DE2226107A1 - Method of flame retarding fibrous materials - Google Patents

Description

dr. W. Schalk d'ipl.-ing. P. Wirth · dipl.-ing.G. Dannenberg

DR.V. SCHMIED-KOWARZIK · DR. P. WEI NHOLD · DR. D. GUDEL

6 FRANKFURT AM MAIN

CR. ESCHENHEIMER STRASSE 39

GAF Corporation
140 West 51st Street New York, NY / USA

SK / SK FDN 191

Method of flame retarding fibrous materials

The present invention relates to a method of making fibrous or to give fiber-containing materials flame-retardant properties. she relates in particular to the use of halogenated tripropargylphosphtee as a flame retardant for fibrous materials.

Most synthetic or natural fiber and the stuff made from it ο .'si nd quite flammable. The dangers posed by possibly combustible substances in the lumbar or on a carrier have led to research into effective flammable oils which can be applied to such fibrous materials. Furthermore, it is angsaolien than desirable that the Anvvt-jsenheit a Flammverzögerungsniittels in a fabric difjücrn Liiu ability are, einzusL burning immediately in Abvjesenhej.t the flame (. ¹ IIt-Ti, whereby the presence of a potentially hazardous Nar.hu] ühifini ; nuch, removal of the flame is eliminated.

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It is therefore an object of the present invention to provide effective flame retardants for fibrous or fibrous materials.

Another object of the present invention is to provide such effective ones Flame retardants that in the absence of a flame no further Burning is possible.

The method of the invention for flame retarding fibrous materials is characterized in that a compound of the

Formula: _v

"? 1 Ϊ1

(H-C-C-CHJl ·}. P »0

ι ι ^{2 y}

Xg Xg

applies, in which each X. can stand independently for chlorine or bromine, or, taken together, can form a bond, each X represents a halogen radical stands or, taken together, can form a bond and the sum the X. and X "atoms in the compound are at least two.

The flame retardants according to the invention can by halogenation ' can be easily produced by tripropargyl phosphate. Will be most expedient the tripropargyl phosphate in a halogenated hydrocarbon solvent, such as carbon tetrachloride, chloroform, methylene chloride, trichlorethylene, Perchlorethylene, etc., dissolved, and a gaseous or liquid halogen

is added to the solution. Uie actlition of at least 2 halogen atoms and ahead

Zugsweisß at least 4 halogen atoms, - the compound is considered necessary, to give the compound flame retardation effectiveness. The used Halogens? are preferably chlorine and bromine; in the highly halo-nated Species can, however, also contain other substances, such as iodine and fluorine, can also be used. The degree of halogenation fol- jt flor Heaktinr,; .- stüchiometry. If, for example, 1 mole of tripropurgylphasphut is used with 3 moles of CJhlor uinjc ^

209853/1157

then tri- ( 2,3-dichloroallyl) phosphate is obtained. When using 6 times chlorine on the other hand is obtained tri- (2,2,3 _f 3-tetrachloropropyl) phosphate. If the halogenation is carried out with less than stoichiometric amounts of the halogen present, only a partial addition is obtained. If, for example, 1 mole of tripropargyl phosphate is reacted with 2 moles of chlorine , di- (2,3-dichloroallyl) propargyl phosphate is obtained.

Typical flame retardants according to the invention are, for example, tri- (2,2,3,3-tetrachloropropyl) -phosphate, tri- (2,2,3,3-tetrabromopropyl) -phosphate , tri- (2,2,3-tribromo-3 chloropropyl) phosphate, tri- (2,3-dichloroallyl) phosphate, tri- (2-bromo-3-chloroallyl) phosphate, tri- (2-bromo-2-fluoro-3,3-dichloropropyl) - phosphate, tri- (2-iodo-2,3,3-tribromopropyl) phosphate, di- (2,3-dibroinallyl) propargyl phosphate, di- (2,3-dichloroallyl) propargyl phosphate, 2,3-dichloroallyl dipropargyl phosphate, 2,3-dibromoallyl dipropargyl phosphate etc. The flame retardants according to the invention with an unsaturated part within the molecule have proven to be more hydrolytically stable than the fully saturated compounds and can therefore be used advantageously in fabrics which are to be washed.

The flame retardant preparations according to the invention can be used in any suitable inert carriers are applied to the fibers and fabrics. Are common these compounds in halogenated hydrocarbons, such as carbon tetrachloride, Chloroform, methylene chloride, trichlorethylene, perchlorethylene, etc., as well as other non-aqueous solvents such as tetrahydrofuran, soluble. Solutions or dispersions that meet the inventive flame retardancy containing bonds in concentrations of about 5-10 weight-ijii are suitable.

209853/1157

The flame retardant compounds can penetrate the fibers and fabrics Appropriate measures such as spraying, dipping, submerging, padding, etc., are applied. If necessary, the flame retardants can be used with synthetic polymeric materials are mixed and coextruded with them to form flame retardant fibers. It is common It is expedient to use about 5-20% by weight of the flame retardant preparation on the fibers or fabrics to be treated for effective flame retardation Dry basis, to be incorporated.

According to the invention, synthetic and natural fibers and those made therefrom can be used manufactured substances are treated. Typical fibers to be treated are e.g. cotton, wool, silk, nylon, rayon, polyester etc.

When applying the halogenated tripropargyl phosphate compounds according to the invention on fibers and fabrics in the manner described above, it was found that the resulting materials did not promote burning and only char in the presence of an open flame. After removal dsr Flame stops burning immediately without afterglow.

The following examples illustrate the present invention without it to restrict. Unless otherwise stated, all specifications are tuile and precise Parts by weight and v / o by weight

209853/1157

Example 1

48 g (0.3 mol) of bromine were added dropwise with cooling to a solution of 10.5 g (0.05 mol) of tripodpargyl phosphate in 100 ecm of carbon tetrachloride. In the initial addition, bromine was rapidly absorbed, "as indicated by the disappearance of the bram color. When the addition was complete, the reaction mixture was stirred for 17 hours at room temperature. The solid formed was filtered off and washed with carbon monoxide and vacuum-dried. It weighed 28.3 g a melting point of 140-154 ° C. (= 48% yield). After recrystallization from chloroform, the solid had a melting point _{of 150-153 ° C. It was obtained as OP (OCH 2 CBr 2} CBr ₂ H) ₃ identified.
Analysis for C ₉ H ₉ Br ₁₂ O ₄ P

Calcd .: C 9.24 H 0.77 Br B 1.88 "P 2.64
Found:, C 9.45 H 0.91 Br 62.80 P 2.80

NMR analysis (based on tetramethylsilane):
6.15 ppm (singlet) intensity 1 CBr ₂ H
4.8 ppm (doublet) intensity 2 OCH ₂

Example 2_

Example 1 was repeated using 42.4 g (0.2 mol) of tripropargyl phosphate, 120 ecm (2.3 mol) of bromine and 500 ecm of partial carbon; 200 g (= 76% _{) of OP (UCH 2 CBr 2} CBr ₂ H) _{3 were obtained in this way} .

Example 3

16 ecm (0.3 mol) of bromine were added with cooling to a solution of 21.2 g (0.1 mol) of tripropargyl phosphate in 100 ecm of carbon tetrachloride. No solid had formed after stirring for 2 hours at room temperature. The solvent was removed in vacuo. 64.8 g (= 92%) of a liquid identified _{as OP (OCH 2} CBr = CBrI-I) _{3 remained.} The IR spec

- 1 strand contained an absorption of a triple bond at 2120 cm-, each had

_1 but a mean C = C absorption at 1610 cm.

209853/1157

B. eis ρ i el

To a solution of 21.2 g (0.1 mol) tripropargyl phosphate in 100 ecm carbon tetrachloride 11 ecm (0.2 mol) of bromine were dropped with cooling. the Solution was allowed to warm to room temperature and the solvent removed in vacuo. This gave 45.6 g of a brown oil, which as

y OCH ₂ CBr = CBrH

OP OCH ₂ CBr = CBrH

OCH ₂ CSCH

was identified.
Example 5

49.5 g (0.7 mol) of gaseous chlorine were passed into a cold solution of 21.2 g (0.1 mol) of tripropargyl phosphate in 100 ecm of carbon tetrachloride over a period of 2 hours. The solution was left to stand at room temperature overnight. The solvent was removed in vacuo, leaving 63.7 g (= · 100 i,} OP (OCH ₂ CCl ₂ CCl ₂ H) ₃ .

Example 6

Example 5 was repeated using 21.2 g (0.1 mol) of tripropargyl phosphate, 21.3 (0.3 mol) of gaseous chlorine and 100 ecm of carbon tetrachloride. In this way 42.5 g (= 100 ° / ₀ ) OP (OCH ₂ CC1 = CC1H) _{3 were obtained} . '

Example 7

Example 5 was prepared using 21.2 g (0.1 mol) of tripropargyl phosphate, 14.2 g (0.2 mol) of gaseous chlorine and 100 ccm of carbon tetrachloride repeated. This gave 35.4 g (= 100%) of the following compound:

OCH ₂ CCI = CCIH

UP OCH ₂ CCI = CCIH

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Bb! Game θ

A solution of 5 g of OP (OCH ₂ CBr ₂ CBr ₂ H) ₃ (prepared according to Example 2), 45 g of tetrahydrofuran, 32.5 g of "Freon 11" and 17.5 g of "Freon 12" was placed in an aerosol bottle. This solution was sprayed onto cotton fabric * ("broad cloth") up to an absorption of 17 % of the dry weight. If the fabric treated in this way was held in the flame of a burning match, it charred. The fabric stopped burning immediately after the flame was removed. There was no afterglow.

B β ispi e 1 9

Following the procedure of Example θ, solutions were prepared from the following compounds:

OP (OCH ₂ CBr-CBrH) ₃

P ^ OCH ₂ CBr-CBrH)

P (OCH ₂ CCI-CCIH) ₂

These solutions were each placed in aerosol containers and placed on an up-

take 17 'of the dry weight sprayed onto cotton fabric. If the fabrics treated in this way were held in the flame of a burning match, they charred. Burning ceased immediately after the flame was blown, and in no case was there any afterglow observed.

Dia indicated in the description above for the preparation and Use of the flame retardant compounds according to the invention are only used of illustration. Various others may have similar results Tripropargyl phosphates, carriers, application methods, fibers and fabrics can be used.

209853/1157

Claims (1)

Claims 1.- A method for making fibrous materials flame-resistant, characterized in that that one on the materials a compound of the following Formula applies: X ₁ X ₁ (HC - C - CHJJl P = D
! I ^{2 3} Xp Xp in which each X- can independently stand for chlorine or bromine or, taken together, can form a bond, each X _? stand for a halogen radical
can or, taken together, can form a bond and the Burr.nie the X,
and X is ₂ 'or more halogen atoms in the compound. 2. - Method according to claim 1, characterized in that the connection in Combination with an inert carrier is applied. 3.— The method according to claim 2, characterized in that the connection in the inert carrier in concentrations between about 5-10 wt. / ·) is present. 4.- The method according to claim 1 to 3, characterized in that the connection is applied to the fibrous material in sufficient quantities, u-n to incorporate into this about 5-20% by weight of the compound (on a dry basis). 5, - Method according to claim 1 to 4, dadux-oh characterized that tri- (2,3-dibrornallyl) ~ phosphate, tri (?., 3-dichloro rillyl) phosphate, tri- (2,2, 3,3-tetrabromopropyl) phosphate, tri- ( Z, 2,3,3-tetre.chloropropyl) phosphate, di- (2,3-dlbraniallyl) propargyl phosphate or di- (2,3-dichloroallylJ-propargyl) - phosphate is used. The patent attorney: 209853/1157