Phosphorous containing compounds and process for synthesis

Abstract

The instant disclosure relates to phosphorus-containing compounds that can be used to form flame retardant phosphorus-containing resins, and also can serve as a hardener for a flame retardant epoxy resin compositions. In particular, the phosphorus-containing compounds are modified with acyloxy groups (O(CO)R), as shown below. Incorporation of the acyloxy groups results in resins that are water resistant and exhibit improved dielectric properties. ##STR00001##

Claims

1. A compound of Formula (II) ##STR00051## wherein, n is an integer from 1 to 4; R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, and C.sub.3-C.sub.10 cycloalkyl; R.sub.5 is independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.10 cycloalkyl, and Ar.sub.a; and Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of ##STR00052## Ar.sub.3 is selected from the group consisting of ##STR00053## R.sub.6 and R.sub.7 are independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl group, C.sub.1-C.sub.10 alkoxy, and a cyclic alkyl group having 3-10 carbon atoms, m and n are independently an integer from 0 to 4; R.sub.8 is absent or is selected from the group consisting of CH.sub.2, (CH.sub.3).sub.2C, CO, SO.sub.2, and O R.sub.9 is absent or is (CH.sub.2).sub.p, wherein p is an integer from 1 to 20; z is 1; A is selected from the group consisting of C.sub.1-C.sub.10 alkyl, ##STR00054## wherein, each R.sub.10 is independently H or C.sub.1-C.sub.10 alkyl; and x is an integer from 0 to 4; and Ep is selected from the group consisting of: ##STR00055## wherein each of R.sub.11 is independently selected from the group consisting of H, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, a cyclic alkyl group having 3-7 carbon atoms, phenyl, and a phenoxyl group.

2. The compound of claim 1, wherein each of R.sub.11 is independently H or a C.sub.1-C.sub.6 alkyl.

3. The compound of claim 1, wherein Ep is selected from the group consisting of: ##STR00056##

4. The compound of claim 3, wherein R.sub.9 is absent.

5. The compound of claim 1, wherein R.sub.5 is H.

6. The compound of claim 1, wherein R.sub.5 is C.sub.1-C.sub.10 alkyl.

7. The compound of claim 1, wherein R.sub.5 is methyl.

8. The compound of claim 1, wherein Ar.sub.1 and Ar.sub.2 are ##STR00057##

9. The compound of claim 1, wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are H.

10. The compound of claim 1, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are H; R.sub.5 is C.sub.1-C.sub.10 alkyl; Ar.sub.1 and Ar.sub.2 are ##STR00058## and R.sub.11 is H.

11. The compound of claim 10, wherein Ep is selected from the group consisting of: ##STR00059##

12. The compound of claim 11, wherein R.sub.9 is absent.

13. A method for synthesizing a compound of Formula (II) ##STR00060## wherein, n is an integer from 1 to 4; R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.10 cycloalkyl; R.sub.5 is independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, and C.sub.3-C.sub.10 cycloalkyl, and Ar.sub.a; and Ar.sub.1 and Ar.sub.2 are independently selected from the group consisting of ##STR00061## Ar.sub.3 is selected from the group consisting of ##STR00062## R.sub.6 and R.sub.7 are independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl group, C.sub.1-C.sub.10 alkoxy, and a cyclic alkyl group having 3-10 carbon atoms, m and n are independently an integer from 0 to 4; R.sub.8 is absent or is selected from the group consisting of CH.sub.2, (CH.sub.3).sub.2C, CO, SO.sub.2, and O R.sub.9 is absent or is (CH.sub.2).sub.p, wherein p is an integer from 1 to 20; z is 1; A is selected from the group consisting of C.sub.1-C.sub.10 alkyl, ##STR00063## wherein, each R.sub.10 is independently H or C.sub.1-C.sub.10 alkyl; and x is an integer from 0 to 4; and Ep is selected from the group consisting of: ##STR00064## wherein each of R.sub.11 is independently selected from the group consisting of H, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, a cyclic alkyl group having 3-7 carbon atoms, phenyl, and a phenoxyl group; comprising performing a catalytic reaction of a compound of formula (I) ##STR00065## with an epoxy monomer of formula (III) ##STR00066##

14. The method of claim 13, wherein each of R.sub.11 is independently H or a C.sub.1-C.sub.6 alkyl.

15. The method of claim 13, wherein Ep is selected from the group consisting of: ##STR00067##

16. The method of claim 13, wherein R.sub.5 is H.

17. The method of claim 13, wherein R.sub.5 is C.sub.1-C.sub.10 alkyl.

18. The method of claim 13, wherein R.sub.5 is methyl.

19. The method of claim 13, wherein Ar.sub.1 and Ar.sub.2 are ##STR00068##

20. A compound selected from the group consisting of: ##STR00069## ##STR00070## wherein n is an integer from 1 to 4.

Description

DETAILED DESCRIPTION OF THE DISCLOSURE

(1) The instant disclosure relates to compound of formula (I):

(2) ##STR00011##

(3) wherein, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected from the group consisting of H, C.sub.1-C.sub.10, C.sub.1-C.sub.10 alkoxy, and C.sub.3-C.sub.10 cycloalkyl;

(4) R.sub.5 is independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.10 cycloalkyl, and Ar.sub.3; and

(5) Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently selected from the group consisting of

(6) ##STR00012##

(7) R.sub.6 and R.sub.7 are independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl group, C.sub.1-C.sub.10 alkoxy, and a cyclic alkyl group having 3-10 carbon atoms,

(8) M and n are independently an integer from 0 to 4;

(9) R.sub.8 is absent or is selected from the group consisting of CH.sub.2, (CH.sub.3).sub.2C), CO, SO.sub.2, and O

(10) R.sub.9 is absent or is (CH.sub.2).sub.p, wherein p is an integer from 1 to 20;

(11) A is selected from the group consisting of C.sub.1-C.sub.10 alkyl,

(12) ##STR00013##

(13) wherein, each R.sub.10 is independently H or C.sub.1-C.sub.10 alkyl; and

(14) x is an integer from 0 to 4.

(15) In some instances, R.sub.5 is H or C.sub.1-C.sub.10 alkyl. In other instances, Ar.sub.1 and Ar.sub.2 are

(16) ##STR00014##
and in some instances R.sub.9 may be absent.

(17) In some instances, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are hydrogen. In other instances, A is C.sub.1-C.sub.10 alkyl,

(18) ##STR00015##
and in some instances, x is zero.

(19) The instant disclosure also relates to a compound of formula (Ia)

(20) ##STR00016##

(21) wherein, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected from the group consisting of H, C.sub.1-C.sub.10, C.sub.1-C.sub.10 alkoxy, and C.sub.3-C.sub.10 cycloalkyl;

(22) R.sub.5 is independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.10 cycloalkyl, and Ar.sub.3; and

(23) Ar.sub.3 is independently selected from the group consisting of

(24) ##STR00017##

(25) R.sub.6 and R.sub.7 are independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl group, C.sub.1-C.sub.10 alkoxy, and a cyclic alkyl group having 3-10 carbon atoms,

(26) M and n are independently an integer from 0 to 4;

(27) R.sub.8 is absent or is selected from the group consisting of CH.sub.2, (CH.sub.3).sub.2CH.sub.2, CO, SO.sub.2, and O

(28) R.sub.9 is absent or is (CH.sub.2).sub.p, wherein p is an integer from 1 to 20; and

(29) A is selected from the group consisting of C.sub.1-C.sub.10 alkyl,

(30) ##STR00018##

(31) wherein, each R.sub.10 is independently H or C.sub.1-C.sub.10 alkyl; and

(32) x is an integer from 0 to 4.

(33) In some cases, R.sub.5 is H or C.sub.1-C.sub.10 alkyl; and in some cases R.sub.5 is methyl. In some cases, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are hydrogen. Furthermore, A can be a C.sub.1-C.sub.10 alkyl,

(34) ##STR00019##
and in some cases x may be zero.

(35) The instant disclosure further relates to a compound selected from the group consisting of:

(36) ##STR00020##

(37) The instant disclosure relates to a compound of Formula (II):

(38) ##STR00021##

(39) wherein, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are independently selected from the group consisting of H, C.sub.1-C.sub.10, C.sub.1-C.sub.10 alkoxy, and C.sub.3-C.sub.10 cycloalkyl;

(40) R.sub.5 is independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.3-C.sub.10 cycloalkyl, and Ar.sub.3; and

(41) Ar.sub.1, Ar.sub.2, and Ar.sub.3 are independently selected from the group consisting of

(42) ##STR00022##

(43) R.sub.6 and R.sub.7 are independently selected from the group consisting of H, C.sub.1-C.sub.10 alkyl group, C.sub.1-C.sub.10 alkoxy, and a cyclic alkyl group having 3-10 carbon atoms,

(44) M and n are independently an integer from 0 to 4;

(45) R.sub.8 is absent or is selected from the group consisting of CH.sub.2, (CH.sub.3).sub.2C, CO, SO.sub.2, and O

(46) R.sub.9 is absent or is (CH.sub.2).sub.p, wherein p is an integer from 1 to 20;

(47) A is selected from the group consisting of C.sub.1-C.sub.10 alkyl,

(48) ##STR00023##

(49) wherein, each R.sub.10 is independently H or C.sub.1-C.sub.10 alkyl; and

(50) x is an integer from 0 to 4; and

(51) Ep is selected from the group consisting of:

(52) ##STR00024##

(53) wherein each R.sub.11 is independently selected from the group consisting of H, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, a cyclic alkyl group having 3-7 carbon atoms, phenyl, and a phenoxyl group. In some cases, R.sub.11 is independently H or a C.sub.1-C.sub.10 alkyl.

(54) In the compound of Formula (II), Ep may be selected from the group consisting of:

(55) ##STR00025##

(56) The instant disclosure further relates to a flame retardant resinous composition comprising a compound of formula (I) as defined above; and to a cured flame retardant resin prepared by cross-linking the flame retardant resinous composition.

(57) Finally, the instant disclosure relates to a method for synthesizing a compound of Formula (II)

(58) ##STR00026##

(59) comprising performing a catalytic reaction of a compound of formula (I)

(60) ##STR00027##

(61) with an epoxy monomer of formula (III)

(62) ##STR00028##

(63) wherein the substituents for Formula (I), (II), and (III), are defined above. In some instances, the reaction temperature is 100-200 C., 100-150 C., or 120-160 C. The equivalent ratio of the epoxy monomer of formula (III) to the compound of formula (I) is 1:1 to 10:1, 1:1 to 5:1, or 1:2 to 5:1. The amount of catalyst used to catalyze the reaction is 0.1-5 wt. %, 0.1-3 wt. %, or 0.2 to 0.5 wt. %, based on the amount of the epoxy monomer defined by the formula (III). In some cases, the catalyst is an imidazole, a tertiary amine, a tertiary phosphine, a quaternary ammonium salt, a quaternary phosphonium salt, a boron trifluoride complex, or a lithium compound. In particular, the catalyst may be an imidazole selected from the group consisting of 2-phenylimidazole and 2-methylimidazole; or the catalyst may be triphenylphosphine (a tertiary amine). In some cases, the catalyst is a quaternary ammonium salt selected from the group consisting of benzyltrimethyl ammonium chloride, benzyltriethyl ammonium chloride, and tetrabutyl ammonium chloride. Finally, the catalyst may be a quaternary phosphonium salt selected from the group consisting of ethyltriphenyl phosphonium acetate and a ethyltriphenyl phosphonium halide.

EXAMPLE 1

Synthesis of Phosphorus Containing Bisphenol Compound A1 (DMP)

(64) ##STR00029##

(65) 10.81 g (0.05 mole) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 23.5 g (0.25 mole) of phenol, 6.81 g (0.05 mole) of 4-Hydroxyacetophenone, and 0.432 g (4 wt % based on the weight of DOPO) of p-toluenesulfonic acid were mixed and stirred in a 250 ml three-necked flask reactor at room temperature in advance. The reactants were stirred constantly at 130.degree. C. for 24 hours to form a mixture, and then the temperature of the mixture was cooled down to the room temperature. The crude products separated out from the cooled mixture were washed by ethanol and then filtrated and dried to obtain a white powder. The white powder was the phosphorus-containing bisphenol, and the chemical structure of the phosphorus-containing bisphneol A1.

(66) The yield of the foregoing phosphorus-containing bisphenol was 85%, and the melting point was 306 C. The measured value of the carbon, hydrogen, and oxygen element were 72.48%, 4.65%, and 14.90%, respectively (the theoretical value, C, 72.89%; H, 4.65%; O, 14.94%.) by element analysis.

EXAMPLE 2

Synthesis of Phosphorus Containing Bisphenol Compound A2

(67) ##STR00030##

(68) 10.81 g (0.05 mole) of DOPO, 36 g (0.25 mole) of 2-naphthol, 6.81 g (0.05 mole) of 4-Hydroxyacetophenone, and 0.432 g (4 wt % based on the Weight of DOPO) of p-toluene sulfonic acid were mixed and stirred in a 250 ml three-necked flask reactor at room temperature in advance. The reactants were stirred constantly at 130 C. for 24 hours to form a mixture, and then the temperature of the mixture was cooled down to the room temperature. The crude products separated out from the cooled mixture were washed by ethanol and then filtrated and dried to obtain a white powder. The white powder was the phosphorus-containing compound A.sub.2.

(69) The yield of the foregoing phosphorus-containing bisphenol was 85%, and the melting point was 317 C. The measured value of the carbon, hydrogen, and oxygen element were 75.54%, 4.58%, and 13.56%, respectively (the theoretical value, C, 75.31%; H, 4.85%; O, 13.38%.) by element analysis.

EXAMPLE 3

Synthesis of Phosphorus Containing Bisphenol A3

(70) ##STR00031##

(71) 10.81 g (0.05 mole) of DOPO, 36 g (0.25 mole) of 2-naphthol, 9.01 g (0.05 mole) of 6-acetyl-2-naphthol, and 0.432 g (4 wt % based on the Weight of DOPO) of p-toluene sulfonic acid were mixed and stirred in a 250 ml three-necked flask reactor at room temperature in advance. The reactants were stirred constantly at 130 C. for 24 hours to form a mixture, and then the temperature of the mixture was cooled down to the room temperature. The crude products separated out from the cooled mixture were washed by ethanol and then filtrated and dried to obtain a white powder. The white powder was the phosphorus-containing compound A3.

(72) The yield of the foregoing phosphorus-containing bisphenol was 80%, and the melting point was 338 C. The measured value of the carbon, hydrogen, and oxygen element were 77.69%, 4.17%, and 12.25%, respectively (the theoretical value, C, 77.26%; H, 4.76%; O, 12.11%.) by element analysis.

EXAMPLE 4

Synthesis of Ester Substituted Phosphorous-Containing Bisphenol Compound B1

(73) ##STR00032##

(74) DMP (Phosphorous containing bisphenol Compound A1) 428 g (1 mol), Potassium carbonate (K.sub.2CO.sub.3)303.9 g (2.2 mol) and acetone 1000 g were placed into a in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. At first, benzoyl chloride 309.5 g (2.2 mol) was dropped into the reactor at 50 C. within 1 hour, then reacted 4 hours. Afterwards, substances were cooled to the room temperature. In the same time, the ester substituted phosphorous bisphenol compound and by-product salt which is generated by the addition reaction precipitated in the reactor. In order to eliminate the reaction byproduct salt, using water to wash the precipitant then isolated the product by filtration. Finally, Dried the product at a temperature of 120 C. The white powder is ester substituted of Phosphorous bisphenol compound B1,

(75) FT-IR analysis indicated that the 3300 cm-1 peak of OH group was not detected and the 1700 cm-1 peak of carbonyl group was detected. The yield of the foregoing ester substituted phosphorus-containing bisphenol was 88%, melting point: 180 C.

EXAMPLE 5

Synthesis of Ester Substituted Phosphorous Containing Bisphenol Compound B2

Dinaphthoyl-DMP

(76) ##STR00033##

(77) DMP (phosphorous containing bisphenol compound A1) 428 g (1 mol), potassium carbonate (K2CO3)303.9 g (2.2 mol) and acetone 1000 g were placed into a in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. At first, naphthoyl chloride 418 g (2.2 mol) was dropped into the reactor at 50 C. within 1 hour, then reacted 4 hours. Afterwards, substances were cooled to the room temperature. In the same time, the ester substituted phosphorous bisphenol compound and by-product salt which is generated by the addition reaction precipitated in the reactor. In order to eliminate the reaction byproduct salt, using water to wash the precipitant then isolated the product by filtration. Finally, dried the product at a temperature of 120 C. The white powder is ester substituted of phosphorous bisphenol compound B2,

(78) FT-IR analysis indicated that the 3300 cm-1 peak of OH group was not detected and the 1700 cm-1 peak of carbonyl group was detected, The yield of the foregoing ester substituted phosphorus-containing bisphenol was 85%. Melting point: 180 C.

EXAMPLE 6

Synthesis of Ester Substituted Phosphorous Containing Bisphenol Compound B3

Diacetyl-DMP

(79) ##STR00034##

(80) DMP (phosphorous containing bisphenol compound A1) 428 g (1 mol), potassium carbonate (K2CO3)303.9 g (2.2 mol) and acetone 1000 g were placed into a in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. At first, acetyl chloride 172.7 g (2.2 mol) was dropped into the reactor at 50 C. within 1 hour, then reacted 4 hours. Afterwards, substances were cooled to the room temperature. In the same time, the ester substituted phosphorous bisphenol compound and by-product salt which is generated by the addition reaction were precipitated in the reactor. In order to eliminate the reaction byproduct salt, using water to wash the precipitant then isolated the product by filtration. Finally, dried the product at a temperature of 120 C. The white powder is ester substituted of Phosphorous bisphenol compound B3

(81) FT-IR analysis indicated that the 3300 cm-1 peak of OH group was not detected and the 1700 cm-1 peak of carbonyl group was detected, The yield of the foregoing ester substituted phosphorus-containing bisphenol was 89%. Melting point: 180 C.

EXAMPLE 7

Synthesis of Ester Substituted Phosphorous Containing Bisphenol Compound B4

(82) ##STR00035##

(83) DMP (phosphorous containing bisphenol compound A1) 428 g (1 mol), Benzoic acid anhydride 497.7 g (2.2 mol) and 1-methyl imidazole 0.173 g were placed into a in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. At first, benzoyl anhydride 497.7 g (2.2 mol) was dropped into the reactor at 50 C. within 1 hour, then reacted 4 hours. Afterwards, substances were cooled to the room temperature. In the same time, the ester substituted phosphorous bisphenol compound and by-product salt which is generated by the addition reaction precipitated in the reactor. In order to eliminate the reaction byproduct salt, using water to wash the precipitant then isolated the product after filtration. Finally, dried the product at a temperature of 120 C. The white powder is ester substituted of phosphorous bisphenol compound B4.

(84) FT-IR analysis indicated that the 3300 cm-1 peak of OH group was not detected and the 1700 cm-1 peak of carbonyl group was detected, The yield of the foregoing ester substituted phosphorus-containing bisphenol was 79%. Melting point: 180 C.

EXAMPLE 8

Synthesis of Ester Substituted Phosphorous Containing Bisphenol Compound B5

(85) ##STR00036##

(86) DMP (phosphorous containing bisphenol compound A1) 428 g (1 mol), acetic acid anhydride 340 g (2.2 mol) and 1-methyl imidazole 0.173 g were placed into a in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. At first, acetic anhydride 340 g (2.2 mol) was dropped into the reactor at 50 C. within 1 hour, then reacted 4 hours. Afterwards, substances were cooled to the room temperature. In the same time, the ester substituted phosphorous bisphenol compound and by-product salt which is generated by the addition reaction precipitated in the reactor. In order to eliminate the reaction byproduct salt, using water to wash the precipitant then isolated the product after filtration. Finally, Dried the product at a temperature of 120 C. The white powder is ester substituted of Phosphorous bisphenol compound B5

(87) FT-IR analysis indicated that the 3300 cm-1 peak of OH group was not detected and the 1700 cm-1 peak of carbonyl group was detected, The yield of the foregoing ester substituted phosphorus-containing bisphenol was 81%. Melting point: 180 C.

EXAMPLES 9-31

(88) The following components are used in Examples 9-26:

(89) TABLE-US-00001 Epoxy A diglycidyl ether of bisphenol A having an epoxy equivalent resin 1 Weight of 175-185 grams/equivalent, a hydrolyzable chloride of below 200 ppm, a viscosity of 7000-10000 cp, under trade name of BE186LG sold and manufactured by Chang Chun Plastic Co., Ltd., Taiwan, R.O.C. Ep = Epoxy A diglycidyl ether of bisphenol F having an epoxy equivalent resin 2 Weight of 163-173 grams/equivalent, a hydrolyzable chloride of below 200 ppm, a viscosity of 2500-4500 cp, under trade name of BFE170 sold and manufactured by Chang Chun Plastic Co., Ltd., Taiwan, R.O.C. Ep = Epoxy A diglycidyl ether of 3,3,5,5-tetramethyl-4,4-biphenol resin 3 having an epoxy equivalent Weight of 180 to 200 grams/equivalent, under trade name of YX4000H sold and manufactured by Yuka Shell Epoxy Co. Ltd., Japan. Ep = Epoxy A polyglycidyl ether of dicyclodipentadiene having an epoxy resin 4 equivalent weight of 240-270 grams/equivalent, under trade name of DNE260 sold and manufactured by Chang Chun Plastic Co., Ltd., Taiwan, R.O.C. Ep = 0 Epoxy A phosphorus containing polyglycidyl ether of phenolic resin 5 condensate having an epoxy equivalent weight of 260-300 grams/equivalent, a solid content of 75% under trade name of BEP280A75 sold and manufactured by Chang Chun Plastic Co., Ltd., Taiwan, R.O.C. R- = Curing Dicyandiamide (DICY), 10% dissolved in dimethylformamide. agent A Curing Nitrogen containing phenolic resin dissolved in cyclohexanol. agent B The solid content is 60% Catalyst A triphenylphosphine. (TPP), 10% dissolved in methylethylketone Catalyst B 2-methylimidazole (hereinafter referred to 2MI)., 10% dissolved in methanol

EXAMPLE 9

Synthesis of Phosphorous Containing Epoxy C1

(90) ##STR00042##

(91) Epoxy resin 1 (100 g) and ester substituted phosphorus compound B1 (Dibenzyl-DMP) (70 g) were placed in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. Nitrogen gas was introduced and the reaction kettle was heated to 130 C. After epoxy resin A and ester substituted phosphorus compound B1 completely melted, the raw materials were dried under vacuum. The steps of introducing nitrogen gas and drying were carried out two more times. When the temperature of the reaction kettle was decreased from 100 C., catalyst A (0.8 g) was added. The stirrer was started to mix the resin and catalyst and the nitrogen gas was introduced. The resulting mixture was heated to 170 C. It was found that the reactants were slowly exothermic. The reactants were maintained at 170 C. for 2.5 hours and the phosphorus-containing epoxy (Epoxy C1) was obtained. The equivalent weight was 507.2, and the theoretical phosphorus content was 2.0 wt %. For uniformity, the product was dissolved in the methyl ethyl ketone (MEK) and the solid content adjusted to 70%.

EXAMPLE 10

Synthesis of Phosphorous Containing Epoxy C2

(92) ##STR00043##

(93) Epoxy resin 2 (100 g) and ester substituted phosphorus compound B1 (Dibenzyl-DMT) (70 g) were placed in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. Nitrogen gas was introduced and the reaction kettle was heated to 130 C. After epoxy resin 2 and ester substituted phosphorus compound B1 completely melted, the raw materials were dried under vacuum. The steps of introducing nitrogen gas and drying were carried out two more times. When the temperature of the reaction kettle was decreased from 100 C., catalyst A (0.8 g) was added. The stirrer was started to mix the resin and catalyst and the nitrogen gas was introduced. The resulting mixture was heated to 170 C. It was found that the reactants were slowly exothermic. The reactants were maintained at 170 C. for 2.5 hours and the phosphorus-containing epoxy (Epoxy C2) was obtained. The epoxy equivalent weight was 455.3, and the theoretical phosphorus content was 2.0 wt %. For uniformity, the product was dissolved in the methyl ethyl ketone (MEK) and the solid content adjusted to 70%.

EXAMPLE 11

Synthesis of Phosphorous Containing Epoxy C3

(94) ##STR00044##

(95) Epoxy resin 3 (100 g) and ester substituted phosphorus compound B1 (Dibenzyl-DMP) (70 g) were placed in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. Nitrogen gas was introduced and the reaction kettle was heated to 130 C. After epoxy resin 3 and ester substituted phosphorus compound B1 completely melted, the raw materials were dried under vacuum. The steps of introducing nitrogen gas and drying were carried out two more times. When the temperature of the reaction kettle was decreased from 100 C., catalyst A (0.8 g) was added. The stirrer was started to mix the resin and catalyst and the nitrogen gas was introduced. The resulting mixture was heated to 170 C. It was found that the reactants were slowly exothermic. The reactants were maintained at 170 C. for 2.5 hours and the phosphorus-containing epoxy (Epoxy C3) was obtained. The epoxy equivalent weight was 545.2, and the theoretical phosphorus content was 2.0 wt %. For uniformity, the product was dissolved in the methyl ethyl ketone (MEK) and the solid content adjusted to 70%.

EXAMPLE 12

Synthesis of Phosphorous Containing Epoxy C4

(96) ##STR00045##

(97) Epoxy resin 4 (100 g) and ester substituted phosphorus compound B1 (Dibenzyl-DMP) (70 g) were placed in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. Nitrogen gas was introduced and the reaction kettle was heated to 130 C. After epoxy resin 4 and ester substituted phosphorus compound B1 completely melted, the raw materials were dried under vacuum. The steps of introducing nitrogen gas and drying were carried out two more times. When the temperature of the reaction kettle was decreased from 100 C., catalyst A (0.8 g) was added. The stirrer was started to mix the resin and catalyst and the nitrogen gas were introduced. The resulting mixture was heated to 170 C. It was found that the reactants were slowly exothermic. The reactants were maintained at 170 C. for 2.5 hours and the phosphorus-containing epoxy (Epoxy C4) was obtained. The epoxy equivalent weight was 870, and the theoretical phosphorus content was 2.0 wt %. For uniformity, the product was dissolved in the methyl ethyl ketone (MEK) and the solid content adjusted to 70%.

EXAMPLE 13

Synthesis of Phosphorous Containing Epoxy C5

(98) ##STR00046##

(99) Epoxy resin 1 (100 g) and ester substituted phosphorus compound B2 (Dinaphthoyl-DMP) (91 g) were placed in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. Nitrogen gas was introduced and the reaction kettle was heated to 130 C. After epoxy resin 1 and ester substituted phosphorus compound B2 completely melted, the raw materials were dried under vacuum. The steps of introducing nitrogen gas and drying were carried out two more times. When the temperature of the reaction kettle was decreased from 100 C., catalyst A (0.9 g) was added. The stirrer was started to mix the resin and catalyst and the nitrogen gas were introduced. The resulting mixture was heated to 170 C. It was found that the reactants were slowly exothermic. The reactants were maintained at 170 C. for 2.5 hours and the phosphorus-containing epoxy (Epoxy C5) was obtained. The epoxy equivalent weight was 617.8, and the theoretical phosphorus content was 2.0 wt %. For uniformity, the product was dissolved in the methyl ethyl ketone (MEK) and the solid content adjusted to 70%.

EXAMPLE 14

Synthesis of Phosphorous Containing Epoxy C6

(100) ##STR00047##

(101) Epoxy resin 1 (100 g) and ester substituted phosphorus compound B3 (Diacetyl-DMP) 50 g) were placed in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. Nitrogen gas was introduced and the reaction kettle was heated to 130 C. After epoxy resin 1 and ester substituted phosphorus compound B3 completely melted, the raw materials were dried under vacuum. The steps of introducing nitrogen gas and drying were carried out two more times. When the temperature of the reaction kettle was decreased from 100 C., catalyst A (0.8 g) was added. The stirrer was started to mix the resin and catalyst and the nitrogen gas was introduced. The resulting mixture was heated to 170 C. It was found that the reactants were slowly exothermic. The reactants were maintained at 170 C. for 2.5 hours and the phosphorus-containing epoxy (Epoxy C6) was obtained. The epoxy equivalent weight was 414.8, and the theoretical phosphorus content was 2.0 wt %. For uniformity, the product was dissolved in the methyl ethyl ketone (MEK) and the solid content adjusted to 70%.

EXAMPLE 15

Synthesis of Phosphorous Containing Epoxy C7

(102) ##STR00048##

(103) Epoxy resin 1 (100 g) and ester substituted phosphorus compound A1 (DMP) (39 g) were placed in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. Nitrogen gas was introduced and the reaction kettle was heated to 130 C. After epoxy resin 1 and ester substituted phosphorus compound A1 completely melted, the raw materials were dried under vacuum. The steps of introducing nitrogen gas and drying were carried out two more times. When the temperature of the reaction kettle was decreased from 100 C., catalyst A (0.7 g) was added. The stirrer was started to mix the resin and catalyst and the nitrogen gas was introduced. The resulting mixture was heated to 170 C. It was found that the reactants were slowly exothermic. The reactants were maintained at 170 C. for 2.5 hours and the phosphorus-containing epoxy (Epoxy C7) was obtained. The epoxy equivalent weight was 370.9, and the theoretical phosphorus content was 2.0 wt %. For uniformity, the product was dissolved in the methyl ethyl ketone (MEK) and the solid content adjusted to 70%.

EXAMPLE 16

Synthesis of Phosphorous Containing Epoxy C8

(104) ##STR00049##

(105) Epoxy resin 2 (100 g) and ester substituted phosphorus compound A1 (DMP) (39 g) were placed in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. Nitrogen gas was introduced and the reaction kettle was heated to 130 C. After epoxy resin 2 and ester substituted phosphorus compound A1 completely melted, the raw materials were dried under vacuum. The steps of introducing nitrogen gas and drying were carried out two more times. When the temperature of the reaction kettle was decreased from 100 C., catalyst A (0.7 g) was added. The stirrer was started to mix the resin and catalyst and the nitrogen gas was introduced. The resulting mixture was heated to 170 C. It was found that the reactants were slowly exothermic. The reactants were maintained at 170 C. for 2.5 hours and the phosphorus-containing epoxy (Epoxy C8) was obtained. The epoxy equivalent weight was 336.6, and the theoretical phosphorus content was 2.0 wt %. For uniformity, the product was dissolved in the methyl ethyl ketone (MEK) and the solid content adjusted to 70%.

EXAMPLE 17

Synthesis of Phosphorous Containing Epoxy C9

(106) ##STR00050##

(107) Epoxy resin 3 (100 g) and ester substituted phosphorus compound A1 (DMP) (39 g) were placed in a five-neck glass reaction kettle equipped with an electric heating jacket, a temperature controller, an electric stirrer and a stirring bar, a nitrogen gas inlet, a thermocouple, a water-cooled condenser, and a feeding funnel. Nitrogen gas was introduced and the reaction kettle was heated to 130 C. After epoxy resin 3 and ester substituted phosphorus compound A1 completely melted, the raw materials were dried under vacuum. The steps of introducing nitrogen gas and drying were carried out two more times. When the temperature of the reaction kettle was decreased from 100 C., catalyst A (0.7 g) was added. The stirrer was started to mix the resin and catalyst and the nitrogen gas was introduced. The resulting mixture was heated to 17 C. It was found that the reactants were slowly exothermic. The reactants were maintained at 170 C. for 2.5 hours and the phosphorus-containing epoxy (Epoxy C9) was obtained. The epoxy equivalent weight was 395.6, and the theoretical phosphorus content was 2.0 wt %. For uniformity, the product was dissolved in the methyl ethyl ketone (MEK) and the solid content adjusted to 70%.

(108) The compositions of Examples 9-17 were evaluated for epoxy equivalent weight (EEW) and solids content according to the following methods:

(109) Epoxy equivalent weight (EEW): the epoxy resin can be determined according to the method in ASTM D1652.

(110) Solid content: 1 gram of sample containing the phosphorus-containing epoxy resin was placed in an oven at 150 C. for 60 minutes after which and the weight percentage of the resulting non-volatile components was measured.

(111) The results are reported in Table 1 below.

(112) TABLE-US-00002 TABLE 1 Examples 9-17 Example No. 9 10 11 12 13 14 15 16 17 Phosphorous-Containing Epoxy Resin C.sub.1 C.sub.2 C.sub.3 C.sub.4 C.sub.5 C.sub.6 C.sub.7 C.sub.8 C.sub.9 Epoxy resin 1 100 100 100 100 Epoxy resin 2 100 100 Epoxy resin 3 100 100 Epoxy resin 4 100 Synthesis example 4 70 70 70 70 Synthesis example 5 91 Synthesis example 6 50 Synthesis example 1 39 39 39 Catalyst A 0.8 0.8 0.8 0.8 0.9 0.8 0.7 0.7 0.7 Methyl Ethyl Ketone 73 73 73 73 82.2 64 60 60 60 EEW 507.2 455.3 545.2 870 617.8 414.8 370.9 336.6 395.6 Phosphorous content 2.0% 2.0% 2.0% 2.0 2.0% 2.0% 2.0% 2.0% 2.0% Solid content 70% 70% 70% 70% 70% 70% 70% 70% 70%

EXAMPLES 18-31

(113) Glass fiber fabric was impregnated with the phosphorus-containing epoxy resins of Examples 9-17 (Phosphorous-Containing Epoxy Resins C.sub.1-C.sub.9) and dried at 160 C. to form prepegs. Five pieces of the prepregs were piled up and a sheet of 35 m copper foil was placed on the top and bottom and laminated at 210 C. under a pressure of 25 kg/cm.sup.2. This resulted in a laminated entity of the phosphorus-containing epoxy resin and glass fiber fabric. The physical properties of each laminated entity were analyzed according to the following procedures.

(114) Dielectric Constant (Dk) and Dissipation Factor (Df) were measured according to IPC-TM-650-2.5.5.9.

(115) Peel Strength(1 oz copper) was measured according to IPC-TM-650-2.4.8.

(116) Glass Transition Temperature (Tg) was measured according to IPC-TM-650-2.4.25 by using Differential Scanning calorimetry(DSC) (Scan Rate: 20 C./min).

(117) Coefficient Thermal Expansion (CTE,ppm/K) was measured according to IPC-TM-650-2.4.24 by TMA (thermo mechanical analysis) (1 is the CTE value before Tg, 2 is the CTE value after Tg).

(118) Decomposition Temperature (Td, 5% weight loss) was measured according to IPC-TM-650-2.3.40 using a thermogravimetric analyzer (TGA) (Scan Rate: 10 C./min).

(119) Water Absorption (Wt %): To calculate the water absorption, the specimens were placed in a 100 C. water and the of increase in weight (wt %) measured after two hours.

(120) Thermal Stability (S-288) are measured according to JIS-C-6481: The laminated entity was immersed into a 288 C. solder furnace and the time to delamination measured.

(121) TABLE-US-00003 Flame Retardancy was measured according to UL94. UL 94 Flammability Ratings Summary 5VA Burning stops within 60 seconds after five applications of Surface five seconds each of a flame (larger than that used in Vertical Burn Burn testing) to a test bar. Test specimens MAY NOT have a burn-through (no hole). This is the highest (most flame retardant) UL94 rating. 5VB Burning stops within 60 seconds after five applications of five Surface seconds each of a flame (larger than that used in Vertical Burn Burn testing) to a test bar. Test specimens MAY HAVE a burn- through (a hole). V-0 Burning stops within 10 seconds after two applications of ten Vertical seconds each of a flame to a test bar. NO flaming drips are Burn allowed. V-1 Burning stops within 60 seconds after two applications of ten Vertical seconds each of a flame to a test bar. NO flaming drips are Burn allowed. V-2 Burning stops within 60 seconds after two applications of ten Vertical seconds each of a flame to a test bar. Flaming drips ARE Burn allowed H-B Slow horizontal burning on a 3mm thick specimen with a Hori- burning rate is less than 3/min or stops burning before the 5 zontal mark. H-B rated materials are considered self-extinguishing. Burn This is the lowest (least flame retardant) UL94 rating.

(122) The composition of Examples 18-31 are shown in Tables 2 and 2(a), and the measurements are reported in Tables 3 and 3(a).

(123) TABLE-US-00004 TABLE 2 Examples 18-26 (Inventive) Examples No. 18 19 20 21 22 23 24 25 26 Phosphorous epoxy C.sub.1 100 100 (From Example 9) Phosphorous epoxy C.sub.2 100 (From Example 10) Phosphorous epoxy C.sub.3 100 (From Example 11) Phosphorous epoxy C.sub.4 100 (From Example 12) Phosphorous epoxy C.sub.5 100 100 (From Example 13) Phosphorous epoxy C.sub.6 100 100 (From Example 14) Curing agent A 16.3 18.1 15.1 9.5 13.4 20.2 Curing agent B 51.7 41.8 63.2 Catalyst B 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Acetone 5 5 5 10 7 0 25 22 23

(124) TABLE-US-00005 TABLE 2(a) Examples 27-31 (Comparative) Examples No. 27 28 29 30 31 Phosphorous epoxy C.sub.7 100 100 (From Example 15) Phosphorous epoxy C.sub.8 100 (From Example 16) Phosphorous epoxy C.sub.9 100 (From Example 17) Epoxy 5 100 Curing agent A 22.2 24.5 20.8 32 Curing agent B 69.1 Catalyst B 0.5 0.5 0.5 0.5 0.5 Acetone 0 0 0 22.5 0

(125) TABLE-US-00006 TABLE 3 Examples 18-26 (Inventive) Examples No. 18 19 20 21 22 23 24 25 26 Dk [1 MHz] 4.54 4.69 4.71 4.45 4.56 4.62 4.5 4.50 4.55 Df [1 MHz] 0.013 0.010 0.012 0.011 0.015 0.013 0.011 0.013 0.010 Peel strength (kgf/cm) 1.8 1.9 1.9 1.8 1.7 1.8 1.9 1.8 1.9 Water absorption (Wt %) 0.24 0.26 0.25 0.28 0.21 0.26 0.20 0.16 0.15 CTE .sub.1(ppm) 26.9 36.5 30 25.4 26.3 25.1 25.2 25.9 23.2 CTE .sub.2(ppm) 232 260 245 219 230 235.0 215.6 221 210.5 Tg 137 123 150 145 141 129 150 156 140 Td 371 372 357 377 376 370 381 386 380 Flame retardancy V0 V0 V0 V0 V0 V0 V0 V0 V0 Thermal stability >180 >180 >180 >180 >180 >180 >180 >180 >180 S-288 (sec)

(126) TABLE-US-00007 TABLE 3(a) Example 27-31 (Comparative) Examples No. 27 28 29 30 31 Dk [1MHz] 4.85 4.89 5.01 4.83 5.05 Df [1MHz] 0.019 0.016 0.014 0.014 0.013 Peel strength(kgf/cm) 2.1 2.1 2.1 2.1 1.5 Water absorption (Wt %) 0.34 0.35 0.32 0.23 0.32 CTE .sub.1(ppm) 40.6 47.4 39.2 34 32 CTE .sub.2(ppm) 260.2 265.5 253 243 253 Tg 146 130 161 162 135 Td 371 373 350 380 367 Flame retardancy V0 V0 V0 V0 V0 Thermal stability >180 >180 >180 >180 >180 S-288 (sec)

(127) The data show that the inventive compositions provide excellent flame retardancy and thermal stability. Furthermore, based on the comparison above, the inventive compositions provide surprisingly better water resistance and dielectric properties than the comparative compositions.

(128) The above embodiments are only used to illustrate the principle of the present disclosure and the effect thereof, and should not be construed as to limit the present disclosure. The above embodiments can be modified and altered by those skilled in the art, without departing from the spirit and scope of the present disclosure. Therefore, the protection scope of the present disclosure is defined in the following appended claims. As long as it does not affect the effects and achievable goals of this disclosure, it should be covered under the technical contents disclosed herein.

(129) The terms comprising, having, and including are used in their open, non-limiting sense. The terms a and the are understood to encompass the plural as well as the singular. The expression at least one means one or more and thus includes individual components as well as mixtures/combinations. The term about when referring to a value, is meant specifically that a measurement can be rounded to the value using a standard convention for rounding numbers. For example, about 1.5 is 1.45 to 1.54. All valued set forth herein can be modified with the term about or recited without the term, regardless of whether the term about is specifically set forth (or is absent) in conjunction with any particular value. All ranges and values disclosed herein are inclusive and combinable. For examples, any value or point described herein that falls within a range described herein can serve as a minimum or maximum value to derive a sub-range, etc.