TWI378993B - Reactive flame retardants and reactive flame retardant compositions - Google Patents

Description

1378993 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a kind of reaction _, which has a structure of phQsphazene for epoxy resin, polypyrene, and polystyrene. It has excellent flame retardancy and can meet the requirements of non-halogenated electronic products. [Prior Art] In recent years, the international Dawei standard, the EU directive tree protection requirements, the insecticide flame retardant will be slightly eliminated. This is because i is in the heat of the towel will be distributed _ release of the iUI MUI and A large number of linings, the shaft can be used to calculate the miscellaneous effect of the coffee season, but it will endanger the physical and ozone layer damage, _ riding _ flame retardant and replace halogen with other non-flammable elements, and then make green products are all miscellaneous in recent years - Trends in the development of agents and flame retardant resins. • Phosphorus compounds have been widely studied and applied as a new generation of environmentally friendly flame retardants, such as direct replacement of dentate flame retardants with red phosphorus or phosphoric acid to improve resin combustion characteristics. The addition of these low molecular weight compounds in the resin causes migration or inferiority of the breaking compound in the resin, and the problem of high temperature and high humidity hydrolysis of the phosphorus compound directly affects the electrical properties and mechanical properties of the resin substrate. Due to environmental and safety considerations, reactive scale flame retardants have gradually gained market mainstream status, among which DOPO (9, l(H)ihydro_9_〇xa_1〇_ _ phosphaphanthrene-10-oxide) is the most important in printed circuits. After the plate has gone into the toothless process, DOPO-type epoxy resin contains D〇p_-based, which makes the fresh-bright epoxy resin more brittle than the traditional TBM-type desert epoxy resin. During the processing of printed circuit boards 5 1378993 Irregular cracking caused by external forces such as trimming and drilling, so that the yield can not be increased. Phosphazene compounds have high phosphorus content, low polarity, low brittleness, high heat and other characteristics, and are suitable as flame retardants for epoxy resins, polyimine resins, and polyether ether resins. The Republic of China Patent No. 572,964 discloses a flame retardant epoxy resin composition characterized by: (A) at least one epoxy resin; and (B) a phosphorus-nitrogen-containing heterocyclic compound having an epoxy resin The epoxy group-reactive group can be used as an epoxy resin hardener, and the reactive group is an amine group, and the disadvantage is that the phosphorus content is 5. 6 to 7.0% or more to pass the flame retardant test. The Republic of China Patent No. 553971 discloses an epoxy resin composition which is a flame retardant which is a cyclic phenoxyphosphorus nitrogen compound or a linear phenoxyphosphorus nitrogen compound which does not react. The disadvantage of the group is that the flame retardant has poor mobility and poor flame retardancy. Japanese Patent No. 575,636, which discloses a heat-resistant composition comprising a solvent-soluble polyimine-based resin (A) and a phosphonium compound (B), which imparts flame retardancy to a composition, The disadvantage is that the phosphonium compound has no reactive group, and has no chemical bond with the polyfluorene resin, and has poor flame retardancy and mobility problems of the phosphonium compound. The Republic of China Patent No. 290150 discloses a flame retardant epoxy resin composition characterized by (A) an epoxy resin and (B) a phosphazene compound which can lead to 1798993, an amine group, an 11⁄2: group, The epoxy group has improved heat resistance and wettability, and its disadvantage is poor flame retardancy. The phosphorus content is 3·3 to 6. 7% has the effect of UL-94/V-0. The Republic of China Patent No. 290160 discloses a halogen-free flame-retardant epoxy resin composition comprising (A) at least one crosslinked phenoxyphosphazene compound (B) at least one type of polyepoxide (C) epoxy Hardener for Resin (9) Hardener accelerator for epoxy resin as an essential component, which contains 2 to 5 % by weight of the crosslinked stearoxyphosphorus compound, and contains 0 to 50% of inorganic filler. More than 3.8% or with hydrazine hydroxide / phosphate can have _ UL-94 / V-0 effect. Known phosphazene (phQ_azene) flame retardant disclosed in the above, the epoxy resin composition reaches the UL-94/V-0 flame retardant standard, and the necessary phosphorus content & SUMMARY OF THE INVENTION The object of the present invention is to provide a reaction-type flame retardant, which has a structure of a nitrile (Ph〇sphazene), which is an oxo-nitrobenzo benzocyclohexane... , (-e) group, phenyl phosphorus _, methyl phosphate, epoxy group, olefinic imine and other reactive functional groups, can produce covalent bonds with epoxy resin, _ resin, polyimide resin The knot reaction improves the defects of the conventional phosphorus guess compound, such as flame retardancy, moisture resistance and migration. Although it provides a kind of reactive flame retardant, it has two or more kinds of difficulty, and it is difficult to chemically oxidize the nitrile. Phosphate ester, epoxy group, ruthenium-containing 7 1378993 chemical structure of the hard-to-be-handling, no chemical reaction of the canister has high thermal decomposition temperature and low thermal decomposition temperature, when the thermal decomposition temperature of the flame retardant resin is at the high thermal decomposition temperature of the flame retardant chemical structure Between the listening temperature and the decomposition temperature, you can call the best axis county. It is difficult to get the minimum age of the composition. The ___ is difficult to burn and the thermal decomposition temperature of the P鸠 structure is too large, resulting in a flame retardant composition. The material required for the material is too high, the physical properties of the flame retardant resin are lowered, and the production cost is high. The reactive flame retardant of the present invention is used for manufacturing a bonded enamel layer, a printed circuit board, a substrate for thickening method, a copper box, a composite material, a laminate adhesive, a flexible substrate covering layer, Flexible substrate insulation 禺 < adhesive, soft primer, potting material, paint, anti-mite ink, light _, packaging, conductive repair tape, and the like.

Structure: Formula (I) [Embodiment] A reactive flame retardant of the present invention having a chemical knot as shown in formula ( )

8 1378993

R2 is selected from:

9 1378993

Epoxy is a Bisphenol F type epoxy resin selected from a bifunctional epoxy group or a difunctional or higher epoxy group in which an epoxy group is activated by an active hydrogen group, a Novolac type epoxy resin, a naphthalene-containing epoxy resin, and a copolymer. Benzene structure epoxy resin, epoxy resin structure containing epoxy resin, Diphenyl phosphine oxide structural ring 'oxyl resin, containing DOPO (9,10-Dihydro-9-oxa-l O-phosphaphanthrene-1 Ο-oxide) structural ring • Oxygen resin; where η is an integer from 0 to 30. The reaction type flame retardant of the present invention is synthesized by reacting a nitrile compound containing one or more phenol groups with an aniline and a roadway to form a reaction type flammable oxynitride benzocyclohexane and a phosphazene structure. Or reacting with an epoxy resin containing one or more ageing bases to form a reactive flame retardant containing an epoxy group and a phosphazene structure, or containing a gamma-based (tetra) nitrile compound and a second county oxygen The reaction is carried out to form a reactive flame retardant containing a phenyl phosphate and a phosphazene structure. The reaction type of the present invention is difficult, and the other synthetic method is to react with a monophenol containing a phosphazene compound having a gas content of 10 1378993 or more, including: using a scaly nitrile compound containing more than one gas and a cumbersome kalmarinic acid The imine reaction is carried out to form a reaction-type flame retardant containing an enelenine and a can-eye structure, or a phosphazene compound containing more than one gas and a p-quinone iodide reaction to form an enelenine-containing imine And a reaction type flame retardant having a phosphazene structure, or reacting a nitrile compound containing more than one gas with a p-phenolic tetrahydroindolizinate to form a reaction type containing an enelimine and a phosphazene structure a flame retardant, or a phosphazene compound containing more than one gas and a phenolic nadidonic acid yttrium imine to form a reactive flame retardant containing an enelimine and a phosphazene structure, or containing more than one gas The phosphazene compound reacts with a phenolic bridged ethylene tetrahydrophthalic acid sulfonium imine to form a reactive flame retardant comprising an enelimine and a phosphazene structure. The synthetic reaction type flame retardant of the present invention, wherein a phosphazene compound containing more than one chlorine is reacted with a monophenol, wherein the monophenol is a dibasic acid anhydride and an amine group to a phenol reactant, wherein the dibasic acid anhydride comprises: hexahydroortylene Dicarboxylic anhydride, methylhexahydrophthalic acid, needle bridge, methylene, six-nine-n-butic acid, methyl-bridged fluorenyl hexahydrophthalic acid, phthalic acid, terephthalic acid Formic acid liver, meta-dicarboxylic anhydride, glutaric acid liver, sebacic anhydride, α-phellandric acid _ maleic anhydride addenda, sebacic anhydride, dodecyl succinic anhydride, and the like. The synthetic reaction type flame retardant of the present invention, wherein the phosphazene compound used comprises: a phenoxyphenoxy compound, a _naphthyloxy compound, a sulfhydryl bisquinoxy compound, an oxyoxyphenoxy group Alkoxy compound, singapore oxygen 11 1378993 bisphenoxy nitrite compound, phenoloxyphenoxybiphenyloxyphosphazene compound, phenoloxyphenoxy phenyloxynaphthyloxynitrile Compound, chlorine-containing phenoxy nitrile compound, gas-containing naphthoxynitrile compound, gas-containing biphenoxyphosphazene compound, chlorophenoxymethyloxy valerate, gas-containing cyclooxybiphenyl oxide A compound, a chlorophenoxybiphenyloxyphosphazene compound, a gas-containing phenoxybiphenyloxynaphthyloxyphosphazene compound, and the like. The invention will be further illustrated by the following examples and comparative examples, which are not intended to limit the scope of the invention.

Synthesis Example 1: Flame Retardant A Dissolve aniline 933 (1 · Omole) in Dioxane 200g, put it into a four-reactor containing mechanical scrambler, condenser, addition funnel, nitrogen, and control the temperature to 5~15 ° in an ice bath. C, 250 g (24% aqueous solution) of furfural was slowly dropped into the reaction vessel over 3 hours, and the temperature was maintained at 5 to 15 ° C for 10 hours after the completion of the dropwise addition, and 459 g (0H) containing a hydroxyphenoxy squalonitrile compound was added. Equivalent = 459) 'Raise to 9 (Tc, reaction for 2 hours, increase temperature 13 CTC, remove water and solvent under reduced pressure, then cool) 'Analysis of formic acid residue 12 〇 ppm, aniline residue

0. 0001% (HPLC), phosphorus content 9.92%. Synthesis Example 2. Flame Retardant B 274 g of hydroxyphenoxyphosphazene compound (〇H equivalent = 274), epoxy resin EPICLON 830S/346g (DIC/epoxy equivalent = 173), toluene l〇〇g, Triethylamine 12 1378993 〇.5g 'Into a four-port reactor equipped with mechanical stirring, condenser and nitrogen, the temperature was controlled at 130~14 (Tc, reaction for 5 hours, cooling 13 (TC, after solvent removal under reduced pressure) After cooling, the analysis of the epoxy equivalent was 207 g/mo and the phosphorus content was 5.61%. Synthesis Example 3: Flame retardant c 274 g (0H equivalent = 274) of hydroxyphenyl hydrazine-containing nitrile compound and 133 g of methyl bis-formic acid (l , 〇mole), phenol 94g (1.0 mole), benzene benzene l〇〇g, put into a four-port reactor equipped with mechanical # stirring, condensing tube, addition funnel, nitrogen, ice bath control temperature to 5~15 °C, 202g (2.0 mole) of triethylamine was slowly dropped into the reaction crucible within 2 hours. After the completion of the dropwise addition, the temperature was maintained at 5 to 15 ° C for 1 hour, and the temperature was controlled at 8 〇 to 9 ( Rc, reaction for 2 hours, cooling to 4 (TC, washed three times, heating 130 ° C, decommissioning to remove residual water and solvent and then cooling, analysis 0H equivalent of 546000g / mole, total gas content * 0.01%, phosphorus content 13 95%.

• Synthesis Example 4: Flame Retardant D 274 g of hydroxyphenoxyphosphazene compound (〇H equivalent = 274), 195 g of phenyl dihydrogen acid (1.0 mole), phenol 94 g (1.0 mole), 100 g of toluene was placed in a reaction vessel equipped with mechanical stirring, a condenser, an addition funnel, and nitrogen, and the temperature of the ice bath was controlled to 5 to 15. (:, 202 g of triethylamine (2.0 mole) was slowly dropped into the reaction vessel within 2 hours, and the temperature was maintained at 5 to 15 t after the completion of the dropwise addition, and the reaction was carried out for 1 hour, and the temperature was controlled at 8 〇 to 9 〇 c gt. ;c, reaction for 2 hours, cooling to 40t, washing three times, heating 130 ° C, removing residual 13 I37§ 993 water and solvent after cooling, cooling, analysis of OH equivalent of 563000g / m〇le, total gas content of 0.01% The phosphorus content is 13.37%.

Synthesis Example 5: Flame Retardant E 116 g of a gas-filled nitrile compound (Hexach 1 oro cyc 1 〇tr i phosphazene ), 195 g of phenyl dichloro acid (l. 〇mole), and 200 g of tetrahydrofuran were charged. a four-port reactor with mechanical stirring, a condensing tube, an addition funnel, and a nitrogen gas; and a solution of hydroxyphenyl stearic acid sulfonium imide sodium tetrahydrofuran (hydroxyphenyl marinar iminoamine 125. 9g/〇. 666mole, sodium 15·3g/0. 666mole, tetrahydrofuran l〇〇g), the temperature of the ice bath is controlled to 20~30 ° C. The solution of hydroxyphenyl marinar imide in tetrahydrofuran is slowly added in 2 hours. In the reaction crucible, the temperature was maintained at 6 〇 to 65 after the completion of the dropping. 〇, the reaction was carried out for 6 hours, and a solution of 4-methoxyphenol sodium salt tetrahydrofuran (4 methoxy phenol i44 g/l. 333 mole, sodium 30.6 g/l. 333 m (.ile, tetrahydrofuran 300 g) was removed under reduced pressure, and tetrahydrofuran was removed under reduced pressure. ^ Add toluene (8) g 'washed twice with 5% aqueous solution of sodium hydroxide, washed once with 3% aqueous solution of hydrochloric acid, washed once with 5% aqueous solution of sodium hydrogencarbonate, washed with water until neutral, cooled under reduced pressure and cooled Adding 40 °g of bitrate hydrochloride, raising the temperature to 21 (TC, reaction for 1 hour, adding 300 g of water to dissolve pyridine hydrochloride after cooling, adjusting the pH to 6~7 with 2% sodium hydroxide water solution, Extracted four times with ethyl acetate, and the combined extracts were evaporated under reduced pressure.

Ethyl ester, total chlorine contains 1〇. 01%, 0H equivalent is 237g/mole, and the scale content is 9.83%. Synthesis Example 6: Flame Retardant F 1378993 116 g of Hexach 1 oro cye 1 〇t; ri phosphezene and 200 g of tetrahydrofuran were placed in a four-port reactor equipped with mechanical stirring, a condenser, an addition funnel, and nitrogen. In addition, the preparation of hydroxy succinic acid succinic acid sodium sulphate tetrahydrofuran; gluten solution (not basal itaconic acid imine 135. 2g / 〇. 666 mole, sodium 15. 3g / 〇. 666 mole , tetrahydrofuran i〇〇g), the temperature of the ice bath is controlled to 2〇~3〇t»c, and the tetrahydrofuran solution of the sodium hydroxyphenyl itaconate is slowly dropped into the reaction tank within 2 hours. After the completion of the temperature of 60~65 ° C, the reaction was carried out for 6 hours, and a solution of 4 methoxy sulfonated salt tetrahydrofuran (4 methoxyphenol 144g / l. 333 mole, sodium 30.6g / l. 333 mole, Tetrahydrofuran 300g) was used to remove tetrahydrofuran under reduced pressure, and 1 〇〇〇g of toluene was added, washed twice with 5% aqueous sodium hydroxide solution, washed twice with 3% aqueous hydrochloric acid solution, washed with 5% aqueous sodium hydrogencarbonate solution, and washed with water. To neutral, remove the solvent under reduced pressure, then cool, add D to 40 唆 hydrochloride 1040g liters to 2i 〇c 'reaction for 1 hour minutes' and then cool to add 3 〇〇g The chlorinated content of the total chlorinated content of the acetonitrile was 0. 01%. 0重量。 The 0H equivalent is 244g / mole, phosphorus content of 9. 54%. Synthesis Example 7: Flame retardant (j) Hexachloro cyclotriphosphazeae 116 g and tetrahydrofuran 2 g were placed in a four-reactor containing mechanical stirring, a condenser, an addition funnel, and nitrogen; Phenyltetrahydrophthalic acid sulfonium imide sodium salt tetrahydrofuran solution (hydroxyphenyltetrahydrophthalic acid ruthenium imide 171g/0. 667 35 1378993 mole, sodium 15.3g/0. 666 mole, tetrahydrogen Bite side 0g), the temperature of the ice bath is controlled to 2〇~3〇°c 'The tetrahydro sulfonate solution of the phenyltetra-phthalic acid-sodium nitrite can be slowly reacted within 2 hours. The shaft is kept at a temperature of 6Q~65〇c after the completion of the dropwise addition, and a solution of 4 oxime sodium salt tetrahydrofuran (4 methoxyphenol 144g/1333 mole, sodium 30. 6g/l. 333 mole, tetrahydrofuran 3) is additionally prepared in the reverse hour. 〇〇g) Remove the tetrahydrofuran under reduced pressure, add 曱 1000 1000g' washed twice with 5% sodium hydroxide solution, wash twice with hydrochloric acid solution, wash once with 5% sodium bicarbonate solution, then wash with water to medium To remove the solvent under reduced pressure, then cool, add pyridine hydrochloride l 40g, warm to 21 (TC, reaction for 1 hour, then cold After adding 300 g of water to dissolve the pyridine hydrochloride, the pH was adjusted to 6 to 7 with 2 (10) sodium hydroxide, and then extracted with ethyl acetate four times. The % '0H equivalent is 277 g/mole and the phosphorus content is 8.40%.

Synthesis Example 8: Refractory Agent G: Hexachloro cyclotriphosphazene U6g and tetrahydrofuran 2〇〇g were placed in a four-reactor containing mechanical stirring, a condenser, an addition funnel, and nitrogen; Base bridge methylenetetrahydrophthalic acid sulfinium iodide sodium salt tetrahydrofuran solution (hydroxyphenyl bridge methylene tetrahydrophthalic acid ruthenium imide 179g / 〇. 666 mole, sodium 15. 3g / 0. 666 Mole, tetrahydrofuran l〇〇g), the temperature of the ice bath is controlled to 20~3 (TC, the hydroxyphenyl bridged methylenetetrahydrophthalic acid sulfinium imide sodium salt in tetrahydrofuran solution slowly dripped in 2 hours In the reaction kettle, after the completion of the dropwise addition, the temperature was maintained at 60 to 65 C 'reaction for 6 hours'. A solution of 4 methoxy sulfonium tetrahydrofuran was prepared (4 16 1378993 methoxy group 144 g/l. 333 mole, Qin 30. 6g/l. 333 mole, tetrahydroanthracene 300g) Remove tetrahydrofuran under reduced pressure, add 1000g of toluene, wash twice with 5% aqueous solution of sodium hydroxide, wash twice with 3% aqueous solution of hydrochloric acid, 5% aqueous solution of sodium bicarbonate Wash once, then wash with water until neutral 'reduced solvent under reduced pressure, then cool, add acridine hydrochloride l 40g, Warm to 2HTC 'reaction for 1 hour, add 300g of water to dissolve pyridine hydrochloride after cooling. Adjust the pH to 6~7 with 20% air-oxidized steel, then extract with acetic acid for four times, decompress the extract. 65%。 The ethyl acetate, the total gas content of 0.01%, 0H equivalent of 304g / mole, phosphorus content of 7. 65%.

Synthesis Example 9··Flame Retardant I 645 g (hydroxyl oxy = 645), epoxy resin EPICLON EXA-9900/1370 g 〇 DIC / epoxy equivalent = 274), toluene 200 g, three Ethylamine 〇.8g, put into a four-port reactor equipped with mechanical stirring, condensing tube 'nitrogen gas, control temperature is 13G~14 (TC, reaction for 5 hours, cooling i〇〇 °c, decompressing solvent after cooling, cooling 'The analytical epoxy equivalent was 5〇4g/mol and the phosphorus content was 4.18%.

Synthesis Example 10: Flame Retardant J 918 g of a hydroxyphenoxy-containing nitrile compound (0H equivalent = 459), and a phenol containing bisphenol A type 22 epoxy resin (epoxy equivalent = 560 / filled content 2.83%) 2, toluene 2 〇〇 g, triethylamine 0.8 g, put into a four-port reactor equipped with mechanical stirring, condensing tube, nitrogen, control temperature is 130~14 (TC, reaction for 5 hours, cooling i〇 (Tc, The 17 I37 & 993 agent was removed under reduced pressure and then cooled, and the epoxy equivalent was analyzed to be 1579 g/in of the phosphorus content of 5.75%.

Synthesis Example 11: Flame Retardant K 861 g of a hydroxy alkanoyloxyphosphazene compound (〇 ii equivalent = 861), a DOPO-containing epoxy resin llOlg (epoxy equivalent = 275 / phosphorus content 2.81%) Toluene 200g 'triethylamine 0.3⁄4, put into a four-port reactor equipped with mechanical stirring, condenser, nitrogen, control temperature is 13〇~i4 (Tc, reaction for 5 hours, cooling l〇〇t: The solvent was removed under reduced pressure and then cooled, and the obtained epoxy equivalent was 674 g/m 〇1 and the phosphorus content was 5.85%.

Synthesis Example 12: Flame Retardant L The D0P0 phenolic epoxy resin llOlg (epoxy equivalent = 275 / phosphorus content 2.81%), toluene 200 g, and triethylamine 0.8 g were placed in a mechanical stirring, condensing tube, Four reactions of nitrogen were used to control the temperature at 13 〇 to K (rc, reaction for 5 hours, cooling 1 G0C, cooling under reduced pressure, cooling, analysis of epoxy equivalent of 692 g / m 〇 i, phosphorus content of 5. 53%. Examples 1 to 19 The flame retardants of Synthesis Examples 1 to 12, N_6_IC/epoxy resin/epoxy equivalent-212), 0PE (Dintims/difunctional polyphenylene (6), sn_9_Hitachi Chemical/Poly Brewing Imine resin), sclerosing agent (dicyandiamine), _2_sodium ethyl -4-tetramyl hydrazine, azobisisobutyronitrile (deleted), difficult (dimethyl methacrylate)丙 0 0g dissolved evenly, and allowed to stand for 12 hours to prepare a resin varnish. The glass fiber 1379993 cloth was impregnated in the prepared epoxy resin varnish, dried at 160 ° C for 1 minute to become a prepreg, Eight sheets of prepreg were laminated, and laminated with epoxy resin fiberglass cloth under pressure of 185 ° C and 25 Kg / cm ^ 2 , and the properties were analyzed. The results are shown in Table 1. 2. The first example: Comparative Example 1: The present invention contains a base-based acetoxylonitrile compound (〇Η equivalent = 274), N-680 (DIC/epoxy resin/epoxy equivalent = 212), (hardener DICY) (Dicyanamide), accelerator 2E4MZ (2-ethyl-tetrafyl imino saliva), _F (dimethyl ketoamine chest, acetone dissolved evenly) allowed to stand for 12 hours, Jingcheng epoxy resin varnish. The fiber cloth is impregnated in the epoxy resin varnish of the chick, and it is cut into minutes by the job. It becomes a pre-impregnated 'like #职亲#合, (4) this, the spider / square centimeter of the ink force is called the epoxy flip glass. The secret of the skin is analyzed and its performance is analyzed. The results are shown in Table 2.

Flame retardant I is a flame retardant 配合 mix ratio (weight)

19 1378993 Flame retardant L 682 N-680 212 1840 848 848 1060 1060 424 424 424 ΟΡΕ 500 500 500 500 SN-9000 DICY 42 168 105 105 2E4MZ 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 AIBN 0.1 0.1 0.1 Plate performance phosphorus content (%) 2.51 2. 53 2.42 2 31 2.34 2.61 2.09 2.0 1.99 1.94 Flame retardant UL-94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Tg (°C) 142 154 155 148 181 185 159 179 181 183 • Table 2

More examples than the implementation of the implementation of the application of the example: Example of the example ratio (weight) 11 12 13 14 15 16 17 18 19 flame retardant A 288 Flame retardant B 207 207 Flame retardant C Flame retardant D Flame retardant E Flame retardant F Flame retardant G Flame retardant Η 304 Flame retardant I 252 Flame retardant J 158 Flame retardant K 135 135 Flame retardant L 138 PZ-3 273 N-680 424 848 106 191 170 170 170 424 OPE 500 500 SN-9000 5750 5750 5750 575Γ 5750 5750 DICY 94.5 21 2E4MZ 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 AIBN 0.1 The phosphorus content of the laminate (%) 1.89 1.64 2. 32 1.95 1.72 1.49 1.30 1.26 1.30 4. 82 Flame retardant UL-94 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-1 Tg (°C) 178 186 153 195 184 183 190 191 187 146 20 1378.993 Test Examples 1 to 19, Comparative Example 1 Epoxy Resin Composition, Polyimide Resin Resin Group, according to the following method The properties of the laminate obtained from the composition of the polyphenylene ether resin: (1) Flame retardancy: The laminate obtained from the epoxy resin composition is made into a test piece of 5吋, 〇5吋 and 1/16吋, according to UL- The specification of 94 is tested for its flame retardancy; the test piece of the laminate obtained from the same composition is taken from Μ 'Every one shot twice' total 1G combustion totaling time does not exceed 50 seconds and each single burning does not exceed 1 second. That means passing the test. (2) Tg: Test the test piece by DSC, and heat up 1{rc per minute to measure the glass transition temperature. It can be seen from the results of Table- and Table 2 that the reactive flame retardant of the present invention is used for epoxy eucalyptus and polyphenyl phthalocyanine polyimine resin, and the required scale content is less than 3%, which is known. Phosphazene is a flame retardant with excellent flame retardancy. The present invention has been combined with the above-mentioned frequency synthesis examples, real customs, and tastes, and those skilled in the art will be able to make various changes based on the above description. [Simple description of the diagram] 21 1378993 [Explanation of main component symbols]

Claims (1)

1378993_ Announcement X. Patent application scope: • 1. A reactive flame retardant having a chemical structure as shown in formula (I): Formula (I) N+rN v R2 R2 wherein R1 is selected from: 23 1378993 R3 is selected from: /^λ, methyl; R4 is selected from methyl; Epoxy is a difunctional epoxy epoxy resin or a difunctional or higher epoxy epoxy resin selected from one of the epoxy groups activated by active hydrogen; An integer from 0 to 30. 2. For the reactive type flame retardant of the first application of the patent scope, it is used for epoxy resin, polyphenylene ether resin, and polyimide resin. twenty four