INTRINSIC FLAME-RETARDANT RESIN WITH LOW POLARITY, AND PREPARATION METHOD THEREFOR AND USE THEREOF

Abstract

Provided are an intrinsic flame-retardant resin with a low polarity, and a preparation method therefor and the use thereof. The intrinsic flame-retardant resin with a low polarity has a structure as shown in formula I and is a phenolic compound or resin which is prepared by a three-step reaction of allyl etherification, rearrangement and terminating with a phosphorus-containing group. The resin does not contain polar hydroxyl groups in the molecular formula thereof, and has a stable molecular structure, low polarity and high reactivity, and does not generate polar hydroxyl groups during application and processing, thereby avoiding the influence of secondary hydroxyl groups on the performance of products thereof. While the resin improves the dielectric performance, same still has crosslinkable groups which lead to no significant change in high temperature resistance after curing. Introduction of the phosphorus-containing capping group allows the resin to have intrinsic flame-retardant performance. Using the resin in the preparation of a metal foil clad laminate facilitates reducing the dielectric constant and dielectric loss of the metal foil clad laminate, and results in higher high temperature resistance and improved flame retardancy, so that the metal foil clad laminate has a good comprehensive performance and broad application prospects.

Claims

1. An intrinsic flame-retardant resin with a low polarity, wherein the intrinsic flame-retardant resin with a low polarity has a structure as shown in Formula I: ##STR00022## wherein R is a linear or branched alkyl, ##STR00023## X and Y are independently selected from the group consisting of hydrogen, allyl, linear alkyl, branched alkyl, and a combination of at least two selected therefrom; A is a phosphorus-containing capping group; and n is an integer of 1-20.

2. The intrinsic flame-retardant resin with a low polarity of claim 1, wherein R is selected from the group consisting of CH.sub.2, ##STR00024## n is an integer of 1-20; X and Y are independently selected from the group consisting of hydrogen, allyl, linear alkyl, branched alkyl, and a combination of at least two selected therefrom; and A is a phosphorus-containing capping group.

3. A process for preparing the intrinsic flame-retardant resin with a low polarity of claim 1, wherein the process comprises the following steps: (1) a phenolic compound or a phenolic resin of Formula II is reacted with an allylation reagent to obtain an allyl etherified resin of Formula III, wherein the reaction formula is as follows: ##STR00025## (2) the allyl etherified resin of Formula III is heated under the protection of a protective gas, and an intramolecular rearrangement reaction occurs to obtain an allylated phenolic resin of Formula IV: ##STR00026## (3) the allylated phenolic resin of Formula IV is reacted with a phosphorus-containing capping reagent to obtain the intrinsic flame-retardant resin with a low polarity of Formula I: ##STR00027## wherein R.sub.1 is selected from the group consisting of linear or branched alkyl, ##STR00028## R.sub.2 is selected from the group consisting of linear or branched alkyl ##STR00029## R.sub.3 is selected from the group consisting of linear or branched alkyl, ##STR00030## R is selected from the group consisting of linear or branched alkyl, ##STR00031## X and Y are independently selected from the group consisting of hydrogen, allyl, linear alkyl, branched alkyl, and a combination of at least two selected therefrom; A is a phosphorus-containing capping group; and n is an integer of 1-20.

4. The process of claim 3, wherein the phenolic compound or phenolic resin in step (1) is phenol, dihydric phenol, polyhydric phenol or derivatives thereof.

5. The process of claim 3, wherein the reaction in step (1) is carried out in the presence of a phase transfer catalyst.

6. (canceled)

7. The process of claim 3, wherein the phosphorus-containing capping reagent in step (3) is anyone selected from the group consisting of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-1,4-hydroquinone, 2-(6H-dibenzo-(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-4-phenol, 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-3-phenol, 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-4-benzyl alcohol, 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-3-benzyl alcohol, and a combination of at least two selected therefrom.

8. A resin composite material made from the intrinsic flame-retardant resin with a low polarity of claim 1.

9. An electronic packaging material made from the intrinsic flame-retardant resin with a low polarity of claim 1.

10. A metal foil clad laminate made from the intrinsic flame-retardant resin with a low polarity of claim 1.

11. The intrinsic flame-retardant resin with a low polarity of claim 1, wherein A is a DOPO-containing group.

12. The intrinsic flame-retardant resin with a low polarity of claim 11, wherein A is anyone selected from the group consisting of: ##STR00032##

13. The intrinsic flame-retardant resin with a low polarity of claim 1, wherein the intrinsic flame-retardant resin with a low polarity is anyone selected from the group consisting of the compounds having the following Formulae A-E, and a combination of at least two selected therefrom: ##STR00033## wherein n is an integer of 1-20.

14. The process of claim 3, wherein the allylation reagent is anyone selected from the group consisting of allyl silanol, allyl chloride, allyl bromide, allyl iodide, allylamine, and a combination of at least two selected therefrom.

15. The process of claim 3, wherein the molar ratio of the phenolic hydroxyl groups in the phenolic compound or phenolic resin to the allyl groups in the allylation reagent is 1:(0.3-1.2).

16. The process of claim 3, wherein the reaction in step (1) is carried out in the presence of a basic substance, which is anyone selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and a combination of at least two selected therefrom.

17. The process of claim 16, wherein the molar ratio of the basic substance to the phenolic hydroxyl groups contained in the phenolic compound or phenolic resin in step (1) is (0.3-1.4):1.

18. The process of claim 3, wherein the temperature of the reaction in step (1) is 60-90 C.

19. The process of claim 3, wherein the heat treatment in step (2) refers to heating to 180-220 C.

20. The process of claim 3, wherein the molar ratio of the phenolic hydroxyl groups in the allylated phenolic resin of Formula IV in step (3) to the phosphorus-containing capping groups in the phosphorus-containing capping reagent is 1:(1-1.2).

21. The process of claim 3, wherein the reaction in step (3) is carried out in the presence of a basic substance.

22. The process of claim 3, wherein the reaction in step (3) is carried out in the presence of carbon tetrachloride.

Description

DESCRIPTION OF THE FIGURES

[0054] FIG. 1 shows an infrared spectrum diagram of the intrinsic flame-retardant resin with a low polarity prepared in Example 1.

EMBODIMENTS

[0055] The technical solutions of the present invention will be further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are used only to understand the present invention, rather than any specific limitations to the present invention.

Example 1

[0056] In the present example, the low-polarity intrinsic flame-retardant resin was prepared by the following method, including the following steps:

(1) 188 g of acetone was added to a three-necked reaction flask. 228 g of bisphenol A was then added to the reaction flask, stirred and dissolved, and 106 g of sodium carbonate was added. 153 g of a chloropropene solution was slowly added dropwise, and then the reaction was stopped after raising the temperature for 4 hours. Filtration, removal of most of the solvent and washing were carried out, and then removal of residual solvent and water gave bisphenol A diallyl ether.
(2) 134 g of bisphenol A diallyl ether prepared in step (1) was placed in the reaction flask, and subjected to a rearrangement reaction by heating for 6 hours. The mixture was cooled to obtain a brown viscous liquid, i.e. diallyl bisphenol A.
(3) An inert gas was introduced into the three-necked reaction flask for protection. 300 g of dichloromethane was added. 134 g of diallyl bisphenol A prepared in step (2) was placed in the reaction flask, stirred and dissolved. 40 g of sodium hydroxide was added, and 152 g of carbon tetrachloride was added. 230 g of 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-4-phenol was slowly added dropwise, and the reaction was stopped after reacting for 4 hours. An aqueous solution of sodium hydroxide was added to wash to neutrality, then washing was conducted several times to remove residual solvent and water, thereby obtaining phosphorus-containing esterified diallyl bisphenol A, i.e. the low-polarity intrinsic flame-retardant resin having the structure thereof as follows:

##STR00018##

[0057] The infrared spectrum diagram of the phosphorus-containing esterified diallyl bisphenol A prepared in this example is shown in FIG. 1 (T % in FIG. 1 indicates % transmittance). It can be seen that the hydroxyl structure at 3300-3500 cm.sup.1 has disappeared and does not contain polar hydroxyl groups, which significantly reduces the molecular polarity.

Example 2

[0058] In the present example, the low-polarity intrinsic flame-retardant resin was prepared by the following method, including the following steps:

(1) 300 g of n-butanol was added to a three-necked reaction flask. 114 g of linear phenolic resin was then added to the reaction flask, stirred and dissolved, and 56 g of potassium hydroxide was added. 153 g of a bromopropane solution was slowly added dropwise, and then the reaction was stopped after raising the temperature for 4 hours. Filtration, removal of most of the solvent and washing were carried out, and then removal of residual solvent and water gave an allyl etherified phenolic resin.
(2) 141 g of the allyl etherified phenolic resin in step (1) was placed in the reaction flask, and subjected to a rearrangement reaction by heating for 4 hours. The mixture was cooled to obtain a brown viscous liquid, i.e. allyl phenolic resin.
(3) An inert gas was introduced into the three-necked reaction flask for protection. 350 g of dichloromethane was added. 141 g of the allyl phenolic resin prepared in step (2) was placed in the reaction flask, stirred and dissolved. 72 g of triethylamine was added, and 152 g of carbon tetrachloride was added. 230 g of 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-4-phenol was slowly added dropwise, and the reaction was stopped after reacting for 4 hours. An aqueous solution of sodium hydroxide was added to wash to neutrality, then washing was conducted several times to remove residual solvent and water, thereby obtaining phosphorus-containing esterified allyl phenolic resin, i.e. the low-polarity intrinsic flame-retardant resin having Mn (converted by using polystyrene measured by gel permeation chromatography) of 1,300 and the structure thereof is as follows:

##STR00019##

Example 3

[0059] In the present example, the low-polarity intrinsic flame-retardant resin was prepared by the following method, including the following steps:

(1) 250 g of toluene was added to a three-necked reaction flask. 118 g of o-cresol novolac resin was then added to the reaction flask, stirred and dissolved, and 100 g of an aqueous solution of sodium hydroxide (having a concentration of 40%) was added, and then 1 g of tetrabutylammonium bromide was further added. After the temperature became constant, 153 g of a chloropropene solution was slowly added dropwise. The reaction was stopped after raising the temperature for 4 hours. Washing and removal of the solvent were carried out to obtain allyl etherified o-cresol novolac resin.
(2) 159 g of the allyl etherified o-cresol novolac resin prepared in step (1) was placed in the reaction flask, and subjected to a rearrangement reaction by heating for 4 hours. The mixture was cooled to obtain a dark brown semisolid, i.e. allyl o-cresol novolac resin.
(3) An inert gas was introduced into the three-necked reaction flask for protection. 350 g of dichloromethane was added. 159 g of the allyl o-cresol novolac resin prepared in step (2) was placed in the reaction flask, stirred and dissolved. 103 g of pyridine was added, and 152 g of carbon tetrachloride was added. 230 g of 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-3-phenol was slowly added dropwise, and the reaction was stopped after reacting for 4 hours. An aqueous solution of sodium hydroxide was added to wash to neutrality, then washing was conducted several times to remove residual solvent and water, thereby obtaining phosphorus-containing esterified allyl o-cresol novolac resin, i.e. the low-polarity intrinsic flame-retardant resin having Mn of 1,200 and the structure thereof is as follows:

##STR00020##

Example 4

[0060] In the present example, the low-polarity intrinsic flame-retardant resin was prepared by the following method, including the following steps:

(1) 250 g of toluene was added to a three-necked reaction flask. 118 g of cyclopentadiene novolac resin was then added to the reaction flask, stirred and dissolved, and 100 g of an aqueous solution of sodium hydroxide (having a concentration of 40%) was added, and then 1 g of tetrabutylammonium bromide was further added. After the temperature became constant, 153 g of allyl silanol was slowly added dropwise. The reaction was stopped after raising the temperature for 4 hours. Washing and removal of the solvent were carried out to obtain allyl etherified cyclopentadiene novolac resin.
(2) 159 g of allyl etherified cyclopentadiene novolac resin prepared in step (1) was placed in the reaction flask, and subjected to a rearrangement reaction by heating for 4 hours. The mixture was cooled to obtain a dark brown semisolid, i.e. allyl cyclopentadiene novolac resin.
(3) An inert gas was introduced into the three-necked reaction flask for protection. 350 g of dichloromethane was added. 159 g of the allyl cyclopentadiene novolac resin prepared in step (2) was placed in the reaction flask, stirred and dissolved. 103 g of pyridine was added, and 152 g of carbon tetrachloride was added. 230 g of 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-4-benzyl alcohol was slowly added dropwise, and the reaction was stopped after reacting for 4 hours. An aqueous solution of sodium hydroxide was added to wash to neutrality, then washing was conducted several times to remove residual solvent and water, thereby obtaining phosphorus-containing esterified allyl cyclopentadiene novolac resin, i.e. the low-polarity intrinsic flame-retardant resin having Mn of 1,280 and the structure thereof is as follows:

##STR00021##

Example 5

[0061] 80 parts by weight of liquid styrene-butadiene resin Ricon 100, 20 parts by weight of phosphorus-containing esterified diallyl bisphenol A prepared in Example 1, 85 parts by weight of silica (525), and 6.5 parts by weight of an initiator DCP were mixed, adjusted to a suitable viscosity with a solvent of toluene, stirred and uniformly mixed to uniformly disperse the filler in the resin, so as to obtain a varnish. 1080 glass fiber cloth was impregnated with the varnish above, and then dried to remove the solvent to obtain a prepreg. Eight sheets of prepared prepregs were laminated, and pressed on both sides thereof with copper foils having a thickness of 1 oz (ounce), and cured in a press for 2 hours at a curing pressure of 50 Kg/cm and a curing temperature of 190 C. to obtain a copper clad laminate.

Example 6

[0062] The only difference from Example 5 was that the phosphorus-containing esterified diallyl bisphenol A prepared in Example 1 was replaced with the phosphorus-containing esterified allyl phenolic resin prepared in Example 2.

Example 7

[0063] The only difference from Example 5 was that the phosphorus-containing esterified diallyl bisphenol A prepared in Example 1 was replaced with the phosphorus-containing esterified allyl o-cresol novolac resin prepared in Example 3.

Example 8

[0064] The only difference from Example 5 was that the phosphorus-containing esterified diallyl bisphenol A prepared in Example 1 was replaced with the phosphorus-containing esterified allyl cyclopentadiene novolac resin prepared in Example 4.

[0065] Comparison Example 1 80 parts by weight of liquid styrene-butadiene resin Ricon 100, 85 parts by weight of silica (525), and 5.8 parts by weight of an initiator DCP were mixed, adjusted to a suitable viscosity with a solvent of toluene, stirred and uniformly mixed to uniformly disperse the filler in the resin, so as to obtain a varnish. 1080 glass fiber cloth was impregnated with the varnish above, and then dried to remove the solvent to obtain a prepreg. Eight sheets of prepared prepregs were laminated, and pressed on both sides thereof with copper foils having a thickness of 1 oz (ounce), and cured in a press for 2 hours at a curing pressure of 50 Kg/cm and a curing temperature of 190 C. to obtain a copper clad laminate.

[0066] The sources of raw materials applied in Examples 5-8 and Comparison Example 1 are shown in Table 1, and the physical property data of the prepared copper clad laminates are shown in Table 2.

TABLE-US-00001 TABLE 1 Manufacturer Product name or Brand Material content Sartomer Ricon 100 Styrene-butadiene resin Homemade Esterified-2-allylphenol Sibelco 525 Silica micropowder Shanghai Gaoqiao DCP Dicumyl peroxide Shanghai Honghe 1080 glass fiber cloth Having a thickness of 0.05 mm and a basis weight of 48 g/m.sup.2

TABLE-US-00002 TABLE 2 Performance Example 5 Example 6 Example 7 Example 8 Comp. Example 1 Dielectric constant 3.62 3.83 3.76 3.58 3.5 (10 GHZ) Dielectric loss tangent 0.0054 0.0058 0.0055 0.0048 0.004 (10 GHZ) Dip soldering resistance >300 >300 >300 >300 15 288 C., (s) Glass transition temperature 156 182 178 185 10 ( C.) (DSC) Flame retardancy No combustion No combustion No combustion No combustion Combustion Glass dipping operation Good, Good, Good, Good, Poor, sticky not sticky not sticky not sticky not sticky

[0067] It can be seen from Table 2 that the low-polarity intrinsic flame-retardant resin prepared according to the present invention can make the copper clad laminates have lower dielectric constant and dielectric loss, and have better high temperature resistance and flame retardancy.

[0068] The applicant claims that the low-polarity intrinsic flame-retardant resin of the present invention, its preparation method and application are described by the above examples. However, the present invention is not limited to the above examples, i.e. it does not mean that the present invention cannot be carried out unless the above examples are applied. Those skilled in the art shall know that any modifications of the present invention, equivalent substitutions of the materials selected for use in the present invention, and additions of auxiliary ingredients, and specific manners in which they are selected, are all within the protection scope and disclosure scope of the present invention.