JPS5959695A - Novel halogenated benzulphosphonate and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel halogenated benzyl phosphonic acid esters, a preferred method of their preparation and their use in rendering fire-retardant flammable materials.

A number of organic compounds containing phosphorus and chlorine or bromine have been proposed in the past as non-functional fire protection additives for plastic materials, synthetic fibers and a variety of other flammable materials. However, only some of these compounds have been developed industrially.

The best known and oldest one is tris-cytochloroethyl) phosphate (coat-r2).
There is no doubt that 011207) 3.

Tris(chloro-isopropyl)phosphate P(J[
0C14(UH20A)C! I■3〕Also mention 3 I: I can do it.

Bis (in pure form or in partially combined form)
,2-chloroethyl)-,z-chloroethylphosphonate 1lcd420H2-PO(00H20H, (1)
Phosphonates such as 2 are also sold directly for the same purpose.

Although these compounds are readily available, they are too volatile and too fluid and therefore often suffer losses due to evaporation or migration during storage and provide insufficiently durable fire protection. In order to remove these drawbacks, tetrakis (, z-1
0 loethyl)-ethylene diphosphate (070H20
H2(J)z P (0) -00H2(!H20-
Compounds with higher molecular weights such as P (0) (OOH20H207)2 have also been proposed, but these compounds, like other similar compounds, either have too large a bath dissolution with water or are hydrolyzable. This property has a detrimental effect on the durability of the fire prevention effect.

Diphosphate (070H20H20) P (U)-
00H2-(CHz(jjlkh -0H20-P
(C)) (OOHzOH20A)2, 2,2-bis(chloromethyl) which does not have the above-mentioned defects
-／、、? - Derivatives of propanediol have also been proposed, but these compounds often pose problems in terms of their use; for example, when making polyurethane foams fireproof, these compounds have too high a viscosity. ,
According to Ponzo, it is said that Innoshima C'''
C-tris(,2,,?-dibromo=/-probil)phosphate PO(OOH20HBrOH2Br
) brominated phosphates such as 3 or tris(nopromo 3-chlorochoglobil) phosph: c, -
11,'O[(JOH(OH2Of!=) OH2B
Chlorobrominated phosphates such as [r]3 have also been proposed or used, but as it became known that these compounds have f7i-producing properties, their use had to be abandoned.The present invention The new halogenated benzyl phosphonates do not suffer from the drawbacks mentioned above and are distinguished in particular by their fire protection effect.

This compound has the following general formula (I): 0-OTI2-CHzX 0-OH20H2X (
In the formula, X represents a chlorine or bromine atom).

The average values m and n (which may be the same or different) of the substituents X in the aromatic nucleus are 0-.1.

The position of the chlorine or bromine atom on the benzene nucleus can be in the ortho, meta or ξ position. The present invention also includes mixtures of two or more phosphonates of general formula (1).

The method for producing the phosphonate' of the present invention is based on the cyclic ethylene diphosphite (Ill)/logenated benzyl side/
It consists of reacting with the same or higher temperature at a total temperature of 10 to 200°C.

Engineering Engineering 0□○ 1 + Tago
II) and cyclic phosphite (II) (81 i ch ; + e 5-Arbu
zov ) condensation occurs selectively with ring cleavage, that is, the reaction formula (
The following competitive reaction (rival reaction
Only 11 reactions were observed to occur without any appreciable occurrence of .

(fV) Competitive reaction (2) is a very unfavorable reaction; this is because, on the one hand, this reaction produces dihalogenated hydrocarbons as by-products, which reduces the weight yield of the Michaelis-Albuzob condensation. Moreover, the final product contains halogen atoms, which are very useful for the desired fire protection activity.
Two pieces may be lost unnecessarily, and on the other hand (IV
Cyclic ethylene phosphonates such as ) are generally very [7
1 part 1 It is easy to undergo water splitting 4).

Cyclic phosphites (II) are prepared by one of the conventional known methods; for example, by transesterification of 2 mol of triethyl or triphenyl phosphite with 3 mol of ethylene glycol, or by transesterification of comol of 2- Hello/
, 3. ．． It can be prepared by reacting 2-dioxaposphocne in the presence of 1 mole of ethylene glycol and 1 mole of tertiary amine.

Benzyl halide (Ill) used in reaction (1)
may be prepared by total chlorination or bromination of toluene and optionally fractionation by distillation.

The halogenated benzyl side where m or n is /-3 is preferred. Depending on the case, the halogen used, bare sil u
It may contain up to 5% polyhalotoluene as an inert but harmless impurity.

The novel halogenated pendyl phosphonates of the present invention can be used in a wide variety of plastic materials, such as polyurethanes, polystyrenes, ABS, vinyl resins and epoxy resins;
Synthetic fibers such as acrylic or modacrylic fibers (
These synthetic fibers may be used alone or in combination with other natural fibers); as fire protection additives in paints; adhesives or other combustible materials for which it is desirable to protect against fire hazards. It is possible.

The fire protection properties of the phosphonates of the present invention are particularly useful in polyurethane foams, where the fire protection effect has been shown to be clearly permanent in accelerated aging tests.

Example/ A flask was charged with 310 gt5(D triphenyl phosphite, 73 parts of ethylene glycol, and 0.2 parts of sodium methoxide.

This mixture was heated at 2 iso<0>C for 1 hour. Phenol produced by transesterification/999. ．．
After distillation under a vacuum of 33 Pa, the residue is 3.
,? , under a vacuum of 2 Pa, /, 2. ? Distilled at °C,
0 parts of co, -2'-, (:/,, 2-ethane-di-yl-bis(/,,?.

Cordioxaphosphora/)] was obtained. This compound was charged into a flask, and dichlorobenzyl chloride c of /Hiroko part was mainly mixed with Ko, Hiroko, 2. J and 3. '1 mixture of isomers) was added. Mixture /l at 0°C/♂hr 7Jl
] After heating, /999. The,? Under vacuum of Pa, /AO
Distilled at ℃ to obtain 2.23 parts of a neutral liquid consisting of the following compound with a refractive index of 0 = 7
J! t3 NMR: 'Ti'' δ,?,,? 90I;I): Gu, 2
0 (Hb, Ilc) and 3. OtsuSpp+n (l
lrl) /3c:δ30. ．． 2 g −30,77((b+);
Otsu,! ;, /4'-1, A, 33 (Ob, Oc) and q, 2.7 ppm (Cd) standard sample S i (OI
T3) 4 Example 1. ? 70 parts triphenyl phosphite, 3 parts ethylene glycol and 0.2 parts
．． ! Part of sodium methoxide? The flask was charged. This mixture was heated at 730 °C for /,j hours and after fC, the phenol produced by transesterification was transferred to /9F?
, ♂ 0 parts of dichlorobenzyl chloride (mixture of isomers) distilled under a vacuum of 3 Pa was added to the straight fan flask. The obtained mixture 'JgJ is /1. O'C:,
After heating for 20 hours, the mixture was allowed to cool to 720°C. The product was then treated with 75 parts of ethyl formate for 30 minutes to neutralize the slight acidity of the product. Thus obtained t'1. /, 399. A liquid containing mainly the product of Example 1, distilled at 1° C. under a vacuum of
0 copies were obtained.

Example 3 A flexible polyurethane foam block was produced using the following composition: Polyol UGIP (JL//, 20 (molecular skeleton 4to
triol up to oo) 100 parts water

3. S part amine contact i (N,N-dimethylethanolamine) 1. ,? o y gold face touch s: (cazolyl forged stannous tin? base material) orsl
'Commercial long surface active agent silicone o, g
o tt Fire protection additive 10
“Toluene diisocyanate LILT et al NE TgoC, index 10t)
173 //The bulk density of polyurethane boot socks obtained by free expansion is approximately? 01
I had a hard time with c7/i.

The fire resistance of the foam was determined by the following commercial laboratory test.

Monoacid Cumulative Index 11: French Standard Test Method NFT, 3
107/ One horizontal combustion test +6;s: ASTM IJ-/l
q, z-7a1i'Z ``A finger'Ml (oxygen
1ndex) measurement is /2. JX/2. on a vertical specimen with a cross section of S- for at least 3 minutes I) 11
The degree of improvement in O refractoriness achieved can be determined by measuring the minimum concentration of the mixture of oxygen and nitrogen necessary for complete combustion (or over a length of 7 Iw). It was recognized that the larger the

ASTM D/lY Co.7q has a horizontal test piece (5
0x1.50x/3van) 3 placed on a wire mesh, and the end of the test piece is placed in contact with the flame of a gas burner for 30 seconds. In this test method, the length of damage caused by combustion (at most, from the end in contact with the fence to a reference line located at node 727) and burning time are measured. If combustion ceases spontaneously before complete failure of the specimen and this occurs for five specimens, the material is said to be "self-extinguishing" (SB) under the test conditions. .

The fire resistance test was carried out before and after the specimens were subjected to accelerated aging (accelerated aging was carried out by leaving them in a sealed container at 70° C. and relative humidity qo9 for 31 or 2 hours).

The fire retardant effects of the compounds of Example/C were evaluated by comparing them with the following two types of commercially available fire retardants.

-2-chloroethylphosphonic acid (AN'l'1BLAZ
B”7za, Mobil Chemica1 product)
Tris (2-10 loethyl) phosphate or T
OgP.

The test results are shown in the table. Accelerated aging tests particularly demonstrate the advantages (durability of fire protection effect) of the compounds according to the invention.

Claims (1)

[Claims] / General formula (I): (wherein, X represents a chlorine or bromine atom, m and n
may be the same or different, and the substituent X in the aromatic nucleus
90 to j). A compound according to claim 1, wherein 1m and n represent /, co or 3. 3. A compound according to item 1 of the scope of patent No. 811, wherein m and n represent ko. A compound according to claim 1, wherein gX represents a chlorine atom. y General formula: C6H, -mXm-CH2X and C
6H6-nX nQH2X (X, m and n in the formula
is characterized in that seven or more of 7 or more benzyl halides (having the meanings given below) are reacted with a cyclic phosphite of the general formula (■):
General formula (■): 0-OT42-0H2)C0-CI■2-0H2X (wherein, X represents chlorine or an odorant, m and n may be the same or different, and A method for producing a novel urogenated benzylphosphonate, which is the average number of substituents X in the compound and is expressed by 0 to J?