TW572954B - Phosphorus-containing compounds and their use in flame retardance - Google Patents

Abstract

A series of novel phosphorus-containing compounds suitable for use as a flame retardant having the following formula are disclosed, wherein R1-R8 independently are H or C1-C4 alkyl; Y is -OH or formula; X is Q or formula; wherein Q is H, -NO2, -NH2, -OH, -CH3, -CHO, -COOH; formula, A is -O-, formula, -CH2-, or -C(CH3)2-, R9 and R10 independently are H, or C1-C4alkyl.

Description

(Amended in March 2003)

TECHNICAL FIELD The present invention relates to a series of novel phosphorus-containing compounds having hard aromatic groups, and their flame-resistant applications. In addition to traditional building materials and textiles in the prior art, organic polymer materials are also required to be flame-resistant when they are used in the manufacture of electronic products, such as printed circuit boards, integrated circuit (1C) packaging materials, electronic connectors, and so on. . In order to improve the flammability of organic polymer materials, whether it is a thermosetting resin or a thermoplastic resin, a flame retardant is usually used to achieve the purpose. Organophosphorus compounds have been widely used as so-called "halogen-free flame retardants" to improve or solve the problems of smoke toxicity, corrosion and dioxin pollution caused by the use of halogen flame retardants. Among them, phosphate ester compounds, including aliphatic or aromatic phosphate compounds, are particularly widely used in current products, such as triphenylphosphate, triresylphosphate, and triethylphosphate. Ester (triethylphosphate), etc. When these phosphorus compounds are added to the resin, they may have disadvantages such as insufficient thermal stability or excessive migration. Therefore, some phosphate oligomers such as the dimers of Resorcinol diphenyl diphosphate and their oligomers (eg, Japanese Patent No. 223158, US Patent No. 5204394, US Patent No. 5618867, etc.) ), Phosphate oligomers with a substituent structure (such as US Patent No. 5,506,313, European Patent EP-A-0456605, European Patent EP-A-0509506, etc.) have also been developed (amended in March 2003). As a non-halogen flame retardant. In addition to being required to be flame-resistant, polymer materials used in electronic products are also required to have excellent electrical properties, thermal stability properties, and dimensional stability. The addition of flame retardants will have a certain degree of influence on the properties of the resin itself, so the performance requirements of the flame retardants used in it will be higher. It is an object of the present invention to provide a series of phosphorus-containing compounds having a novel chemical structure. Another object of the present invention is to provide a series of novel phosphorus-containing compounds for use as flame retardants. Another object of the present invention is to provide a flame retardant resin composition comprising a phosphorus-containing compound of the present invention as a flame retardant. Another object of the present invention is to provide a hardened flame retardant resin prepared by hardening the flame retardant resin composition of the present invention. Another object of the present invention is to provide a flame-retardant polymer, which is prepared by polymerizing the phosphorus-containing compound of the present invention as a monomer, or polymerizing the phosphorus-containing compound monomer of the present invention with other monomers. . SUMMARY OF THE INVENTION In order to achieve the above-mentioned object of the present invention, a phosphorus-containing compound synthesized according to the present invention has the following chemical formula (I): 572954 (as amended in March 2003)

(I) wherein Ri-Rs are independently H or C-C4 alkyl; Y is -0H or

Ri; X is Q or 'wherein Ri-R4 has the same definition as above; Q is Η, -N〇2, -NHa, -OH, -CH3, -CH〇, -C〇〇H,

Q corpse, 〇 corpse, Yan ~ -N —OCH2CHCH2, —C—OCH2CHCH2, —N—CH2CHCH2, or

R9 & R1Q is independently H, or G-C4 alkyl; and 〇—〇-CA 是 -〇-, —C-Ο— '0,-, -CH2-, or -C (CH3) 2 Preferably, X is Q in formula (2). Preferably, X is -A in formula (2).

Rio -Q Preferably, Ri-R8 in formula (I) is Η, Y is

Preferably, Q in formula (I) is -NIL ·. Preferably, Q in formula (I) is -0Η. 572954 (Amended in March 2003)? Preferably, Q in formula (i) is -0CH2CHCH2. Preferably, eight in formula (I) is _〇_. 〇 Preferably, A in formula (I) is a C-0—. —〇—Q- Preferably, A in formula (I) is δ. The present invention also provides a flame retardant resin composition comprising a phosphorus-containing compound of the above formula (I) as a flame retardant. The present invention also provides a hardened flame retardant resin, which is prepared by hardening the aforementioned flame retardant resin composition of the present invention. The present invention further provides a flame-retardant polymer, which is obtained by polymerizing a phosphorus-containing compound having the formula (I) as a monomer, or a phosphorus-containing compound monomer having the formula (I) and other monomers. Prepared by polymerization. The phosphorus-containing compound (I) of the present invention has the advantages of simple synthesis steps, high phosphorus content, high heat resistance, and the like, and is suitable for being added or prepared with various types of organic high molecular materials, and imparting flame resistance. Embodiments The present invention discloses a phosphorus-containing compound having a novel chemical structure, simple synthesis steps, high phosphorus content and high heat resistance, and a method for preparing the same. It improves the previously invented phosphorus-based flame retardants with complex processes, low phosphorus content, and insufficient heat resistance. . The phosphorus-containing compound synthesized in one embodiment of the present invention has the following structure: 9 572954 (revised in March 2003)

Where Ri-Rs is H or Ci-C4 alkyl, and Y is -OH or

, X is -Η, -N〇2, -NH2, -OH, -CH3, -CHO A corpse 〇 corpse ch2chch2 ^ -COOH, one OCH2CHCH2, -C one OCH2CHCH2, N CH2CHCH2, 〇

〇 The phosphorus-containing compound synthesized in another embodiment of the present invention may also have the following structure:-A R10 where H or G-C4 alkyl; Y and X have the same definitions as above; and A 0-〇-C — It is -〇-, -co- > 6, single bond, -ch2-, -c (ch3) 2-. A method suitable for preparing the phosphorus-containing compound of the present invention comprises the step of adding 9,10-dihydro-9-oxy-10-phosphophenanthrene 10-oxide having the formula

10 572954 (Amended in March 2003) (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide j for short)

(Wherein R—R4 is H or Ci-C * alkyl group), obtained by reacting with a compound having a -C = 0 group, such as a benzophenone derivative, at a temperature of 100-200 ° C . The benzophenone derivative having a reactive functional group can be used to synthesize the phosphorus-containing compound of the present invention having a reactive functional group. The phosphorus-containing compound obtained by the above reaction can be synthesized by a conventionally-known organic synthesis method.

The phosphorus-containing compound of the present invention has a reactive functional group, can be polymerized with other monomers, and grafted or cross-linked with a polymer to synthesize a corresponding flame-retardant phosphorus-containing polymer, or directly added as a flame-retardant. As a polymer material, it can be applied to the manufacture of various electronic products with flame retardant effects. The present invention can be described in more detail with reference to the following examples, which are only used for illustration and are not intended to limit the scope of the present invention. The reactions involved in the following examples are shown in the following reaction scheme 1: Scheme 1 11 572954 (Amended in March 2003)

Example 1 (Synthesis of Compound A) In a 1-liter three-necked flask reaction vessel with a temperature control and indicating device, 512 g of DOPO and 107 g of dihydroxy-benzophenone were added, and the temperature was raised to 180 ° C. The temperature of the reaction system was maintained at 180 ° C. After three hours of reaction, 500 ml of toluene was added, and the mixture was filtered and separated. The solid was washed twice with 500 ml of tetrahydrofuran and then filtered. The product was treated under vacuum at 80 ° C for two hours. , To obtain a white solid DOPO derivative compound A with a dihydroxy group. The FTIR spectrum, 1HNMR spectrum and 31PNMR spectrum of Compound A are shown in Fig. 1, Fig. 2a and Fig. 3, respectively. 12 572954 (Amended in March 2003) Example 2 (Synthesis of Compound B) · Repeat the steps of the example, but replace the dihydroxy-benzophenone with diamino phenone and react to obtain a diamine with a white solid. The DOPO derivative compound B. The FTIR spectrum, 1H NMR spectrum and 31P NMR spectrum of Compound B are shown in FIG. 1, FIG. 2 b and FIG. 3, respectively. Example 3 (Synthesis of Compound C) At a temperature and pressure control and indicating device, and 3 liters of water and epoxy halopropane co-distillation mixture can be condensed and separated into oil phase and water phase device In a four-necked flask reaction vessel, 300 g of a DOPO derivative A having a dihydroxy group and 1,000 g of epichlorohydrin were added. After the mixture was dissolved under atmospheric pressure to dissolve into a homogeneous solution, it was heated to 70 ° C at an absolute pressure of 190 mmHg, and at the equilibrium temperature and pressure of this solution, 80.2 g of 49.3% hydroxide was added at a rate within four hours. When the sodium solution and sodium hydroxide solution are added, the water in the reaction system is distilled off azeotropically. After condensing, the azeotrope is separated into an oil phase and an aqueous phase, and the oil phase is continuously returned to the reaction system. The water phase is excluded from the reaction system. After the reaction is completed, the unreacted epichlorohydrin and solvent are distilled off under reduced pressure. The resulting crude epoxy resin is dissolved with methyl ethyl ketone and deionized water, and the resin is washed with water. Sodium chloride. The methyl ethyl ketone was then distilled off under reduced pressure to obtain a pale yellow epoxy-containing DOPO derivative C with an epoxy equivalent of 378. Example 4 (Synthesis of Compound D) In a 1-liter three-neck flask with a temperature control and indicating device, a reaction capacity of 13 572954 (revised in March 2003), 100 g of a dihydroxy DOPO derivative A, 50 grams of p-chloronitrobenzene and 44 grams of potassium carbonate were dissolved in 600 ml of dimethylformamide (DMF), and the temperature was raised to reflux for 8 hours to reduce the temperature to room temperature. The reaction mixture was precipitated with a 1: 1 methanol-water mixture, washed with toluene and tetrahydrofuran, and dried under vacuum at 80 ° C. for 3 hours to obtain a solid product D. Example 5 (Synthesis of Compound E) In a 1-liter three-necked flask reaction vessel with a temperature control and indicating device, 80 g of Compound D, 110 g of stannous chloride, 500 ml of ethanol, and 150 ml After stirring at room temperature for 4 hours, the reaction solution was concentrated on a rotary evaporator, and the precipitate was filtered and neutralized with a 25% sodium hydroxide aqueous solution to neutrality. The product was recrystallized from ethanol to obtain a solid product as compound E. Example 6 (Synthesis of Compound F) In a 1-liter three-necked flask reaction vessel with a temperature control and indicating device, 30 grams of maleic anhydride was dissolved. This solution was ice-bathed in 200 ml of acetone. Another 60 grams of Compound B (synthesized by Example 2) was dissolved in 400 ml of acetone, and after reacting for four hours, 50 ml of acetic anhydride and 8.5 g of sodium acetate were added and reacted at 60 ° C for 4 hours. The solution was concentrated on a rotary evaporator and precipitated with ethanol. After filtration, the product was recrystallized from ethanol to obtain a solid product as compound F. 14 572954 (Amended in March 2003) Example 7 (Synthesis of Compound G)-In a 1-liter three-necked flask reaction vessel with a temperature control and indicating device, equipped with a reaction device of dry nitrogen, 62 g of the compound A (synthesizer of Example 1) was dissolved in 400 ml of DMF, 23 g of triethylamine was added, and the mixture was ice-baked. 41 g of nitrophosphonium chloride was slowly added over 1 hour. After the addition was complete, the reaction was continued at room temperature for 4 hours. The reaction was filtered and recrystallized with DMF to obtain solid product compound G. Example 8 (Synthesis of Compound IX) A solid product of Compound IX was prepared by repeating the steps of Example 5 except that Compound G was substituted for Compound D for reaction. Example 9 (Preparation of a flame-resistant epoxy resin) Compound C of Example 3 and a commercial bisphenol-A epoxy resin (Changchun Artificial Resin Factory Co., Ltd., code: Β188) were mixed at different ratios (such as Table 1), flame retardant epoxy resin can be prepared. Table 1. Preparation of flame-resistant epoxy resin finger compound No. C (g) BE188 (g) Flame-resistant epoxy 5 95 Flame-resistant epoxy-B 20 80 50 50 Flame-resistant epoxy-D 70 30 Flame-resistant ring Oxygen Resin-E 90 10 Flame Retardant Epoxy Resin-F 95 5 Example 10 (Preparation of Flame Retardant Plastics) 15 572954 (Amended in March 2003) As shown in Table 2 below, take the compound A of Example 1 and 1. The general thermoplastic plastic is mixed with a hot-melt method to obtain a flame-resistant plastic (the hot-melt method is used in this embodiment, and the solution method can also be used). The thermoplastic plastics used in this embodiment include polycarbonate, polystyrene, acrylic-butadiene-styrene copolymer (ABS), and polyphenyloxide. , PPO), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc. Table II. Preparation of flame-resistant plastics No. Compound A (g) Plastic (g) Flame-resistant plastic-A 15 Polycarbonate 100 Flame-resistant plastic-B 15 Polystyrene 100 Flame-resistant plastic-C 15 Polypropylene-Dinger Olefin-styrene copolymer 100 flame retardant plastic-D 15 polystyrene oxide 100 flame retardant plastic-E 15 polyethylene terephthalate 100 flame retardant plastic-F 15 polybutylene terephthalate 100 First (hardened flame retardant resin) The flame retardant epoxy resin C prepared in Example 9 is mixed with a generally known epoxy resin hardener (such as diaminodiphenylmethane) or as shown in Example 2 of the present invention. Compound B or Compound E of Example 5 and the like are uniformly mixed and then hardened by a commonly known hot hardening method, and the flame retardant resin can be slowed to harden (see Table 3). 16 572954 (Amended in March 2003) Table III. Preparation of hardened flame retardant epoxy resin No. Flame retardant epoxy resin-c (g) Diaminodiphenylmethane (g) Compound B (g) Compound E (g) 0 Hardened flame retardant resin-1 20 3 0 Hardened flame retardant resin-2 20 2 2 0 Hardened flame retardant resin-3 20 2 1 1 Hardened flame retardant resin-4 20 2 0 2 Hardened flame retardant resin · 5 20 0 4 0 Hardened and difficult to show fat- " βΐ 20 0 0 4 Hardened and flame-retardant resin-7 C20 0 2 2 Example 12 (Synthesis of flame-retardant polymer-epoxy polymer) Compound A of Example 1 After mixing with a commercial bisphenol-A epoxy resin (Changchun Artificial Resin Factory Co., Ltd., code BE188) in different proportions (as shown in Table 4), 1000 ppm of triphenylphosphine and After methylethyl ketone is reacted at 140 ° C for 3 hours, a flame-resistant epoxy polymer can be obtained. Table 4. Preparation of flame-resistant epoxy polymer No. Compound A (A) BE188 (g) Flame-resistant epoxy polymer-1 10 50 Flame-resistant epoxy polymer-2 10 40 Flame-resistant epoxy polymer-3 10 30 Flame-retardant epoxy polymer-4 10 20 Example Thirteen (synthesis of flame-retardant polymer-polyamidoamine) 6 g of the compound B of the above-mentioned Example 2 and 1.6 g of m-benzene 17 572954 (2003 3 (Amended) Η Dicarboxylic acid is mixed together, add 0.8 g of calcium chloride, 32 ml of triphenylphosphite, 32 ml of pyridine, and 30 ml of N-shen N-methylpyrollidone (NMP) is reacted at 100 ° C for 4 hours. After cooling to room temperature, it is precipitated with methanol. The precipitate is collected, washed with hot water and methanol, and dried under vacuum at 150 ° C for 24 hours. Polyphosphonium compounds containing phosphorus can be obtained. Brief Description of the Figures Figure 1 is an FTIR spectrum chart of compound A & B synthesized in Examples 1 and 2 of the present invention. Figures 2a and 2b are 1H NMR spectra of compounds A and B synthesized in Examples 1 and 2 of the present invention, respectively. 3 is a 31P NMR spectrum chart of compounds a and B synthesized in Examples 1 and 2 of the present invention. 18

Claims (1)

572954 Amendment and Replacement ^ > Year and Month 丨 g Yue (Amended in March 2003) 1. A phosphorus-containing compound having the following chemical formula (I) ⑴ where 11 and 118 are independently H or Ci-C% alkyl; y is _011 or X is Q or R 10 where R1-R4 has the same definition as above; Q is Η, -N〇2, -NH2, -OH, -CH3, -CH0, -C00H ο -NR? \ 9? \ F2CHCH2j -OCH2CHCH2, -C-OCH2CHCH2, -N-CH2CHCH2, or ό ;. Is independently H, or 0-C4 alkyl; and o-o-c-A is -0-, -C-ο-, &, mono, -CH2-, or -C (CH3) 2-. 2. The compound according to item 1 of the scope of patent application, wherein X is Q in formula (I). 3. The compound according to item 1 of the scope of patent application, wherein X in the formula (I) is A 19 572954 (Amended in March 2003) 4. The compound described in item 3 of the patent application, where A is 5. The compound described in item 3 of the patent application, where A is 〇 II —〇—〇— 〇6. The compound according to item 3 of the scope of patent application, wherein A is -0-C-II 〇 7. The compound according to any one of scopes 2 to 6 of patent application scope, wherein, formula (1 ) 1-1 ^ is H, and Y is 8. The compound according to any one of claims 2 to 6 of the scope of patent application, wherein Q in formula (I) is -NH2. 9. The compound according to any one of items 2 to 6 of the scope of patent application, wherein 0 in formula (I) is _011. 10. The compound 20 572954 (revised in March 2003) according to any one of the items 2 to 6 of the scope of patent application, wherein Q in the formula is -OCH 2CHCH2 11. A flame retardant resin composition, The compound (I) described in item 1 of the scope of patent application as a flame retardant is contained. 12. A hardened flame retardant resin prepared by hardening the flame retardant resin composition described in item 11 of the patent application scope. 13. A flame-retardant polymer, which is obtained by polymerizing the compound (I) described in item 1 of the patent application as a monomer, or the phosphorus-containing compound (I) described in item 1 of the patent application ) Prepared by polymerizing a monomer with other monomers. twenty one