PHOSPHAZENE COMPOUND COMPRISING CYANO GROUP, PREPARATION METHOD AND USES THEREOF

Abstract

The present invention relates to a phosphazene compound comprising cyano group having a molecular structure of Formula (I); wherein, Y and Y are independently selected from organic groups; M.sub.1 and M.sub.2 are independently selected from phosphazene groups, and M.sub.1 contains m.sub.1 phosphorus atoms, and M.sub.2 contains m.sub.2 phosphorus atoms; X.sub.1, X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from any one of the sixth main-group elements; R and R are independently selected from divalent organic groups; a is an integer greater than or equal to 0; b is an integer greater than or equal to 1; and c is an integer greater than or equal to 0; and a+b=2m.sub.1, d+2=2m.sub.2. The present invention achieves a synergistic effect with P and N of phosphazene group by introducing cyano group to the phosphazene group, and thus improves thermal stability and flame retardancy of the phosphazene compound, and the compatibility thereof with other components is excellent. The resin composition comprising the phosphazene compound of the present invention has good heat resistance, water resistance, adhesive properties and mechanical properties, and thus the application thereof is widened.

Claims

1. A phosphazene compound comprising cyano group, having a molecular structure as shown in Formula (I): ##STR00020## wherein, Y and Y are independently selected from organic groups; M.sub.1 and M.sub.2 are independently selected from phosphazene groups, and M.sub.1 contains m.sub.1 phosphorus atoms, and M.sub.2 contains m.sub.2 phosphorus atoms; X.sub.1, X.sub.1, X.sub.2, X.sub.3 and X.sub.4 are independently selected from any one of the sixth main-group elements; R and R are independently selected from divalent organic groups; a is an integer greater than or equal to 0; b is an integer greater than or equal to 1; and c is an integer greater than or equal to 0; and a+b=2m.sub.1, d+2=2m.sub.2.

2. The phosphazene compound of claim 1, wherein M.sub.1 and M.sub.2 are independently selected from cyclic phosphazene having a structure of Formula (II) or linear phosphazene having a structure of Formula (III); ##STR00021## in Formula (II) or Formula (III), n.sub.1 is an integer greater than or equal to 2, and n.sub.2 is an integer greater than or equal to 1.

3. The phosphazene compound of claim 1, wherein M.sub.1 and M.sub.2 are any one of cyclotriphosphazene, cyclotetraphosphazene or non-cyclic polyphosphazene, or a combination of at least two of them.

4. The phosphazene compound of claim 1, wherein Y and Y are independently selected from the group consisting of substituted or unsubstituted straight chain alkyl, substituted or unsubstituted branched alkyl, or substituted or unsubstituted aryl.

5. The phosphazene compound of claim 1, wherein Y and Y are independently selected from the group consisting of C.sub.1-C.sub.30 substituted or unsubstituted straight chain alkyl, C.sub.1-C.sub.30 substituted or unsubstituted branched alkyl, or C.sub.6-C.sub.30 substituted or unsubstituted aryl.

6. The phosphazene compound of claim 1, wherein Y and Y are independently selected from the group consisting of phenyl, tolyl, xylyl, ethylphenyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, or isobutyl.

7. The phosphazene compound of claim 1, wherein Y and Y are independently phenyl, tolyl, xylyl or ethylphenyl.

8. The phosphazene compound of claim 1, wherein R and R are independently selected from the group consisting of substituted or unsubstituted straight chain alkylene, substituted or unsubstituted branched alkylene, and substituted or unsubstituted arylene.

9. The phosphazene compound of claim 1, wherein R and R are independently selected from the group consisting of C.sub.1-C.sub.30 substituted or unsubstituted straight chain alkylene, C.sub.1-C.sub.30 substituted or unsubstituted branched alkylene, and C.sub.6-C.sub.30 substituted or unsubstituted arylene.

10. The phosphazene compound of claim 1, wherein R and R are independently selected from the group consisting of phenylene, methylphenylene, dimethylphenylene, ethylphenylene, ##STR00022## methylene, ethylene, propylene, ##STR00023## n-butylene, or isopropylene.

11. The phosphazene compound of claim 1, wherein R and R are independently phenylene, methylphenylene, dimethylphenylene, ethylphenylene, or ##STR00024##

12. The phosphazene compound of claim 1, wherein each X.sub.1, X.sub.1, X.sub.2, X.sub.3 and X.sub.4 is O.

13. The phosphazene compound of claim 1, wherein the phosphazene compound is selected from ##STR00025## wherein each M.sub.1, M.sub.2, a, b, R and R has the same selection scopes as that in claim 1.

14. The phosphazene compound of claim 1, wherein the phosphazene compound is selected from the group consisting of ##STR00026## wherein each M.sub.1, M.sub.2, a and b has the same selection scopes as that in claim 1.

15. The phosphazene compound of claim 1, wherein the phosphazene compound is selected from ##STR00027##

16. A method for preparing the phosphazene compound comprising cyano group of claim 1, comprising the step of carrying out a nucleophilic substitution reaction of phosphazene chloride and a first raw material compound; the phosphazene chloride is M.sub.1(Cl).sub.p and/or M.sub.2(Cl).sub.q, p=2m.sub.1, and q=2m.sub.2; the first raw material compound is any one of YX.sub.1H, YX.sub.1H, HX.sub.2RCN or HX.sub.4RX.sub.3H, or a combination of at least two of them; the first raw material compound must comprise HX.sub.2RCN or HX.sub.4RX.sub.3H; wherein, each X.sub.1, X.sub.1, X.sub.2, X.sub.3, X.sub.4, Y, R and R has the same meaning as that in claim 1, and R and Y are substituted or unsubstituted phenyl.

17. A prepreg prepared by impregnating a substrate with a cyanate ester resin composition comprising the phosphazene compound of claim 1 or coating an cyanate ester resin composition comprising the phosphazene compound of claim 1 onto a substrate.

18. The prepreg of claim 17, wherein the substrate is a glass fiber substrate, a polyester substrate, a polyimide substrate, a ceramic substrate or a carbon fiber substrate.

Description

EMBODIMENTS

[0048] The technical solutions of the present invention are further described by the following embodiments.

[0049] Those skilled in the art should appreciate that the embodiments only help understand the present invention and shall not be deemed as limitations to the present invention.

Example 1

[0050] A phosphazene compound 1 having the following structure:

##STR00016##

[0051] The preparation method thereof is as follows:

(1) in a reactor, 714 g (6 eq) of p-cyanophenol with a hydroxyl equivalent of 119 g/eq was dissolved into dioxane, and then 170.5 g (6 eq) of hexachlorocyclotriphosphazene with a chlorine atom equivalent of 28.4 g/eq and 318 g (6 eq) of sodium carbonate with a sodium atom equivalent of 53 g/eq were added therein, and the mixture was reacted for 24 hours at a reflux temperature under nitrogen protection;
(2) the salts and water in the system of the product obtained in step (1) were removed by physical method; the insoluble substance in the system was removed by filtration; and the solvent in the system was distilled off; and the phosphazene compound 1 with a cyano group equivalent of 140.7 g/eq was obtained after drying.

Characterizations:

[0052] Infrared Spectroscopy: 1400-1600 cm.sup.1 (benzene ring); 2220-2230 cm.sup.1 (cyano group); 1260-1280 cm.sup.1 (PN); 1170-1185 cm.sup.1 (PN); 955-960 cm.sup.1, 1005-1015 cm.sup.1, 1065-1075 cm.sup.1 (POC); in addition, the peak at 510 cm.sup.1 (PCl) is disappeared;

[0053] Nuclear Magnetic Resonance .sup.1H-NMR (DMSO-d6, ppm): 6.85-6.95 (hydrogen at an ortho-position to phenolic hydroxyl in cyanophenol group, 12H), 7.3-7.4 (hydrogen at a meta-position to phenolic hydroxyl in cyanophenol group, 12H).

Example 2

[0054] A phosphazene compound 2 having the following structure:

##STR00017##

[0055] The preparation method thereof is as follows:

(1) in a reactor, 357 g (3 eq) of p-cyanophenol with a hydroxyl equivalent of 119 g/eq and 282 g (3 eq) of phenol with a hydroxyl equivalent of 94 g/eq were dissolved into dioxane, and then 170.5 g (6 eq) of hexachlorocyclotriphosphazene with a chlorine atom equivalent of 28.4 g/eq and 318 g (6 eq) of sodium carbonate with a sodium atom equivalent of 53 g/eq were added therein, and the mixture was reacted for 24 hours at a reflux temperature under nitrogen protection;
(2) the product obtained in step (1) was washed by alkali, and then the residual materials were removed, and the phosphazene compound 2 with a cyano group equivalent of 256.2 g/eq was obtained after drying.

Characterizations:

[0056] Infrared Spectroscopy: 1400-1600 cm.sup.1 (benzene ring); 2220-2230 cm.sup.1 (cyano group); 1260-1280 cm.sup.1 (PN); 1170-1185 cm.sup.1 (PN); 955-960 cm.sup.1, 1005-1015 cm.sup.1, 1065-1075 cm.sup.1 (POC); in addition, the peak at 510 cm.sup.1 (PCl) is disappeared;

[0057] Nuclear Magnetic Resonance .sup.1H-NMR (DMSO-d6, ppm): 6.85-6.95 (hydrogen at an ortho-position to phenolic hydroxyl in cyanophenolichydroxyl, 6H), 7.3-7.4 (hydrogen at an ortho-position to cyano group in cyanophenolichydroxyl, 6H), 6.73 (hydrogen at an ortho-position to phenolic hydroxyl in phenol group, 6H), 7.05-7.12 (hydrogen at a meta-position to phenolic hydroxyl in phenol group, 6H), 6.80-6.84 (hydrogen at a para-position to phenolic hydroxyl in phenol group, 3H).

Example 3

[0058] A phosphazene compound 3 having the following structure:

##STR00018##

[0059] The preparation method thereof is as follows:

(1) in a reactor, 357 g (3 eq) of p-cyanophenol with a hydroxyl equivalent of 119 g/eq and 324 g (3 eq) of para-methylphenol with a hydroxyl equivalent of 108 g/eq were dissolved into dioxane, and then 170.5 g (6 eq) of hexachlorocyclotriphosphazene with a chlorine atom equivalent of 28.4 g/eq and 318 g (6 eq) of sodium carbonate with a sodium atom equivalent of 53 g/eq were added therein, and the mixture was reacted for 24 hours at a reflux temperature under nitrogen protection;
(2) the product obtained in step (1) was washed by alkali, and then the residual materials were removed, and the phosphazene compound 3 with a cyano group equivalent of 270 g/eq was obtained after drying.

Characterizations:

[0060] Infrared Spectroscopy: 1400-1600 cm.sup.1 (benzene ring); 2220-2230 cm.sup.1 (cyano group); 1260-1280 cm.sup.1 (PN); 1170-1185 cm.sup.1 (PN); 955-960 cm.sup.1, 1005-1015 cm.sup.1, 1065-1075 cm.sup.1 (POC); 2960 cm.sup.1, 2870 cm.sup.1 (methyl); in addition, the peak at 510 cm.sup.1 (PCl) is disappeared;

[0061] Nuclear Magnetic Resonance .sup.1H-NMR (DMSO-d6, ppm): 6.85-6.95 (hydrogen at an ortho-position to phenolic hydroxyl in cyanophenolichydroxyl, 6H), 7.3-7.4 (hydrogen at an ortho-position to cyano group in cyanophenolichydroxyl, 6H), 6.73 (hydrogen at an ortho-position to phenolic hydroxyl in phenol group, 6H), 7.05-7.12 (hydrogen at a meta-position to phenolic hydroxyl in phenol group, 6H), 6.80-6.84 (hydrogen at a para-position to phenolic hydroxyl in phenol group, 3H), 2.3-2.4 (hydrogen in methyl, 9H).

Example 4

[0062] A phosphazene compound 4 having the following structure:

##STR00019##

[0063] The preparation method thereof is as follows:

(1) in a reactor, 357 g (3 eq) of p-cyanophenol with a hydroxyl equivalent of 119 g/eq, 216 g (2 eq) of para-methylphenol with a hydroxyl equivalent of 108 g/eq and 110 g (2 eq) of hydroquinone with a hydroxyl equivalent of 55 g/eq were dissolved into dioxane, and then 170.5 g (6 eq) of hexachlorocyclotriphosphazene with a chlorine atom equivalent of 28.4 g/eq and 318 g (6 eq) of sodium carbonate with a sodium atom equivalent of 53 g/eq were added therein, and the mixture was reacted for 24 hours at a reflux temperature under nitrogen protection;
(2) 170.5 g (6 eq) of hexachlorocyclotriphosphazene with a chlorine atom equivalent of 28.4 g/eq, 432 g (4 eq) of para-methylphenol with a hydroxyl equivalent of 108 g/eq, 110 g (2 eq) of hydroquinone with a hydroxyl equivalent of 55 g/eq and 318 g (6 eq) of sodium carbonate with a sodium atom equivalent of 53 g/eq were added into the product obtained in step (1), and the mixture was reacted for 24 hours at a reflux temperature under nitrogen protection;
(3) 170.5 g (6 eq) of hexachlorocyclotriphosphazene with a chlorine atom equivalent of 28.4 g/eq, 357 g (3 eq) of para-cyanophenol with a hydroxyl equivalent of 119 g/eq, 216 g (2 eq) of para-methylphenol with a hydroxyl equivalent of 108 g/eq, and 318 g (6 eq) of sodium carbonate with a sodium atom equivalent of 53 g/eq were added into the product obtained in step (2), and the mixture was reacted for 24 hours at a reflux temperature under nitrogen protection;
(4) the product obtained in step (3) was washed by alkali, and then the residual materials were removed, and the phosphazene compound 4 with a cyano group equivalent of 364.5 g/eq was obtained after drying.

Characterizations:

[0064] Infrared Spectroscopy: 1400-1600 cm.sup.1 (benzene ring); 2220-2230 cm.sup.1 (cyano group); 1260-1280 cm.sup.1 (PN); 1170-1185 cm.sup.1 (PN); 955-960 cm.sup.1, 1005-1015 cm.sup.1, 1065-1075 cm.sup.1 (POC); 2960 cm.sup.1, 2870 cm.sup.1 (methyl); in addition, the peak at 510 cm.sup.1 (PCl) is disappeared;

[0065] Nuclear Magnetic Resonance .sup.1H-NMR (DMSO-d6, ppm): 6.85-6.95 (hydrogen at an ortho-position to phenolic hydroxyl in cyanophenolichydroxyl, 20H), 7.3-7.4 (hydrogen at an ortho-position to cyano group in cyanophenolichydroxyl, 20H), 6.58-6.63 (hydrogen at an ortho-position to hydroxyl in para-methylphenol group, 8H), 6.85-6.95 (hydrogen at an ortho-position to methyl in para-methylphenol group, 8H), 2.3-2.4 (hydrogen in methyl, 30H).

Application Example 1

[0066] A halogen-free flame retardant cyanate ester resin composition comprising the following components by weight parts:

[0067] 22.5 g of the phosphazene compound 1 obtained in Example 1 and 88.2 g of phenolic resin with a phenolic hydroxyl equivalent of 105 were added into 187 g of liquid bisphenol A epoxy resin, and the mixture was dissolved into solution using an appropriate amount of acetone. A copper-clad laminate was obtained by using standard glass cloths, sizing and pressing. The obtained copper-clad laminate is named as copper-clad laminate a and the properties thereof are shown in Table 1.

Application Example 2

[0068] A halogen-free flame retardant cyanate ester resin composition comprising the following components by weight parts:

[0069] 25.6 g of the phosphazene compound 1 obtained in Example 1 and 94.5 g of phenolic resin with a phenolic hydroxyl equivalent of 105 were added into 187 g of liquid bisphenol A epoxy resin, and the mixture was dissolved into solution using an appropriate amount of acetone. A copper-clad laminate was obtained by using standard glass cloths, sizing and pressing. The obtained copper-clad laminate is named as copper-clad laminate b and the properties thereof are shown in Table 1.

Application Example 3

[0070] A halogen-free flame retardant cyanate ester resin composition comprising the following components by weight parts:

[0071] 27 g of the phosphazene compound 1 obtained in Example 1 and 94.5 g of phenolic resin with a phenolic hydroxyl equivalent of 105 were added into 187 g of liquid bisphenol A epoxy resin to obtain cyanate ester resin C, which was dissolved into solution using an appropriate amount of acetone. A copper-clad laminate was obtained by using standard glass cloths, sizing and pressing. The obtained copper-clad laminate is named as copper-clad laminate c and the properties thereof are shown in Table 1.

Application Example 4

[0072] A halogen-free flame retardant cyanate ester resin composition comprising the following components by weight parts:

[0073] 29.15 g of the phosphazene compound 1 obtained in Example 1 and 96.6 g of phenolic resin with a phenolic hydroxyl equivalent of 105 were added into 187 g of liquid bisphenol A epoxy resin to obtain cyanate ester resin D, which was dissolved into solution using an appropriate amount of acetone. A copper-clad laminate was obtained by using standard glass cloths, sizing and pressing. The obtained copper-clad laminate is named as copper-clad laminate d and the properties thereof are shown in Table 1.

Comparative Example 1

[0074] The difference of Comparative Example 1 from Application Example 1 lies in: the phosphazene compound 1 was replaced with hexaphenoxylcyclotriphosphazene based on the same quality, and an epoxy resin composition E was obtained.

[0075] The epoxy resin composition E was dissolved into solution using an appropriate amount of acetone. A copper-clad laminate was obtained by using standard glass cloths, sizing and pressing. The obtained copper-clad laminate is named as copper-clad laminate e and the properties thereof are shown in Table 1.

[0076] The tested results of products of Examples and Comparison Examples are shown in Table 1 below.

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 Tg (DSC) ( C.) 245 218 248 250 142 Peeling strength 2.21 2.30 2.34 2.37 1.52 (N .Math. mm.sup.1) Combustibility (UL-90) V0 V0 V0 V0 V0 Water absorption (%) 0.32 0.31 0.25 0.22 0.52 Bending strength (at 600 620 640 680 490 room temperature) (MPa, in longitudinal direction) Bending strength 540 580 570 590 100 (180 C.) (MPa, in longitudinal direction) Average coefficient of 2.3 2.2 2.2 2.2 2.8 linear expansion (50-250 C.) (10.sup.6/ C.)

[0077] Test methods for the above characteristics are as follows:

(1) Water Absorption

[0078] A 100 mm100 mm1.6 mm board was placed in an oven at 105 C. to dry for 1 h, and was weighted after cooling and then steamed under a vapor pressure of 105 kPa for 120 min, and finally wiped and weighted, and then the water absorption thereof was calculated.

(2) Glass Transition Temperature Tg

[0079] A sample with a width of about 8-12 mm and a length of 60 mm was prepared and the glass transition temperature Tg thereof was measured on NETZSCH DMA Q800 by setting the measurement mode as bending mode and the scanning temperature as from room temperature to 200 C., and by reading the corresponding temperature at which the loss tangent value was maximum.

(3) Bending Strength

[0080] A 25.4 mm63.5 mm sample was prepared, and the thickness thereof was measured using a vernier caliper, and the bending strength thereof were measured on a universal material testing machine by adjusting the test mode as bending test mode, the space as 15.9 mm, and the test speed as 0.51 mm/min. An average value of three parallel tests was taken, and the test temperature was room temperature and 180 C. respectively.

(4) Peeling Strength

[0081] The copper-clad laminate was cut into a 100 mm3 mm test piece. The peeling strength of copper foil and resin was measured by stripping the copper foil and delaminating it at a speed of 50.8 mm/min using a peeling resistance test device. A larger value represents a better adhesive force between resin and copper foil.

(5) Combustibility

[0082] The combustibility was tested according to standard ANSL UL94-1985.

(6) Coefficient of Linear Expansion

[0083] The coefficient of linear expansion was tested according to standard GB 5594.3-1985.

[0084] The present invention describes the detailed technological process by the aforesaid examples, but the present invention is not limited by the aforesaid detailed technological process. That is to say, it does not mean that the present invention cannot be fulfilled unless relying on the aforesaid detailed technological steps. 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 ingredients, the selection of specific embodiments and the like all fall into the protection scope and the disclosure scope of the present invention.