JPS6216207B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a flame retardant for making synthetic resin flame retardant, and more specifically, the present invention relates to a flame retardant for making synthetic resin flame retardant. (In the formula, X represents a halogen atom, m is 1 to 2,
n is an integer of 1 to 2. R ₁ represents an alkylidene group or an alkylene group having 1 to 4 carbon atoms. ) Halogenated dihydroxy compound (A)
and general formula (In the formula, X represents a halogen atom, l is an integer of 1 to 3, and _R2 represents H or an alkyl group having 1 to 4 carbon atoms.) A halogenated monoglycidyl ether (B) represented by The general formula (In the formula, X represents a halogen atom, o is 0 to 2,
p is an integer from 0 to 2. R ₃ is an alkylidene group or alkylene group having 1 to 4 carbon atoms. Q indicates 0-4. This invention relates to a flame retardant for synthetic resins having a molecular weight of 900 to 2,900, which is obtained by further reacting the diglycidyl ether compound (C) represented by (C) at a ratio of 0.1 to 1.0 mol of C to 1 mol of A. The purpose of this study is that the thermally stable flame retardants found in conventional flame retardants for synthetic resins have a small flame retardant effect, and the flame retardants that have a large flame retardant effect are thermally unstable. Many flame retardants, even if they are thermally stable, color the product or give it a bad odor.However, it is thermally stable and has excellent heat resistance, has no bad odor or coloration, and has flame retardant effects with just a small amount of addition. The major goal lies in the development of superior flame retardants for synthetic resins. Due to the remarkable development of petrochemistry, the production of synthetic resins derived from this has become enormous.Synthetic resins have been used in a wide range of areas by skillfully utilizing their excellent properties, and will continue to be used in a wide range of areas. Although their uses are becoming more widespread, strict regulations have been put in place due to the disadvantage that synthetic resins are easily flammable. The UL standard described herein is one of them. UL is a public safety organization called Underwriters Laboratories, Inc., and its No. 94 is the Flammability Standard for Plastic Materials (UL-94). The flame retardant evaluation stipulated in the standard is rated in the order of 94V-0, 94V-1, 94V-2, and 94HB depending on the degree of flame retardancy. The test method is to prepare 5 test pieces of a specified size, clamp the upper end of the test piece, set the test piece vertically, apply a burner flame of a specified length to the lower end for 10 seconds, and then perform the test. Measure the burning time of the pieces. Immediately after extinguishing the fire, apply the flame again for 10 seconds and measure the burning time. Let T be the total burning time of the test of 5 pieces, and let M be the maximum value. If T is 50 seconds or less and M is 10 seconds or less, the flame will not burn to the clamp, and the flaming molten material will fall and cause the cotton below the specified level to burn. If it does not ignite, it is UL94V-0. If T is 250 seconds or less, M is 30 seconds or less, and the other conditions are the same as V-0, it is UL94V-1. If a flaming molten material falls and ignites cotton under the same conditions as T and M as V-1, it is UL94V-2. Items that fail V-0, V-1, and V-2 are subjected to a horizontal combustion test, and if the fire is extinguished before the designated marking line, they will be evaluated as UL-94HB. As a trend in the world, requirements for flame retardancy are becoming stricter year by year, and at present most of the products are UL94V-
I've come to demand 0. On the other hand, flame retardant synthetic resins are made using halogen compounds, phosphorus compounds,
This has been achieved through the synergistic effect of a combination of nitrogen compounds or metal oxides, etc. Adding flame retardants to synthetic resins improves flame retardancy, but on the other hand it impairs various properties such as heat resistance, mechanical properties, and electrical properties. It was inevitable that the characteristics would deteriorate. Therefore, there has been a strong demand for flame retardancy that minimizes the deterioration of these physical properties. Conventionally, various improvements have been made to halogen compounds, which have the greatest flame retardant effect and are essential as flame retardant components. For example, Tokkosho
In Publication No. 47-44537, the formula (In the formula, R is H or a lower alkyl group) In JP-A-53-56290, the compound represented by the formula In JP-A-56-118414, the compound represented by the formula (In the formula, Z is -CH ₂ OH or halogen, X is halogen, R is H or a hydrocarbon group, Y and Y' are H
Alternatively, compounds represented by CH ₃ , T.T' is -CH ₂ CH ₂ O-, etc.) have been proposed. All of these flame-retardant compounds had a large number of aromatic rings and were therefore quite thermally stable.
However, although all of these flame-retardant compounds showed effective flame retardancy for certain types of synthetic resins, their flame-retardant effects were small for other synthetic resins.
It was unsatisfactory. In other words, a self-extinguishing synthetic resin such as polyester resin with 20% by weight of these flame-retardant compounds and 5% by weight of antimony trioxide exhibited flame retardancy of UL-94/V-0. However, with flammable synthetic resins such as polystyrene resin, only UL-94/V-2 could be achieved. In order to make polystyrene resin UL-94/V-0, it is necessary to add a larger amount of flame retardant compounds, but on the other hand, there is a risk that other properties, such as mechanical properties, will be significantly reduced. The present inventors discovered that the synthetic resin has excellent mechanical properties,
We focused on the fact that, despite having electrical properties, heat resistance, water resistance, chemical resistance, moldability, processability, etc., the development of flame retardants was significantly hindered due to the lack of excellent flame retardants. The present invention was completed as a result of intensive research into ways to eliminate the drawbacks of flame retardants. In other words, the advantage of the present invention is that compared to conventionally known flame retardants, the obtained flame retardant has a high halogen content because it uses a large amount of halogen compounds as raw materials, so it can be added in small amounts to synthetic resins that are desired to be flame retardant. It is possible to achieve flame retardancy by adding it alone, and since the amount added is small, there is almost no effect on other properties such as deterioration of mechanical properties. Another advantage of the present invention is that the new flame retardant of the present invention contains many aromatic rings in its molecular structure, so it has a high thermal decomposition temperature and is thermally stable, even when added to synthetic resins. It must not have any adverse effects such as deterioration of heat resistance. Furthermore, because the decomposition temperature is high, there is almost no discoloration or unusual odor. The present invention is based on the general formula (In the formula, X represents a halogen atom, m is 1 to 2,
n is an integer of 1 to 2. R ₁ represents an alkylidene group or an alkylene group having 1 to 4 carbon atoms. ) Halogenated dihydroxy compound (A)
and general formula (In the formula, X represents a halogen atom, l is an integer of 1 to 3, and _R2 represents H or an alkyl group having 1 to 4 carbon atoms.) A halogenated monoglycidyl ether (B) represented by The general formula (In the formula, X represents a halogen atom, o is 0 to 2,
p is an integer from 0 to 2. R ₃ is an alkylidene group or alkylene group having 1 to 4 carbon atoms. Q indicates 0-4. ) Diglycidyl ether compound (C)
This relates to a flame retardant for synthetic resins having a molecular weight of 900 to 2,900, which is further reacted with C0.1 to 1.0 mole per mole of A. The flame retardant according to the present invention will be specifically shown in the experimental examples described below, but ideally it can be represented by the following general formula. i.e. (In the formula, X represents a halogen atom, l is 1 to 3,
m is an integer of 1 to 2, and n is an integer of 1 to 2. R ₁ is carbon number 1
~4 alkylidene group or alkylene group, and _R2 represents H or an alkyl group having 1 to 4 carbon atoms. ) In the present invention, the ratio of reaction between the halogenated dihydroxy compound and the halogenated monoglycidyl ether is ideally 1 mol of the former to 2 mol of the latter, and in this case, the flame retardant effect is the greatest and the heat resistance is also improved. It was expensive. This constitutes the molecular composition of the former
This is thought to be because the OH groups were completely processed and thermal stability increased. However, in reality, even if 2 moles or more than 2 moles of halogenated monoglycidyl ether are reacted with 1 mole of the halogenated dihydroxy compound, a considerable amount of a compound in which 1 mole of the latter is added to 1 mole of the former is produced. It was not possible to completely treat the former OH group. Then, a small amount of diglycidyl ether compound was further added and reacted to completely treat the OH groups. In the present invention, the reaction charge ratio of halogenated monoglycidyl ether to 1 mol of halogenated dihydroxy compound is preferably 2 to 2.5 mol,
Practically speaking, even those prepared and reacted at a ratio of 1 to 3 moles were considerably superior to conventionally known flame retardants. When it was less than 1 mole, thermal stability was poor, causing bad odor and discoloration, and when it was more than 3 moles, flame resistance decreased. Further, the reaction charge ratio of diglycidyl ether to be further reacted with this is preferably 0.3 to 0.7 mol, but may be 0.1 to 1.0 mol for practical purposes.
If it is less than 0.1 mol, the amount necessary to treat OH groups will be insufficient, and if it is more than 1.0 mol, there is a risk of gelation. As a method for reacting a dihydroxy compound and glycidyl ether in the present invention,
48-6639, this method involves reacting 2 moles of low molecular weight diglycidyl ether with 1 mole of a dihydroxy compound to produce high molecular weight diglycidyl ether, and the product is further reacted. It has a reactive group that can In the method of the present invention, monoglycidyl ether rather than diglycidyl ether is reacted with 1 mole of dihydroxy compound to produce a low molecular weight compound, and if ideally reacted, this compound no longer has a reactive group. . Of course, in the detailed description of the invention in Japanese Patent Publication No. 48-6639, it is stated that monoglycidyl ether may be used as the glycidyl ether, but its purpose is as an auxiliary raw material as a reaction terminator or reaction regulator. Even in the examples, the amount added was only 5% or less of the total. This is because if a large amount is used, the purpose of increasing the molecular weight cannot be achieved, and the invention described in Japanese Patent Publication No. 48-6639 cannot be achieved with monoglycidyl ether alone, as in the present invention. A method for reacting a dihydroxy compound, a monoglycidyl ether, and a diglycidyl ether compound in the present invention is disclosed in JP-A-53-42298. A flame-retardant resin composition is created by mixing and reacting functional epoxy resins at once. Although this known document does not explain the role and effect of each ingredient, in the synthesis example, if the amount of monofunctional epoxy resin added is large, the softening point of the product will be low, and if it is small, the softening point will be high. Therefore, it is thought that the monofunctional epoxy resin is used as a reaction regulator or a reaction terminator, and in this sense, it is very similar to Japanese Patent Publication No. 48-6639.
In addition, in this known document, each ingredient is mixed and reacted all at once, but the product produced by this method is a reaction in which monofunctional and difunctional epoxy resins randomly react with difunctional phenols, resulting in a combination of difunctional and difunctional epoxy resins. This creates a very dangerous product, such as high molecular weight due to epoxy resin and residual unreacted OH groups of difunctional phenols. In the method of reacting a dihydroxy compound, a monoglycidyl ether, and a diglycidyl ether compound in the present invention, a low molecular weight compound of a dihydroxy compound and a monoglycidyl ether is first prepared, and then a diglycidyl ether compound is added to the low molecular weight compound. This is a method in which the unreacted OH groups of the dihydroxy compound of the present invention are added and reacted in order to further improve the thermal stability of the flame retardant of the present invention, to prevent bad odor and discoloration, and to completely eliminate it. One of the important points is the order of this reaction. Further, in the present invention, monoglycidyl ether is one of the main raw materials, and rather, the diglycidyl ether compound is an auxiliary raw material. General formula in the present invention Examples of halogenated dihydroxy compounds represented by include bis(4-hydroxy-2-
Bromphenyl)methane, bis(4-hydroxy-3-bromphenyl)methane, bis(4-hydroxy-3-chlorophenyl)methane, bis(4-hydroxy-3-chlorophenyl)methane,
-hydroxy-3,5-dibromphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, 1,1-bis(4-hydroxy-3-chlorophenyl)ethane, 1,1-bis(4 -Hydroxy-3-bromphenyl)ethane, 1,1-bis(4-hydroxy-3,5-dichlorophenyl)ethane, 1,1-bis(4-hydroxy-3,5-dibromphenyl)ethane,
1,2-bis(4-hydroxy-3-chlorophenyl)ethane, 1,2-bis(4-hydroxy-
3-bromphenyl)ethane, 1,2-bis(4
-Hydroxy-3,5-dichlorophenyl)ethane, 1,2-bis(4-hydroxy-3,5-dibromphenyl)ethane, 2,2-bis(4-hydroxy-2-bromphenyl)propane, 2,
2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-
3-bromphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)
Propane, 2,2-bis(4-hydroxy-3,
5-dibromphenyl)propane, 1,1-bis(4-hydroxy-3-chlorophenyl)butane, 1,1-bis(4-hydroxy-3-bromphenyl)butane, 1,1-bis(4-hydroxy-3, 5-dichlorophenyl)butane, 1,1
-bis(4-hydroxy-3,5-dibromphenyl)butane and the like. General formula in the present invention Examples of halogenated monoglycidyl ethers represented by include monochlorophenyl monoglycidyl ether, dichlorophenyl monoglycidyl ether, trichlorophenyl monoglycidyl ether, monobromphenyl monoglycidyl ether, dibromphenyl monoglycidyl ether, Tribromphenyl monoglycidyl ether, monochlorocresyl monoglycidyl ether, dichlorocresyl monoglycidyl ether,
Examples include monobromocresyl monoglycidyl ether and dibromocresyl monoglycidyl ether. General formula in the present invention Examples of diglycidyl ether compounds represented by include bisphenol A diglycidyl ether or bisphenol A type epoxy resin with a molecular weight of 1000 or less, bisphenol F diglycidyl ether or bisphenol F type epoxy resin with a molecular weight of 1000 or less, halogen Examples include halogenated bisphenol A diglycidyl ether or halogenated bisphenol A type epoxy resin with a molecular weight of 1500 or less, halogenated bisphenol F diglycidyl ether or halogenated bisphenol F type epoxy resin with a molecular weight of 1500 or less. The method of reacting a halogenated dihydroxy compound, a halogenated monoglycidyl ether, and a diglycidyl ether compound in the present invention is to charge the halogenated dihydroxy compound and the halogenated monoglycidyl ether into a reactor, then add a catalyst, and then The mixture is reacted by stirring at a temperature of 120° C. for 1 to 8 hours, then the diglycidyl ether compound is added, and the mixture is further stirred and reacted at the same temperature for 1 to 4 hours to produce the product. Examples of catalysts include amine-based ones, such as ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, triethanolamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, benzyldimethylamine, tris(dimethylaminomethyl)phenol, and metaphenylenediamine. ,
Diaminodiphenylmethane, diaminodiphenyl sulfone, dicyandiamide, boron trifluoride,
Monoethylamine, menthanediamine, xylene diamine, ethylmethylimidazole, 1,8-
Diazabicyclo(5,4,0) undecene
7 etc. Synthetic resins to which the flame retardant of the present invention can be applied include polyethylene resin, polypropylene resin, polystyrene resin, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, polyvinyl chloride resin, and ethylene-vinyl acetate. Copolymers, polymethacrylic acid resins, polyvinyl acetate resins, polybutene resins, polyamide resins, polyacetal resins, polycarbonate resins, saturated polyester resins, phenolic resins, epoxy resins, polyurethane resins, alkyd resins, unsaturated polyester resins, melamine resins , synthetic resins such as urea resin, diallyl phthalate resin, and polybutadiene resin, but also acrylonitrile and natural resins such as cellulose acetate.
It can also be used as a flame retardant for elastic bodies such as butadiene rubber. The flame retardant of the present invention has a remarkable flame retardant effect, and 20% by weight of the flame retardant of the present invention is added to a self-extinguishing synthetic resin such as polyester resin or a flammable synthetic resin such as polystyrene resin. All products containing 5% by weight of antimony oxide exhibit flame retardancy of UL-94/V-0.
Furthermore, there was no decrease in other properties such as mechanical properties. The method of mixing the flame retardant according to the present invention and synthetic resins is, for example, before molding, the flame retardant according to the present invention is mixed into synthetic resin powder by a powder mixing method, a roll kneading method, a Banbury kneading method, an extrusion kneading method, etc. Either method may be used, such as dry mixing, or wet mixing, in which a solution of the flame retardant of the present invention dissolved in a solvent is mixed with a melt or solution of the synthetic resin. The flame retardant may be contained in the surface of the molded article by immersing the molded article in a solution dissolved in a solvent or applying the solution to the molded article. When using the flame retardant of the present invention, other known flame retardants such as nitrogen compounds, phosphorus compounds, and halogen compounds may be used in combination, and if necessary, antimony oxide, molybdenum oxide, tin oxide, etc. Compounds conventionally used as flame retardant aids, such as, can also be used in combination. In addition, the resin composition using the flame retardant of the present invention may further contain known plasticizers, curing agents, curing accelerators, surface treatment agents, surfactants, protective colloids, heat stabilizers, and light stabilizers. , colorants, fillers, lubricants, and other additives can be added. The present invention will be explained below using experimental examples. Experimental Example 1 1.0 mol of 2,2-bis(4-hydroxy-3,5-dibromphenyl)propane and 7544 g of 1,8-diaza-bicyclo-(5,4,0)undecene as a catalyst were placed in a stirrer and a cooling tube. , a thermometer, and a dropping funnel into a two-four-necked flask;
200 ml of toluene was added and stirred to create a suspension. Next, 2.2 mol of dibromocresyl monoglycidyl ether was dissolved in 200 ml of toluene,
Addition was made slowly using a dropping funnel at 40° C. over a period of 1 hour. After the dropwise addition was completed, stirring was continued while gradually raising the temperature over 1 hour until it reached 100°C, and then the reaction was further carried out at 100°C for 3 hours (the average molecular weight of the intermediate product was 1050). . Next, while maintaining the temperature at 100°C, a solution of 0.6 mol of bisphenol A diglycidyl ether dissolved in 200 ml of toluene was gradually added using a dropping funnel over 30 minutes, and the reaction was further carried out at the same temperature for 2 hours. After the reaction, the viscosity (20
1650 g of a brown transparent flame retardant solution with an average molecular weight of 1200 of the final product were obtained. A composition was prepared by blending various synthetic resins as shown in Table 1 with 20% by weight of the flame retardant of the present invention and various flame retardants as shown in Table 1 and 5% by weight of antimony trioxide, and after molding. When tested, the results shown in Table 1 were obtained.

[Table] As shown in Table 1, the flame retardant of the present invention is an excellent flame retardant that can improve the flame resistance of many types of synthetic resins to UL-94/V-0. Furthermore, the flame retardant of the present invention had excellent thermal stability, and was free from discoloration and off-odor. On the other hand, flame retardant A had an excellent flame retardant effect, but had poor thermal stability, caused discoloration, and emitted a strange odor. Further, flame retardant B can be expected to have a flame retardant effect depending on the resin to which it is applied, but it was not very effective for many resins. Also, flame retardant C
Although it had excellent thermal stability and was free from discoloration and strange odor, flame retardant effects could not be expected depending on the resin to which it was applied. Experimental Example 2 The reaction was carried out in the same manner as in Experimental Example 1 except that 2.2 moles of dibromucresyl monoglycidyl ether was changed to 0.5 to 3.5 moles of dibromphenyl monoglycidyl ether, and the combination with the synthetic resin and the tests were also carried out. The same procedure was carried out, and the results shown in Table 2 were obtained.

【table】

[Table] As shown in Table 2, when the amount of dibromphenyl monoglycidyl ether added to 2,2-bis(4-hydroxy-3,5-dibromphenyl)propane is small, thermal stability is poor and discoloration occurs. and emit a strange odor. On the other hand, if the amount of preparation is large, the range of application of the synthetic resin that can provide flame resistance of UL-94/V-0 is limited. The preferred reaction charge ratio in the present invention is 2,2-bis(4-hydroxy-3,5-dibromphenyl)propane 1
The amount of dibromphenyl monoglycidyl ether is 1.5 to 2.5 mol, but in practice it is 1.0 to 3.0 mol.
Can also be used in moles. Experimental Example 3 In Experimental Example 1, except that 0.6 mol of bisphenol A diglycidyl ether was changed to 0.1 to 2.0 mol of bisphenol F diglycidyl ether, the reaction was carried out in the same manner, and the combination with the synthetic resin and the test were also carried out. The same procedure was carried out, and the results shown in Table 3 were obtained.

【table】

[Table] As shown in Table 3, the amount of bisphenol F diglycidyl ether charged to the reaction product of 2,2-bis(4-hydroxy-3,5-dibromphenyl)propane and dibromocresyl monoglycidyl ether If the reaction product is small, it is impossible to completely eliminate the OH groups remaining in the reaction product, and the thermal stability is less than 250°C. If you increase the amount of bisphenol F diglycidyl ether,
Although the OH group is eliminated and the thermal stability is improved to 250° C. or higher, the flame resistance is slightly lowered due to the decrease in the bromine content in the total product due to the increase in bisphenol F diglycidyl ether. If the amount of bisphenol F diglycidyl ether charged is further increased, it will gel during the reaction. The preferred reaction charge ratio in the present invention is 2,2-bis(4-hydroxy-3,5-dibromphenyl)propane 1
The amount of bisphenol F diglycidyl ether is 0.3 to 0.7 mol per mole, but 0.1 to 1.0 mol can also be used in practice. As is clear from the above experimental examples, the flame retardant for synthetic resins of the present invention not only imparts excellent flame resistance to a wide variety of synthetic resins, but is also thermally stable and has no fear of discoloration or strange odors. It is a flame retardant.

Claims (1)

[Claims] 1. General formula (In the formula, X represents a halogen atom, m is 1 to 2,
n is an integer of 1 to 2. R ₁ represents an alkylidene group or an alkylene group having 1 to 4 carbon atoms. ) Halogenated dihydroxy compound (A)
and general formula (In the formula, X represents a halogen atom, l is an integer of 1 to 3, and _R2 represents H or an alkyl group having 1 to 4 carbon atoms.) A halogenated monoglycidyl ether (B) represented by The general formula (In the formula, X represents a halogen atom, o is 0 to 2,
p is an integer from 0 to 2. R ₃ is an alkylidene group or alkylene group having 1 to 4 carbon atoms. Q indicates 0-4. ) Diglycidyl ether compound (C)
A flame retardant for synthetic resins with a molecular weight of 900 to 2,900, which is further reacted with C at a ratio of 0.1 to 1.0 mole to 1 mole of A.