dielectric loss 0.0048 0.0042 0.0049 0.0038 0.0036 0.0057 0.0048 tangent (10 GHz) Dip resistance >120 >120 >120 >120 >120 >120 >120 weldability 288 C. (sec) Prepreg not not not not not not not stickiness sticky sticky sticky sticky sticky sticky sticky Bending 330 340 320 380 365 267 287 strength (MPa) T288 (min) >15 >15 >15 >15 >15 >15 >15

(46) The test method of the above properties are described below:

(47) (1) Glass transition temperature (Tg) was tested according to the DMA testing method in PC-TM-6502.4.24.

(48) (2) Dielectric constant (Dk) and dielectric loss tangent (Df) were measured according to SPQR method.

(49) (3) The mixed glue stood to observe whether the glue was a uniform and transparent solution. After standing for 24 hours, the resin composition was observed whether delamination phenomenon was existed. The test method of the volatility was described below. The prepared prepregs were baked at 155 C. for 10 minutes. The weight loss of the prepregs was measured. The volatility of the resin composition is great if the weight loss was over 2%. The fluidity of the resin was measured by the known measuring method in the art.

(50) Physical Properties Analysis

(51) According to the physical properties in Table 3, it can be known that among applied example 1-5 the resins using olefin resins containing styrene segment and functionalized poly(arylene ether) resin have good compatibility, and the prepared laminated sheets have good heat resistance and dielectric properties. The comparison examples 1-2 use low molecular compound having multi-functional groups, triallyl isocyanurate (TAIC) and divinyl benzene (DVB), to be the crosslinking agent. Although the cross-linking effect is very good, but triallyl isocyanurate (TAIC) and divinyl benzene (DVB) have very strong volatility.

(52) As described above, comparing with the general copper clad laminate, the copper clad laminate prepared from the polyphenylene oxide resin composition of this invention has better dielectric properties, i.e. lower dielectric constant and dielectric loss tangent, and has very good heat resistance and moisture resistance. The copper clad laminates of this invention are suitable to be used in high-frequency and high-speed printed circuit board field, and used in the processing of multilayer printed circuit board.

(53) Although this invention has been practiced according to preferred embodiments, but the persons skilled in the art will understand that the elements may be changed and replaced by the equivalents thereof without departure the scope of this invention. Moreover, many improvements may be made to make a certain condition or material to be suitably used in the technical content taught by this invention without departure the scope of this invention. Therefore, this invention was not limited by particular embodiments of the invention disclosed in the best way contemplated, and comprises all of the embodiments in the appended claims.

(54) Although the embodiments of the present invention have been disclosed as above, it is not intended to limit the present invention. Any person skilled in the art can make various modifications and variations without departing from the spirit and scope of the present invention. Therefore, the scope of the invention should be as defined by the appended claims.