Phosphazene compound, and a composition, a prepreg and a wiring board comprising the same

Abstract

The present invention relates to a phosphazene compound and a composite metal laminate. The phosphazene compound with a partial structure of carboxylic esters has a structure as shown in Formula (I). The present invention obtains a phosphazene compound with a partial structure of carboxylic esters using an M group having specific components. The cured products of the phosphazene compound have good flame retardancy, heat resistance, mechanical properties, flame retardancy, and low dielectric constant, and are a low dielectric flame retardant material having great economic properties and being environmental friendly.

Claims

1. A phosphazene compound, characterized in that, it has a molecular structure as shown in Formula (I): ##STR00015## in Formula (I), R.sub.1 represents any organic group; R is an inert nucleophilic group provided by a nucleophile; M is any one of cyclotriphosphazene groups M.sub.1, cyclic ring consisting of four or more phosphazene groups M.sub.2, or non-cyclic polyphosphazene groups M.sub.3, or a combination of at least two of them; a is an integer of 1-4; c is an integer greater than or equal to 1, with the sum of a and c being greater than or equal to 6.

2. The phosphazene compound of claim 1, characterized in that, R.sub.1 is an aliphatic and/or aromatic hydrocarbon group.

3. The phosphazene compound of claim 2, characterized in that, R.sub.1 is any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aralkyloxy, substituted or unsubstituted alkylaryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or a combination of at least two of them.

4. The phosphazene compound of claim 3, characterized in that, R.sub.1 is any one of unsubstituted straight-chain or branched alkyl, unsubstituted cycloalkyl, unsubstituted aralkyl, unsubstituted alkoxy, unsubstituted cycloalkoxy, unsubstituted aralkyloxy, unsubstituted alkylaryloxy, unsubstituted aryl or unsubstituted heteroaryl, or a combination of at least two of them.

5. The phosphazene compound of claim 1, characterized in that, R.sub.1 does not contain a reactive group which can react with epoxy resin to produce a secondary hydroxyl.

6. The phosphazene compound of claim 1, characterized in that, the inert nucleophilic group R has a structure of YX; X is O, C, N; Y is an aliphatic and/or aromatic hydrocarbon group.

7. The phosphazene compound of claim 6, characterized in that, Y is any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aralkyloxy, substituted or unsubstituted alkylaryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or a combination of at least two of them.

8. The phosphazene compound of claim 1, characterized in that, R is any one selected from the group consisting of OR.sub.13, ##STR00016## CCR.sub.18, R.sub.22COO, ##STR00017## or a combination of at least two of them; R.sub.13 is any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aralkyloxy, substituted or unsubstituted alkylaryloxy, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group, substituted or unsubstituted phosphonate group, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or a combination of at least two of them; R.sub.14 is any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aralkyloxy, substituted or unsubstituted alkylaryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or a combination of at least two of them; R.sub.15, R.sub.16 and R.sub.17 are independently any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aralkyloxy, substituted or unsubstituted alkylaryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or a combination of at least two of them; R.sub.18 is any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aralkyloxy, substituted or unsubstituted alkylaryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or a combination of at least two of them; R.sub.22 is any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aralkyloxy, substituted or unsubstituted alkylaryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or a combination of at least two of them; R.sub.23 and R.sub.24 are independently any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aralkyloxy, substituted or unsubstituted alkylaryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or a combination of at least two of them; R.sub.26 and R.sub.27 are independently any one of substituted or unsubstituted straight-chain or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted aralkyloxy, substituted or unsubstituted alkylaryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or a combination of at least two of them.

9. The phosphazene compound of claim 1, characterized in that, the phosphazene compound is any one of the phosphazene compounds having the following structures or a mixture of at least two of them: ##STR00018## ##STR00019##

10. The phosphazene compound of claim 1, characterized in that, the structure of M.sub.1 is: ##STR00020## the structure of M.sub.2 is: ##STR00021## wherein, x is greater than or equal to 4; the structure of M.sub.3 is: ##STR00022## wherein, y is greater than or equal to 3.

11. A method for preparing the phosphazene compound of claim 1, characterized in that, the phosphazene compound is obtained by carrying out a nucleophilic substitution reaction of phosphazene chloride and nucleophile.

12. The method of claim 11, characterized in that, the preparation method is that the phosphazene chloride firstly reacts with RNa, and then reacts with R.sub.1COOH to obtain the phosphazene compound of claim 1.

13. A prepreg, characterized in that, it is prepared by impregnating a substrate with an epoxy resin composition comprising the phosphazene compound of claim 1 or coating an epoxy resin composition comprising the phosphazene compound of claim 1 onto a substrate.

14. The prepreg of claim 13, characterized in that, the substrate is a glass fiber substrate, a polyester substrate, a polyimide substrate, a ceramic substrate or a carbon fiber substrate.

Description

EMBODIMENTS

(1) The technical solution of the present invention is further described by the following examples.

Example 1

(2) The phosphazene compound of the present example has the following structure:

(3) ##STR00012##

(4) 1 mol of hexachlorocyclotriphosphazene, 200 ml of acetone, 6 mol of benzoic acid were added to a 3-neck glass reactor having a volume of 2000 ml and having a stirring apparatus. While stirring, nitrogen was fed therein, and the reactor was heated to 60 C. 620 g of 20% sodium hydroxide solution was dripped within 60 min, and then the mixture was held at 60 C., stirred and reacted for 15 hours. After reaction, the salts and water in the system were removed by physical method; the insoluble substance in the system was removed by filtration; and the solvent in the system was distilled to obtain a low dielectric flame retardant compound. The flame retardant compound was measured to have an ester equivalent of 150 g/eq, and such target compound was named as compound A.

(5) 150 g (1 eq) of the above A product, 200 g (1 eq) of o-cresol novolac epoxy resin with an epoxy equivalent of 200 g/eq and 0.2 g of pyridine were dissolved into solution using an appropriate amount of butanone. A copper clad laminate a with a resin content of 50% is prepared by using standard glass cloths according to a generally used production process. The properties of copper clad laminate a are shown in Table 1.

(6) The obtained compound A was characterized by nuclear magnetic resonance hydrogen spectrum, and the results are as follows:

(7) .sup.1H NMR (CDCl.sub.3, 500 MHz): 8.13, (s, 12H, hydrogen at an ortho-position to ester group in phenyl), 7.47 (m, 12H, hydrogen at a meta-position to ester group in phenyl), 7.60 (m, 6H, hydrogen at a para-position to ester group in phenyl).

(8) Characteristic peak positions in infrared spectroscopy: ester carbonyl, 1730-1740 cm.sup.1; COC in ester group, 1200 cm.sup.1.

Example 2

(9) The phosphazene compound of the present example has the following structure:

(10) ##STR00013##

(11) 1 mol of hexachlorocyclotriphosphazene, 200 ml of acetone, 3 mol of benzoic acid and 3 mol of sodium methoxide were added to a 3-neck glass reactor having a volume of 2000 ml and having a stirring apparatus. While stirring, nitrogen was fed therein, and the reactor was heated to 60 C. 620 g of 20% sodium hydroxide solution was dripped within 60 min, and then the mixture was held at 60 C., stirred and reacted for 15 hours. After reaction, the salts and water in the system were removed by physical method; the insoluble substance in the system was removed by filtration; and the solvent in the system was distilled to obtain 1 mol of a flame retardant compound. The flame retardant compound was measured to have an ester equivalent of 80 g/eq, and such target compound was named as compound B.

(12) .sup.1H NMR (CDCl.sub.3, 500 MHz): 3.39 (m, 15H, hydrogen in methyl), 8.13, (s, 12H, hydrogen at an ortho-position to ester group in phenyl), 7.47 (m, 12H, hydrogen at a meta-position to ester group in phenyl), 7.60 (m, 6H, hydrogen at a para-position to ester group in phenyl).

(13) Characteristic peak positions in infrared spectroscopy: ester carbonyl, 1730-1740 cm.sup.1; COC in ester group, 1200 cm.sup.1.

(14) 100 g of o-cresol novolac epoxy resin with an epoxy equivalent of 200 g/eq and 0.2 g of pyridine were added into 1125 g of the above B product and the mixture was dissolved into solution using an appropriate amount of butanone. A copper clad laminate b with a resin content of 50% is prepared by using standard glass cloths according to a generally used production process. The properties of copper clad laminate b are shown in Table 1.

Example 3

(15) 200 g of bisphenol-A novolac epoxy resin with an epoxy equivalent of 200 g/eq and 0.2 g of pyridine were added into 75 g of the above A product and 110 g of an ester compound with an ester equivalent of 220 g/eq as shown in the following formula (a product of Guangdong Guangshan New Materials Co., Ltd, YEH-6611), and the mixture was dissolved into solution using an appropriate amount of butanone. A copper clad laminate c with a resin content of 50% is prepared by using standard glass cloths according to a generally used production process. The properties of copper clad laminate c are shown in Table 1.

(16) ##STR00014##

Comparative Example 1

(17) 105 g linear phenolic resin curing agent with a phenolic hydroxyl group equivalent of 105 g/eq, 70 g of hexaphenoxyphosphacyanogen used as a flame retardant and 0.2 g of 2-methylimidazole were added into 200 g of o-methyl phenolic epoxy resin with an epoxy equivalent of 200 g/eq, and the mixture was dissolved into solution using an appropriate amount of butanone. A copper clad laminate d with a resin content of 50% is prepared by using standard glass cloths according to a generally used production process. The properties of copper clad laminate d are shown in Table 1.

Comparative Example 2

(18) 70 g of hexaphenoxyphosphacyanogen used as a flame retardant, 220 g of YEH-6611 and 0.2 g of pyridine were added into 200 g of o-methyl phenolic epoxy resin with an epoxy equivalent of 200 g/eq, and the mixture was dissolved into solution using an appropriate amount of butanone. A copper clad laminate e with a resin content of 50% is prepared by using standard glass cloths according to a generally used production process. The properties of copper clad laminate e are shown in Table 1.

(19) The test results of products of Examples and Comparative Examples are shown in Table 1 (the specific test methods are not described considering that they are well-known by those skilled in the art).

(20) TABLE-US-00001 TABLE 1 Comparison of properties of each copper clad laminate copper clad copper clad copper clad copper clad copper clad Test Item laminate a laminate b laminate c laminate d laminate e combustibility V0 V0 V0 V0 V0 (UL-90) Dielectric constant 3.2 3.3 3.4 4.5 4.6 (5 MHz) Dielectric loss 0.004 0.004 0.005 0.015 0.018 (5 MHz) water absorption 0.32 0.31 0.38 0.52 0.58 (%) Tg( C.) 178 173 170 148 150 Peeling strength 2.21 2.03 2.02 2.02 2.02 (N .Math. mm.sup.1)

(21) The present invention describes the detailed technological equipment and process by the aforesaid examples, but the present invention is not limited by the aforesaid detailed technological equipment and process. That is to say, it does not mean that the present invention cannot be fulfilled unless relying on the aforesaid detailed technological equipment and process. Those skilled in the art shall know that, any modification to the present invention, any equivalent replacement of each raw material of the product of the present invention and the addition of auxiliary ingredient, the selection of specific embodiment and the like all fall into the protection scope and the disclosure scope of the present invention.