JPS5953523A - Flame-retardant for synthetic resin - Google Patents

Abstract

PURPOSE:To obtain titled flame-retardant highly effective with only a small amount, thermally stable, with outstanding heat resistance, free from any odor and coloring, by reaction between a halogenated dihydroxyl compound and halogenated monoglycidyl ether. CONSTITUTION:The objective flame-retardant with a molecular weight of 700- 1,400, pref. of formula III, can be obtained by reaction between (A) a halogenated dihydroxyl compound of formula I (X is halogen; m and n are each 1-2; R1 is 1-4C alkylidene or alkylene) [e.g., bis(4-hydroxy-2-bromophenyl)methane] and (B) a halogenated monoglycidyl ether of formula II(l is 1-3; R2 is H 1-4C alkyl) (e.g., monochloro-phenyl monoglycidyl ether) in a molar ratio (A)/(B) of 1/1-3.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame retardant for making synthetic resin flame retardant.
For details, refer to the general formula (in the formula or a halogen atom, m is 1 to 2, n is 1 to
An integer of 2. 11, represents an alkylidene group or an alkylene group having 1 to 4 carbon atoms. ) A halogenated dihydroxy compound IA) represented by the general formula (where X represents a halogen atom and l is an integer of 1 to 3).

M: represents iH or an alkyl group having 1 to 4 carbon atoms. ) halogenated monoglycidyl ether (B
This invention relates to a flame retardant for synthetic resins having a molecular weight of 700 to 1,400, which is obtained by reacting B with ~3 moles per 1 mole 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. Although many flame retardants are thermally stable, they still color the product or give it a bad odor.However, it is thermally stable, has excellent heat resistance, has no odor or coloration, and has a flame retardant effect when added in small amounts. The goal lies in the development of highly 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 grow in the future. Although their use is 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 same standard is 94V-0, 94V-0, depending on the degree of flame retardancy.
1,! ) 4V-2, 94HB.

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, and apply a burner flame of a specified length to the lower end for 10 seconds. Measure the burning time. 10 again immediately after extinguishing the fire.
Apply the flame for 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, then T
is 50 seconds or less, M is 10 seconds or less, and if the clamp does not burn and the flaming molten material falls and does not ignite the specified cotton, UL94V-O oT is 250 seconds or more and F%M is 30 seconds or less. , other conditions are UL94V if the same conditions as V-0 are met.
-1 If oT and M are the same as v-1, if a molten material with flame falls and ignites cotton, it will be UL94V-2oV-Q.
, V-iV-2, a horizontal combustion test is conducted and the fire is evaluated as UL-94HB if the fire is extinguished before the specified marked line. As a trend in the world, requirements for flame retardancy are becoming stricter every year, and at present most of the products are UL94V-0.
has come to demand. In contrast, synthetic resins have been made flame retardant through the synergistic effect of combinations of halogen compounds, phosphorus compounds, nitrogen compounds, or metal oxides, but flame retardants can be added to synthetic resins to improve their flame resistance. However, on the contrary, various properties such as heat resistance, mechanical properties, and electrical properties inevitably deteriorated. Therefore,
There has been a strong demand for flame retardancy that minimizes the deterioration of these physical properties.

Conventionally, various efforts have been made to improve halogen compounds, which have the greatest flame retardant effect and are essential as flame retardant components.

For example, (Fb Publication No. 47-44537 Publication +1 & ″
c is a compound represented by the formula (wherein R is H or a lower alkyl method) and 14F Kaisho 53-5 (3
In Publication No. 290, the formula LF 'F'; t ka, i fC 'l
'? f l. Ii1:lfi 5(i-1 1.8
414 ->y・In the medical newsletter, Te( hard medium Z id. -OJ{20H-i fi i,i
: Har-1, X is a halogen, R is H or a hydrocarbon group, Y, 'i'& i H mfc. i:D[I
3. For 'r' and 'Σ', a compound represented by an a such as -OH20H20- has been proposed.

All of these flame-retardant compounds have a large number of aromatic rings and are therefore quite thermally stable. However, the flame retardant effect was unsatisfactory compared to other synthetic resins. In other words, when 20% by weight of these compounds and 5% of antimony trioxide are added to a self-sublimating synthetic resin such as polyester resin, d1l-9
4V-(.1), but combustible synthetic resins such as polystyrene resins cannot achieve UL-94V-2L or JL-94V-O.
K -1' b K rt-. Although it is necessary to add a flame retardant compound in an amount of L Ni, there is a risk that other properties, such as mechanical properties, will be significantly reduced.

The researchers found that synthetic resin has excellent mechanical and electrical properties.
Although they have heat resistance, water resistance, chemical resistance, workability, etc., their development is significantly hindered due to the lack of excellent flame retardant properties.We focused on the various drawbacks of conventionally known flame retardants. As a result of intensive research on how to solve this problem, we have completed the present invention.

That is, 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, and therefore, it is necessary to add a small amount to the flame retardant synthetic tree. It can be made flame retardant just by adding it, 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. There should be no adverse effects of stroking that reduce heat resistance. Also, because the decomposition temperature is high, there is almost no discoloration or bad odor.

The present invention is based on the general formula (wherein X represents a halogen atom, m is 1 to 2, and n is 1 to
An integer of 2. R1 represents an alkylidene group or an alkylene group having 1 to 4 carbon atoms. ) A halogenated dihydroxy compound (A) represented by the general formula (wherein, X represents a halogen atom, and l is an integer of 1 to 3. R
2 represents H or an alkyl group having 1 to 4 carbon atoms. ) halogenated monoglycidyl ether (B
) in a ratio of 1 to 3 moles of B to 1 mole of A, and the flame retardant has a molecular weight of 700 to 1,400.

The flame retardant according to the present invention will be specifically shown in the experimental examples described below, but it can be conceptually represented by the following general formula.

That is, (in the formula, X represents a halogen atom, l is 1 to 3, m is 1
~2, n is an integer from 1 to 2. Rl represents an alkylidene group or alkylene group having 1 to 4 carbon atoms, and R2 represents H or an alkyl group having 1 to 4 carbon atoms. ) The reaction ratio of the halogenated dihydroxy compound and the halogenated monoglycidyl ether in the present invention is ideally 1 mol of the former to 2 mol of the latter, and this case provides the greatest flame retardant effect and high heat resistance. Ta. This is the molecular structure of the former, OH
This is thought to be due to the fact that the base was completely processed and the thermal stability was increased. However, in practical terms, even those prepared and reacted at a ratio of 1 to 3 moles of the latter to 1 mole of the former were considerably superior to conventionally known flame retardants. 1
If the amount is less than mol, the thermal stability will be poor, and there will be strange odor and discoloration.
When the amount was more than 3 moles, flame resistance decreased.

The method of reacting the dihydroxy compound and glycidyl ether in the present invention is described in Japanese Patent Publication No. 18-6.
639, this method involves adding 2 low molecular weight diglycidyl ethers to 1 mole of dihydroxy compound.
The molar reaction produces a high molecular weight diglycidyl ether, and the product has reactive groups that can be further reacted. The method according to the invention is not a diglycidyl ether, but a low molecular weight compound obtained by reacting 2 moles of monoglycidyl ether with 1 mole of a dihydroxy compound, and this compound no longer has reactive groups.

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 is achieved, and the invention described in Japanese Patent Publication No. 48-6639 cannot be achieved with monoglycidyl ether alone, as in the present invention.

Examples of the halogenated dihydroxy compound represented by the general formula in the present invention include bis(4-hydroxy-2-bromphenyl)methane, bis(4-hydroxy-3-bromphenyl)methane, bis(4-hydroxy-3-bromphenyl)methane, and bis(4-hydroxy-3-bromphenyl)methane. -chlorophenyl)methane, bis(4-hydroxy-3,5-dibromphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, 1,1-bis(4-hydroxy-3-chlorophenyl)ethane , 1,l-bis(4-
Hydroxy-3-bromphenyl)ethane, 1. l-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-dichloropheny)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,l. -bis(4-hydroxy-3,5-dibromphenyl)butane and the like.

Examples of the halogenated monoglycidyl ether represented by the general formula in the present invention include monochlorophenyl monoglycidyl ether, dichlorophenyl monoglycidyl ether, trichlorophenyl monoglycidyl ether, monobromphenyl monoglycidyl ether, dibromphenyl monoglycidyl ether, Examples include tribromphenyl monoglycidyl ether, monochlorocresyl monoglycidyl ether, dichlorocresyl monoglycidyl ether, monobromocresyl monoglycidyl ether, dibromocresyl monoglycidyl ether, and the like.

In the method of reacting a halogenated dihydroxy compound and a halogenated monoglycidyl ether in the present invention, after charging both into a reactor, a catalyst is added, and the reaction temperature is 40°C to 120°C.
This is carried out by stirring at a temperature of 1 to 8 hours at a temperature of 0.degree. C., but this is not particularly limited. Examples of catalysts include amine-based catalysts, such as ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, triethanolamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, benzyldimethylamine, and tris(dimethylaminomethyl).
Phenol, metaphenylenediamine, dizminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, boron trifluoride/monoethylamine, methanediamine, xylenediamine, ethylmethylimidazole, 1,8-diaza-bicyclo-(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/vitadiene copolymer, styrene/butadiene/acrylonitrile copolymer, polyvinyl chloride resin, ethylene/vinyl acetate copolymer, polymethacrylic acid resin, polyvinyl acetate resin, polybutene Synthetic resins such as resins, polyamide resins, polyacetal resins, polycarbonate resins, saturated polyester resins, phenolic resins, epoxy resins, polyurethane resins, alkyd resins, unsaturated polyester resins, melamine resins, urea resins, diallyl phthalate resins, and polybutadiene resins. However, it can also be used as a flame retardant for natural resins such as cellulose acetate and facultative materials such as acrylonitrile-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 are UL-94.
It exhibited flame retardancy of V-0, and there was no deterioration in other properties such as mechanical properties.

The method of mixing the flame retardant of the present invention and synthetic resins is, for example, before molding, the flame retardant of 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 the 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,
For example, nitrogen-based compounds, phosphorus-based compounds, and halogen-based compounds may be used in combination, and if necessary, compounds conventionally used as flame retardant aids such as antimony oxide, molybdenum oxide, and tin oxide may be used in combination. You can also do that. Also,
The resin composition using the flame retardant of the present invention may further include known plasticizers, curing agents, curing accelerators, surface treatment agents, surfactants, protective colloids, heat stabilizers, light stabilizers,
Additives such as colorants, fillers, lubricants, etc. 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 1,8 as a catalyst
-Diaza-bicyclo-(5,4rO)undecene-75.44g was placed in a 2L four-necked flask equipped with a stirrer, condenser, thermometer, and dropping funnel, and 200mg of toluene was added and stirred. A suspension was made.

Next, add 200 ml of 2.2 moles of dibromucresyl monoglycidyl ether! was dissolved in toluene and added slowly using a dropping funnel at 40° C. over a period of 1 hour. After dropping, continue stirring while gradually raising the temperature over 1 hour until it reaches 100°C, then continue stirring at 100°C for 3 more hours.
A time reaction was performed. After the reaction was completed, the boiling process was repeated 5 times with 500 ml of boiling water to obtain 1,100 g of a brown transparent flame retardant solution with a viscosity (20°C) of 16 poise and an average molecular weight of 1,050.
I got it.

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.

Ai2,2-bis(4-hydroxy-3,5-dibromphenyl)propane.

B: dibromocresyl monoglycidyl ether.

C: Tetrabrom biphenyl ether.

Flame resistance: According to UL-94 (V-Q is the best).

Thermal stability...Those that do not decompose when heated at 230°C are ○, and those that decompose are x.

Discoloration/Odor: Presence of discoloration and odor due to decomposition gas.

As shown in Table 1, the flame retardant of the present invention is an excellent flame retardant that can improve the flame resistance of multi-glaze synthetic resins to UL-94V-Q. Furthermore, the flame retardant of the present invention had excellent thermal stability, and was free from discoloration and unusual 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 retardants B and C can be expected to have a flame retardant effect depending on the resin to which they are applied, but they were not very effective for many resins.

As described above, the flame retardant of the present invention is an excellent flame retardant that can be applied to many types of synthetic resins.

Experimental Example 2 The reaction was carried out in the same manner as in Experimental Example 1 except that 2.2 mol of dibromocresyl monoglycidyl ether was changed to 0.5 to 3.5 mol of dibromphenyl monoglycidyl ether, The blending with the synthetic resin and the tests were carried out in exactly the same manner, and the results shown in Table 2 were obtained.

As shown in Table 2, 2,2-bis(4-hydroxy-3
, 5-dibromphenyl) propane, when the amount of dibromphenyl monoglycidyl ether charged is small,
(poor thermal stability, causing discoloration and emitting a strange odor).

On the other hand, when the amount of preparation is large, the range of application of the synthetic resin that can provide flame resistance of UL-94/V-Q is limited. The preferred reaction charge ratio in the present invention is 2,2-bis(
The amount of dibromphenyl monoglycidyl ether is 1.5 to 2.5 mol per 1 mol of 4-hydroxy-3,5-dibromphenyl)propane, but in practice it is 1.0 to 3.
It can be used even at 0 mol.

As is clear from the above series of experiments, the flame retardant for synthetic resins of the present invention not only imparts excellent flame resistance to many types of synthetic resins, but is also thermally stable and free from the risk of discoloration and off-odor. Not an excellent flame retardant.

Claims (1)

[Claims] General formula (wherein X represents a halogen atom, m is 1 to 2, and n is 1 to 2)
An integer of 2. R1 represents an alkylidene group or an alkylene group having 1 to 4 carbon atoms. ) A halogenated dihydroxy compound (A) represented by the general formula (wherein or a halogen atom is shown, l is an integer of 1 to 3. R
2 represents H or an alkyl group having 1 to 4 carbon atoms. ) halogenated monoglycidyl ether (B
) is reacted with 1 mol of A at a ratio of 3 mol of Bl to 1 mol of molecules +17oo to 1400 for synthetic resins.