DE2724243A1 - HALOGENIC ORGANIC PHOSPHORUS COMPOUNDS AND THEIR USE AS FLAME PREVENTION AGENTS, IN PARTICULAR IN PLASTICS - Google Patents

Description

The invention relates to novel, halogen-containing, organic Phosphorus compounds, particularly those having a reactive functionality, which act as flame retardants and as intermediates for the production of reactive flame retardants for a wide variety of materials and especially for plastics are suitable.

The use of organic phosphorus and halogen-containing compounds as flame retardants, including Counting flame retardants is known. These have, among other things, the disadvantage that they have to be effective in large quantities Quantities must be used that they reflect the chemical or physical properties of the materials with which they are are used together, change that they are not constantly held in the material, but after some time sweat out or washed out that they are thermally unstable and when heated, chlorine, bromine, hydrogen chloride or give off hydrogen bromide and that they are toxic in many cases.

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It is also known to use such halogen-containing organic phosphorus compounds as flame inhibitors, which have reactive functional groups, so that the flame prevention agent reacts with the material to which it is added and has better retention compared to the material shows. Such reactive flame retardants are better than the conventional flame retardants Retention, but still show the disadvantages mentioned above. Such flame retardants are disclosed in U.S. Patent 3,840,622 and also 3883,620, 3,886,237, 3,888,844, and 3,920,685.

The invention has the task of proposing new halogen-containing organic phosphorus compounds that the above-mentioned disadvantages no longer show and especially as a flame retardant or as an intermediate product the manufacture thereof are suitable and which have exceptionally good flame retardancy and thermal properties Have stability and also contain reactive functional groups, so that the flame retardants themselves easily chemically combine with the materials to which they are added.

Halogen-containing organic phosphorus compounds are used to solve the problem the following general formula is suggested

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P - (ACHCX ₃ ) _n

in the

η the number 1 or 2,

X chlorine or bromine,

Z oxygen or sulfur,

A is a divalent radical with one or more oxygen bonds,

B a chlorine, bromine, hydroxy, alkoxy, alkenyloxy, or ureidohydrocarbyl isocyanate radical,

R _{1 is} a bromine, chlorine, hydroxy, hydrocarbyl or Hydrocarby1-oxy radical,

R _{2 is} a bromine, chlorine, amino, hydrazino, hydroxy, -R ₁ radical or an -OMe radical, in which Me is the salt of a metal from the group Na, K, Li, Zn, Mg, Ni, Ca, Ba, Sb, Ti, V, Sn, or an -OQ radical in which Q is an epoxy esber derivative of an acrylic or methacrylic acid and wherein

In _{the case of η = 1, R 1} and R_ together represent a divalent arylenedioxy radical

mean.

The invention also relates to compounds of the general formula

Ra

^ P-A'-CHCXn

H '

^H B

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in which X is chlorine or bromine, Z is oxygen or sulfur, A ^{1 is} a direct PC bond or a divalent radical with one or more oxygen bonds, R is a hydrocarbyl or hydrocarbyloxy group.

In the compound of the formula I, the radical R _{1 can be} a reactive functional group, such as chlorine, bromine or a hydroxy radical, or a hydrocarbyl or hydrocarbyl-oxy radical, i.e. in the latter case a substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, heterocyclic radical or be an acyl radical. If R _{1 is} an aliphatic radical, this can be a substituted or unsubstituted alkyl, alkenyl or alkynyl radical which is optionally interrupted by one or more oxygen atoms. In the case of substituted radicals, the substituent is preferably a reactive radical, such as chlorine or bromine, a hydroxy, haloalkyl, amino or epoxy radical.

Substituted or unsubstituted hydrocarbyl or hydrocarbyl-oxy radicals R ₁ can be the following radicals:

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~ ^CH 3 ^; ~ ^C 2 ^H 5 ^? -OCH ₃ ;

-CH ₉ CH ₇ X; -OCHCX- ,; -OCHCH ₁ ; 2 2, J, J

X CH ₃

-CH ₀ CHCX ,; -OCHOCH-CX ,; OH CX ₃

-OCII CHCX ,; -CH-CHCONH.,; -OCH-CHOH; 2 | 3 2, 2 2 ₍

XX CH ₂ X

-0 (CH ₂ CHO) ₂ H;

CH ₂ X

Cl O I I

-CH-CHCO-N-CH ₉ OCH ₉ -N-COCHCh ₇ -P-OCHCCI ,; 2,, 22, * \ \ 3 Cl CH ₂ OH CH ₂ OH Cl Cl

-OCH NCO; -OCH ₂ CHCH ₂ (glycidol);

0 I.

-OCH ₂ CHCO ₂ C = CH ₂ ; -0-P-OCH ₃ ;

OH CH ₃

II

-OC- (polyhalo-cyclo or polycyclo-aliphatic);

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-OCH ₀ CH-OCHCX ₁ ; 2 2, J

OH

-OCH ₂ CH ₂ OCH ₂ CH ₂ OCHCx ₃ ;

OH

(CH ₂ X) ₂

-N.

(CH ₂ X) ₂

-N

■
0 CH
\ "Γ"
0 • «3 b where R = H, CHX ₀
I ² CHCH-
\ /
0 CH X
I ² CHCH-
\ /
0 CHCH-,
\ /
0 or

- (CH ₂ ) - (hydantoin derivatives, haloalkyl derivatives, haloaryl derivatives, alkyl epoxy derivatives, aryl epoxy derivatives, unsaturated epoxy derivatives and halocycloalkyl derivatives);

χ χ

-0

X X

-CHOC (O) N CX.

CO

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-O-carbohydrates such as -0 (glucosan);
-0- (sucrose) ;
-0- (fructose); -0- (sorbitol); -O- (Soforose) .

In the above radicals, X corresponds to the meaning given above for bromine or chlorine.

R ₂ can represent a reactive phosphorus bound functional group, such as bromine, chlorine, amino, hydrazino, or hydroxy, or the meaning of R may have ₁ or may further have the rest -OMe with the above meaning for Me, where such residues by the reaction of a metal salt of the specified class with a hydroxyl radical can be obtained. R ₂ can also mean the group -0-Q, where Q is an epoxy ester derivative of acrylic or methacrylic acid. Epoxyesterderivate are alkyl, among others, acrylates and methacrylates of epoxy, Epoxyalkenyl, Epoxycycloalkyl, Epoxyaryl and heterocyclic epoxy compounds, such as Glycidolacrylat and glycidol methacrylate.

If η in the compound according to formula I has the value 1 , R. and R ₂ can be linked to one another as a divalent arylenedioxy radical, such as, for example, catechol.

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The radical A of the compound according to formula I is a divalent radical with one or more oxygen bridges. The remainder A closes alsoden oxygen radical (-0-) and divalent radicals of alkanes, which are interrupted by one or more oxygen atoms. In the latter case, this radical can be substituted or unsubstituted be, wherein the alkanes preferably have 1 to 6 carbon atoms. Residues of this group include bivalent ones Free radicals from polyols such as ethylene glycol or diethylene glycol. The bivalent radicals also include the oxy radical (-O-), Alkyleneoxy (-R0-), oxyalkylene (-0R-), alkylenedioxy (-0R0-), oxydialkylene (-R0R-), (oxydialkylene) -dioxy (-ORORO-), (aminodialkylene) -dioxy (-ORN (H) RO-) and (alkylaminodialkylene) -dioxy (-ORN (R) RO -) radical. In the above, R is an alkyl or Alkylene radical. The following residues are particularly suitable:

CX ₃

-CHO-; -CH CH CO-;

CX OH

OCH CH 0-; -OCHpCH OCH ₉ CH 0-

OH I

CH ₂ CH ₂ OCHCX ₃

-OCH CH ₂ N (H) CH ₂ CH ₂ O- -OCHjCHjNCHjCHjO-

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The radical B of the compounds according to the invention is preferred a reactive radical, such as reactive halogen, preferably chlorine or bromine, or a hydroxy radical. B can too be an alkoxy or an alkenyloxy radical, preferably with one or more halogen atoms, in particular chlorine or bromine are substituted. The remainder B is in particular:

-OCH ₂ CX ₃ ; -OCH ₂ CHXCH ₂ X;

X X I I

-OCHC = CH -OCHC-CH;

¹ · Il

XX XX

-OCHCX -OCHCX ₇

I 3, 3

OCHC = CH OCHC - CH

Il Il

XX X ₂ X2

If B is a ureidohydrocarbyl isocyanate radical, the can Hydrocarbon radical in this radical can be an alkyl, cycloalkyl, aryl or polyaryl. Case in point for the remainder B is the ureidotoluyl isocyanate of the following formula:

NCO

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The compounds according to the invention according to formula I and formula II all have the remainder -CHCX ,, as a typical configuration

that occurs at least once. This residue is derived from chloral or bromal, which serve as the starting compound. This group enables the separation of the -CX ^ group from the phosphorus atom, so that it has good thermal stability and UV stability and good resistance to hydrolytic reactions is obtained.

Compounds of the formula I can be further defined according to their structural formula. A class of connections analogous to formula I have the following formula

Z
I.

(R ₁ J ₂ - P - A - CHCX ₃ (III)

I. B.

Particularly suitable compounds of the formula III are those in which

(i): A has the meaning of

-0-, -CHO-, -OCH ₂ CH ₂ N (H) CH ₂ CH ₂ O- or CX ₃

OH
I.

CH ₂ CH ₂ OCHCX ₃

-OCH ₂ CH ₂ NCH ₂ CH ₂ O-

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(ii): B = -Cl, -Br, -OH or -OCH ₂ CHXCH ₂ X or (ill): A has the meaning as above under (i) and B has the meaning as above under (ii).

Also particularly suitable are those compounds of the formula III in which R _{1 is} a lower C ₁ to C alkoxy radical and B is a hydroxy, chlorine or bromine radical.

Furthermore, suitable compounds according to formula III are those in which R _{1 are} the following two radicals:

_U CHCX ₃ OH

-O (CH ₂ CHO) _U H
CH ₂ X

where u has the value 1 or 2 and B in the first case is chlorine or bromine and in the second compound a halogen-substituted one Is alkoxy. They are also used as reactive flame retardants and also as an intermediate product in manufacture Another reactive flame retardant is the tetrahaloalkyl phosphorodihalidate or phosphothiodihalidate suitable according to the following formula:

Z
Y ^ I

^ - P-A- CHCX, (IV)

Y ^ I

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wherein A, X and Z have the above meaning according to formula I and Y is independently of the meaning of X is also chlorine or bromine. The corresponding tetrahaloalkyl acids of the compound according to formula IV are also suitable.

Also suitable as flame retardants are urethanes according to formula I in which R. = R_ = a ureidohydrocarby1-isocyanate derivative and B is ureido hydrocarbyl.

Further compounds according to the invention according to formula I correspond the following formula

Z R, I

^ T-A- CHCX, (V)

in which A, B, R ₁ , X and Z are as defined above and R. is a chlorine, bromine, amino, hydrazino, hydroxy, -OMe or OQ radical.

Particularly suitable compounds of this class contain an oxy radical for A, while B is chlorine or bromine. Other preferred compounds of this class have a chlorine, bromine, amino, hydrazino or hydroxy radical as the R. radical.

Further compounds according to formula I have the general formula

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R ₁ -P-

compounds in which A is an oxy radical or a divalent radical of glycol or are particularly preferred Is diethylene glycol.

Furthermore, halogen-containing organic phosphorus compounds according to formula II

Z
R, I

"^ rP - a'-chcx ₃ (H)

OH

suitable, in which X and Z have the meaning given above and A 'has a direct P-C bond or a divalent radical a content of one or more oxygen bonds and R represents a hydrocarbyl or hydrocarbyl oxy radical.

Preferred compounds of this class are phosphonic acids according to formula II, in which R _{3 is} a lower C ..- to C.-alkoxy radical and A 'is a direct PC bond or a -CHO bond

CX ₃ mean.

Compounds according to formula I show an excellent one in the presence of at least one oxy bond in the divalent radical A

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Heat and UV stability and resistance to hydrolysis by allowing a separation of the halogen atom from the phosphorus atom enable. These compounds show good stability and hydrolysis resistance, which is the case with similarly structured compounds other organic phosphorus compounds are absent when the chloral or bromal radical is directly on the phosphorus atom is bound.

However, monoalkyl phosphoric acid esters result in reaction with Chloral or bromal compounds according to formula II and thus lead to products that have excellent heat resistance, UV resistance and resistance to hydrolysis show even when the chloral or bromal radical is directly attached to the phosphorus atom is bound.

The compounds according to the invention can be used in a wide variety of ways Way to be prepared, but in all cases chloral or bromal with certain organic and / or inorganic phosphorus compounds is implemented. The preparation of numerous compounds according to the invention is based for example on the implementation of chloral or bromal with PClj- or PBr ,. and a subsequent treatment with water or sodium hydroxide or H-S according to the following equation:

CX ₃ CHO + PY ₅

[NaOH / H ₂ O or triethylamine / H ₂ O or H

: pochcx, (viii)

I ³

7Ο98 ίθ / Ο967

in which X and Y denote bromine or chlorine and Z denote oxygen or sulfur.

This reaction product (VIII) is used directly or can be used further with various reactive compounds can also be derived from bromal or chloral itself, converted to other highly reactive polyhalogenates Obtain organic phosphorus compounds according to the invention, wherein in the following equation R is a reactive functional connection is.

(viii) T ^

, VIII) ^

Other compounds of the invention are made by reaction obtained from chloral or bromal with mono- or dialkyl phosphites, which in turn further with bromal or chloral and / or with other reactive compounds such as aryl diisocyanates.

0 o

1 . ear'

KP + CX CHO ^ PCHCX ₃ (IX)

OH

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R I

(IX) + CX ₁ CHO »" ^ PCHOCHCX,

³ H ^ II

CX ₃ OH

0 OO

1 s OH II ^ R

(IX) + RP ^ ■ »- CX-CHOP-O-P

^X H ³ II ^ H

X X

0 0

1 I.

-PH + CX ₃ CHO > ■ (R) ₂ -PCHCX ₃ (X)

OH

(X) + CX CHO (R) ₉ -PCHOCHCX ₁

CX ₃ OH

The compounds according to the invention show an extraordinary one good flame retardancy and thermal stability and are particularly useful as flan preventers for numerous natural and synthetic polymers are suitable, such as acrylic resins, polyacetals, polyurethanes, polyolefins, polycarbonates, ABS resins, polyesters, polyamides, wood, proteins, natural and synthetic polymer cellulose compounds and rubber. The compounds can either be with the material during polymerization or in the melt be mixed or can be applied superficially, as is the case with natural polymers or natural and synthetic

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table textile fibers is the case. The connections can also be made with cellulose fibers such as with cotton and rayon and with natural or synthetic silk or wool fibers are used.

The compounds are reactive and combine chemically with the materials to which they are added. They mark is also characterized by a relatively high ratio of phosphorus and halogen to the alkylene bonds, the attributed at least in part the desired flame retardancy and the low toxicity and ability of the compounds can be combined with materials without affecting the physical properties of these materials change. The compounds according to the invention also have the advantage that they are essentially neutral, that is to say none contain free acid.

The compounds according to the invention can be used in any amount can be used to achieve the desired level of flame retardancy without disadvantages of the desired properties the materials occur. The exact mixing ratios vary depending on the phosphorus and halogen content of the respective Connection and the desired flame prevention.

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In the following, the invention will be explained in more detail with the aid of examples.

Production of the halogen-containing organic phosphorus compounds

example 1

For the production of ßßß-Trichloro- o ^ -hydroxyäthyl-ß-äthoxyphosphonat of the following formula:

C2H5O-P-CHCCI3 OH

a three-necked flask with an open-top reflux condenser, a mechanical stirrer, a thermometer and a cryostat / thermostat temperature control and a dropping funnel with a drying tube was used to protect the reaction mixture from atmospheric moisture. The flask was charged with 1 mole of O-ethylhydroxyphosphite C ₇ H ₁ -O-POH (O) H prepared from diethyl phosphate and metallic sodium or sodium hydroxide under reflux under inert conditions. 1 mol of chloral was slowly added dropwise from the dropping funnel while maintaining the reaction ^{temperature below 60 °} C. and under a nitrogen blanket. The mixture was stirred for a further 20 minutes and left at 50 ° C. The reaction mixture was then treated with an inert solvent at 35 ° C. and purified. The analysis values are as follows:

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calculated: Cl / P = 3.44 found: Cl / P = 3.40

Example 2

For the production of ßßß-tribroin-oti-hydroxyethyl-ß-ethoxyphosphonate of the following formula:

0 l / H

C ₂ H ₅ OP-CHCBr ₃

OH

the procedure was analogous to Example 1, but now 1 mol of bromal was used instead of chloral.

Analysis values:

C ₄ H ₈ Br ₃ O ₃ P

calculated: bromine / P = 7.74 found: bromine / P = 7.69

Example 3

For the preparation of Ο, Ο-diethyl-oc; - (ßßß-trichlorethylene-oxy- 06 ¹ -hydroxy-ßßß-trichloroethylene) phosphonate of the following formula

0 I.

(C ₇ HrO) ₉ - P-CH-O-CHCCl-, * ^b II

CCl ₃ OH

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a device according to Example 1 with 1 mole of ßßß-trichloro-Q ^ -hydroxyäthyl- (or hydroxymethyl) phosphonic acid diethyl ester (Product A), 150 ml of dioxane and 0.08% by weight of one charged strongly acidic cation exchange resin. This material A was made by reacting with diethyl phosphite Chloral prepared analogously to Example 1, with 1 mol of chloral slowly while maintaining a temperature of the reaction mixture of less than 60, preferably 50 C below Nitrogen was added dropwise. The mixture was left at 50 C for an additional 20 minutes after the exothermic reaction ended. The product was cooled to room temperature, filtered and purified analogously to Example 1. Analysis data from

calculated: Cl / P = 6.87
found: Cl / P = 6.80

Example 4

For the production of O-ethyl-C ^ -ßßß-trichloroethylene-oxy-Q £ '-hydroxy-ßßß-trichloroethylene-phosphonate the formula

C, HcO-P-CH-O-CHCCl ₃ CCl ₃ OH

was carried out analogously to Example 3, but now the material A by 1 mole of O-ethyl-ßßß-trichloro-o ^ -hydroxy-

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ethyl phosphonic acid was replaced. Analysis words of C ₆ H ₉ Cl ₆ O ₄ P:

calculated: Cl / P = 6.87 found: Cl / P = 6.80

Example 5

For the production of Ο, Ο-diethyl-Qir-ßßß-tribromoethylene-oxy- «*? hydroxy-ßßß-tribromoethylene phosphonate the formula

0 I.

(C ₂ H ₅ O) ₂ - P-CH-O-CHCBr ₃ CBr ₃ OH

the procedure was analogous to Example 3, but now 1 mol of bromal was used instead of chloral. Analysis values:

^C 8 ^H 13 ^Br 6 ° 5 ^P.

calculated: bromine / P = 15.48 found: bromine / P = 15.39

Example 6

For the production of tetrachlorethylene phosphorus dichloridate, a device according to Example 1 was charged with an inert solvent with a low freezing point (300 ml) and 2.8O to 7 mol, preferably 3 mol PCl ₁ -. There were 0.97 to 2.40 moles of chloral or chloral hydrate and preferably

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1 mol added so that the reaction temperature remained below 40.degree. The reaction mixture was filtered off and it became Tetrachlorethylene phosphorus tetrachloride of the formula

CCl ₁ - CH-OP (Cl) ₄ ³ I.
Cl

obtain.

The resulting solution was cooled to 5 to 0 ° C.

A concentrated sodium hydroxide solution of 39 g in 39 g of water was added dropwise so that the temperature did not exceed 5 ° C rose, which took 1.10 hours. The mixture was lasted for 20 to 40 minutes, preferably 30 minutes longer Stirred 12 to 25 ° C.

The reaction took place according to the following equation:

Cl
) -pCT +2 Na OH /

¹ \ Cl
Cl Cl

I ^ Cl

CCl -, - CH-OP. + 2 NaCl + 2 H ₀ O

Cl

The salt was then filtered and the solution over Na_S0. dried. The drying agent was filtered off, whereupon with

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45 ml of methylene dichloride was washed. The methylene dichloride was distilled off at normal pressure, with almost complete yield tetrachlorethylene phosphorodichloridate in the form of a straw-yellow colored liquid, namely

0 CCl, -CH-O- p '

I ^N ci

Cl was obtained .

Example 7

For the production of tetrachlorethylene phosphate bis (methoxyisocyanate) the formula

O 1

CX ₃ -CH-OP- (OCH ₂ -NCO) ₂ Cl

in which X = Cl or Br, tetrachlorethylene phosphorus dichloride (Example 6) or tetrahaloethylene chlorophosphate OC · chloroethyl phosphorodichloride of the formula

0 0

1 I.

CX ₇ CHO-P-CH ₅ CH-P- (Cl) - ³ II ^l \

Cl Cl Cl

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which had been prepared from the tetrachlorethylene phosphorus dichloride (Example 6) and vinylphosphonic acid dichloride, in an amount of 2 54 g and paraformaldehyde in an amount of 127 g at 30 to 14 5 ° C in an autoclave and preferably Heated at 138 ° C for 160 minutes. After cooling and cleaning the following reaction products were obtained:

0 O

1 1

CX ₃ CHO-P- (OCH ₂ Cl) ₂ and CX ₃ CHO-P- (OCH ₂ Cl) ₂

Cl OCH ₂ Cl

50.8 g of tetrachlorethylene bis (dichloromethyl) phosphate or trichlorethylene Q ^ -chloromethyl-bis (dichloromethyl) phosphate were added to 381 ml of dry benzene, which 111.76 g of a metal cyanate of Group I of the periodic table as for example contained sodium cyanate, the rate of addition being such that the reaction temperature remained below 30 to 35.degree. The reaction mixture was then refluxed for 160 minutes, cooled and filtered. After distilling off benzene, a di- and triisocyanate phosphate was obtained,
calculated: Cl / P = 4.57
found: Cl / P = 4.33

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Example 8

For the production of tetrachlorethylene phosphothiodichloridate of the formula

CCl ₃ CHO-P _x Cl

the procedure was analogous to Example 6, except that 2 moles of H ₂ S were used instead of 2 moles of sodium hydroxide.

Example 9

For the preparation of tetrachlorethylene phosphoric acid or tetrachlorethylene thiophosphoric acid of the formula

O S

ι ι

CCl ₃ CHO-P- (OH) ₂ and CCl ₃ CHO-P- (OH) ₂ Cl Cl

were carried out analogously to Examples 6 and 8 using 4 moles of sodium hydroxide or 4 moles of HS instead of 2 moles.

example

For the production of tetrabromethylene phosphorodibromidate of the formula

CCl-, CHOP. "Ί Br

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was carried out analogously to Example 6 using 1 mol of PBr and 1 mol of bromal instead of PCI, - and chloral, the corresponding acid and thio derivatives being prepared analogously to Examples 8 and 9.

Example 11

For the production of ßßß-trichloro- <fci-bromoäthylenphosphordibromidat the formula

I / Br

CCl., CHOP.
³ I.
Br

was carried out analogously to Example 6 using 1 mol of PBr ₁ . and 1 mole of chloral worked. The corresponding acid and thio derivatives were prepared analogously to Examples 8 and 9.

Example 12

For the production of 2,2'-bis (ßßß-trichlorethylene-methoxyßßß-trichlorethylene-Qd-oxy) -tetrachlorethylene-phosphate the formula

(CCI ₃ CHOcH ₂ CCI ₃ ) 2

P = O

0 —CHCCl-,

Cl

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27242A3

Was' worked analogously to Example 1, 150 ml of benzene and 1 MbI ßßß-Trichloräthylen-Od-hydröxy- o ^ -methoxy-ßßß-trichloroethane (prepared by reacting chloral and 2 £ 2-trichloroethanol) were used. This mixture was cooled to about 10 ° C. The dropping funnel contained 0.2 mol of tetrachlorethylene phosphorus dichloridate according to Example 6, 50 ml of benzene and 50 ml of triethylamine, all of which were slowly stirred in while maintaining the temperature of the reaction mixture below room temperature. After the addition, the mixture was stirred for a further 80 minutes at 20 to 30 ° C., the benzene solution was washed to the neutral point, filtered off and the solvent was removed under reduced pressure. A compound of the general formula C | _Jt-Ci- _e OP was obtained, calculated: Cl / P = 18.31 found: Cl / P = 16.89

Example 13 For the production of bis (ßßß-trichlorethylene-methoxy-ßßß-tri-

chlorethylene-Q £ -oxy) -2-chloroethyl phosphonate of the formula

CCl.

CH ₂

CH-O I

CCl,

0 I.

P-CH ₂ CH ₂ Cl

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was carried out analogously to Example 12 with 1 mol of 2 -chloroethyl-phosphorus dichloride instead of tetrachlorethylene phosphorus dichloridate and a product of the following formula was obtained:

^C 1O ^H 1O ^C1 13 ° 5 ^P
calculated: Cl / P = 14.88

found: Cl / P = 14.82

Example 14

For the production of tetrachlorethylene-bis-ißßß-trichlorethylene-Qi-chloropropyl) phosphonate the formula

0
P.

CCl ₃ CH-OP- (OCH ₂ CHCX ₃ ) ₂

Cl X

in which X = Cl or bromine, a device according to Example 1 and 250 ml of benzene, 0.65 mol of tetrachlorethylene phosphorus dichloridate according to Example 6 and 11.81 g of anhydrous aluminum chloride were used, with 2 mol of ßßß-trihalo-1, from the dropping funnel. 2-epoxyalkyl (C ₁ to C,) or cycloalkyl such as ßßß-trichloro-1,2-epoxypropane was slowly added dropwise while maintaining the temperature of the reaction mixture of 50 to 60 ° C. After the exothermic reaction had ended, the temperature was increased to 70 ° C. when 0.35 mol of Ti phosphorus dichloridate was added.

temperature increased to 70 ° C, than 0.35 mol of tetrachlorethylene

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The end product was purified as in Example 1 and the solvent was removed at 60 ° C. and below 12 mm Hg.

Analysis data of CgH ₇ Cl ₁₂ O ₄ P calculated: chlorine / P = 13.73 found: chlorine / P = 13.68

Example 15 For the production of 5,5 ^ -Bis- (chloromethyl) -ß-chloroethyl-1-

hydantoin phosphorochloridate of the formula

(ClCH ₂ J ₂ °

O I.

ClCH ₅ CH ₀ - P - N NH Cl

an apparatus according to Example 1 and 25Ο ml of toluene, 1 mol of triethylamine and 2 mol of 5,5-bis (chloromethyl) -hydantoin, prepared from 1,3-dichloroacetone and sodium cyanate and / or potassium »used. Were added dropwise 0.65 ml o ^ -Chloräthylphosphoro dichloride in a small amount of toluene, whereby the temperature of the reaction mixture to 55 to 60 ⁰ C in analogy to Example was maintained fourteenth After filtration, the solvent was distilled off in vacuo at 95 ° C. and 10 mm Hg. Analysis values of C _{7 HqCl 4} N ₃ O ₃ P
calculated: Cl / P = 4.58
found: Cl / P = 4.49

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Example 16

For the preparation of 5,5-bis (chloromethyl) -Qo-tetrachlorethylene oxy-Od ¹ -chlor-1-hydantoinphosphonate of the formula

(ClCH ₂ ) ₂

? π

CCl ₃ CH-O-P -N NH

Cl Cl I ^

was carried out analogously to Example 15, with ^ -Chloräthylphosphordichloridat was replaced by tetrachlorethylene phosphorus dichloridate (Example 6).

Analysis values of C ₇ H ₆ Cl ₇ N ₃ O ₄ P calculated: Cl / P = 8.01 found: Cl / P = 7.8O

Example 17

For the production of bis (ßßß-trichlorethylene-C ^ -hydroxy-ß-oxyßßß-trichlorethyleneod'-hydroxy-bis (methyl) -1,2-pyrocatechol phosphate the formula

CCl CCl. , 3.3

CH-O-CCH ₀ ClI - P OH OH

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were analogous to Example 1 with 250 ml of benzene, 1OO ml of triethylamine , 1 mol of ßßß-trichlorethylene-Oki-hydroxy-ß-oxy- oc ' -hydroxy trichlorethylene, prepared by reacting chloral with chloral hydrate, and 5 g of MgCl- worked. The reactor was washed with N_, whereupon 1 mol of 1- chloroethyl-1,2-pyrocatechol phosphate was added at room temperature at such a rate that the reaction temperature remained at about 55 to 60.degree. After the exothermic reaction had subsided, the mixture was heated and the temperature increased to 65 ° C. and left there for a further two hours. The reaction mixture was cooled to room temperature, filtered and purified analogously to Example 1, the solvent being removed in vacuo at 60 ° C. and 13 mm Hg. Analysis values of C ₁₂ H ₁₁ Cl ₆ O,? calculated: Cl / P = 8.87 found: Cl / P = 8.82

Example 18

For the preparation of (ßßß-Tribromäthylen-O ^ -hydroxy-ß-oxy-ßßß- trichlorethylene-G ^ * -hydroxy-bis (methyl) -1,2-pyrocatechol- _v phosphate of the formula

CBr ₁ CCl _n

II ³

CH-O-CCH ₂ CH ₂ -P

CH OH

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was carried out analogously to Example 7, with ßßß-Trichloräthylen- <V ~ hydroxy-ß-oxy-Oi'-hydroxy-trichlorethylene by 1 mol ßßß-Tribrom-ce-hydroxy-ß-oxy-c ^ '- hydroxy-ßßß-trichlorethylene was replaced.

Analysis values of C ₁₂ H ₁₁ Cl-JBr ^ O ,?

calculated: Br / P = 7.74

found: Br / P = 7.71

Example 19

For the production of bis (ßßß-trihalo-cvr-hydroxyethylene-ß ¹ oxy-diethylene glycol tetrachlorethylene phosphate of the formula

0
i

CCl.CH-OP- (OCH ₂ CH ₂ OCIi ₂ CH ₂ OCHCX ₃ ) ₂

Cl ^0H

in which X = Cl or Br, a device according to Example 1 and 10 moles of tetrachlorethylene phosphorus dichloridate and 200 ml of benzene were used, including 2 moles of (ßßß-tribromo- ° <r-hydroxyethane) -ß '-oxy via a dropping funnel -2, 2-oxydiethanol, 150 ml of benzene and 210 g of triethylamine were added dropwise while maintaining a temperature of less than 18 C. After the exothermic reaction had ended, the solution was ^{left at 30 °} C. for 30 minutes. The salt was filtered off and the resulting solution was heated under NL and purified under vacuum at 55 ° C. and 18 mm Hg.

70985 n / 0967

Analysis values of C.JL.Cl.Br 0. P
calculated: Br / P = 15.48
found: Br / P = 15.38

Example 20

For the production of ßßß-trihalo-Qc-hydroxyethylene-ß'-oxydiethylene glycol-2-tetrachlorethylene-aminophosphate the formula

CCI ₃ CHO-P-OCH ₂ CH ₂ OCH ₂ Ch ₂ O - CHCX ₃ Cl NH ₂ OH

in which X = Cl or bromine, was in a solution of 0.1 mole ßßß-trichloro-0 (: - hydroxyethylene-ß ^l -oxy-diethylene glycol-2-tetrachlorethylene chlorophosphate, prepared according to Example 19, but with a ratio of the reactants of 1: 1 and 200 ml of CCl., ammonia were added dropwise with stirring at temperatures of 20 to 35 ° C. The reaction mixture was mixed with 80 ml of water while stirring to dissolve the by-product ammonium chloride was then stirred into chloroform, filtered and distilled at 50 ° C./12 mm Hg.
Analysis values of C ₈ H ₁₃ Br-Cl ₄ NO ₆ P
calculated: Br / P = 7.74
found: Br / P = 7.67

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Example 21

For the production of ßßß-trihalo-Qci-hydroxyethylene-ß'-oxydiethylene glycol-2-tetrachlorethylene hydrazine phosphate the formula

0 i

CCl ₃ - CH - 0 - P - OCH ₂ CH ₂ OCH ₂ CH ₂ -O - CH - CX ₃

Cl NH OH

I HH-

in which X = chlorine or bromine, the procedure was analogous to Example 20, 1 mol of hydrazine hydrate was used instead of ammonia.

Analysis values of CgH ₁₄ Cl ₇ N ₂ O ₆ P after purification: calculated: Cl / P = 8.01 found: Cl / P = 7.92

Example 22

For the production of Od-tetrachlorethylene-ß-chlorpropionamidphosphorochloridate the formula

O I

CX - CH - 0 - P - CH ₂ - CH - C (O) HH ₂ ³ III

Cl Cl Cl

in which X = chlorine or bromine, a device according to Example 1 with 1 mol of acrylamide or its derivative and 600 ml

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272A2A3

Dioxane charged. 1 mol of tetrachlorethylene phosphorus dichloride was slowly added dropwise while maintaining a temperature of 30 ° C. The mixture was then stirred at 30 to 35 ° C. for 10 minutes and at 45 ° C. for 35 to 40 minutes. The product was purified under nitrogen at 45 ° C / 15 mm Hg. Analysis values of C ₅ H _{6 CIgNO 3} P
calculated: Cl / P = 6.86
found: Cl / P = 6.82

example 23

For the production of poly (halopropane) -o ^ -oxy-ßßß-trihaloethylene-OC ¹ -bis- (ß'-halo-methylpropanol) -phosphate of the formula

RR 0

Il I

CH-C-CH ₇ O-CHO -PIO (CH ₂ CHO) ₂ H] ₂

1I ² II

Br Br CX ₃ CH ₂ X

in which R = H or Br and X = Cl or Br, a device according to Example 1 was charged with 1 mol of οί, β-dibromopropanol or c * r, oc ' , β, β'-tetrabromopropanol under nitrogen, the temperature being with the addition of 1 mol of bromal or chloral was increased to 45 to 55 ° C. The reaction mixture was cooled to 10 ° C. with the addition of 1 mol of P ₃ ^O S ′ ^, the temperature of the solution being kept below 15 ° C. After the exothermic reaction was continued at the slow addition of 4 moles of epichlorohydrin or epibromohydrin to 45 to 50 ° C

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warmed up. The temperature was kept below 70 ° C. It was then cleaned and cooled at room temperature. Analysis values of C ₁₇ H ₂₇ Cl ₇ Br ₂ O ₉ P calculated: Br / P = 5.16 found: Br / P = 5.10

Example 24

For the production of bis (2,3-dibromo-2-propene-1-oxy-ßßß-tribromoethylene-0 £ -oxy) -phosphate-bis (ß-chloromethylpropane glycol) the formula

CH = CCH ₀ OCHO Br Br CX

0 I.

-PO- (CH ₂ CHO) 2 H

CH ₂ Cl

were carried out analogously to Example 23 in the presence of 2,3-dibromo-2-propene-1-oxy-ßßß-tribromo-O £ -hydroxyethylene. Analysis values of C., H ₁ -Cl ₂ Br ₁₀ OoP calculated: Br / P = 25.88 found: Br / P = 25.79

Example 25

For the production of bis (ßßß-trichlorethylene-1,1'-carboxyaminophenyl isocyanate) -phosphono-2-oxy-ßßß-trichlorethylene-O ^ -carboxyamino-phenyl-isocyanate the formula

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CCl. O

ι ³ ι

O - ClI - O - C - NH / ^WC0

CCl ₃ CH - P - CHOC - NH NGO

0 O CCl ₃

¹ CH,
O = C- KR .NCO

CH ₃ ^ V = /

was worked with a device similar to Example 1, which with 1 mole of bis (ßßß-trichlorethylene-1,1'-hydroxy) -phosphonooxy-o ^ -hydroxy-ßßß-trichlorethylene, produced by reacting broma1 or chloral or chloral hydrate with Me (I, II, III) (phosphides), was loaded as

OH

I.
0 CHCCl-

CCl _ CH-P- CHCCl-, -3 I 11 1 J

OH 0 OH

Were 3 moles alkyl or aryl from the dropping funnel or polyaryl-diisocyanate such as toluene diisocyanate (80/20) was slowly added dropwise while maintaining a reaction temperature below 8O ⁰ C under a nitrogen blanket. The reaction mixture was left with stirring at this temperature for a further 90 minutes. 5.58 mol of further toluene diisocyanate with 25% NCO residues were then added, which was obtained by heating

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TDI or other aryl polyisocyanates with lithium acetate had been obtained. It became a pale yellow liquid received the following composition:

^C 33 ^H 24 ^C1 9 ^N 6 ° 11 ^P calculated: Cl / P = 10.30

found: Cl / P = 10.26

Example 26

For the preparation of ßßß-trichloropropane-o ^ -carboxy-aminoisocyanate-phosphono-bis- (trichlorethylene-oxy-Qd ¹ -carboxy-amino isocyanate) of the formula

CCl ₃ CHCH ₂

0 I.

0 I.

0 = C - NH

NCO

(-OCHCCl ₃ ) 2 0

C-NII

NCO

was carried out analogously to Example 25, with bis- (Q ^ -hydroxyßßß-trichlorethylene) -phosphono-ßßß-trichloro-Qii-hydroxy-propane, made from Od-hydroxy-methy1-phosphonic acid, HOCH_POHOH, and chloral, was used, viz

CCl ₃ CHCH ₂

ρ - ~ *

OCHCCl I
OH

0 - CHCCl.

OH

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The product obtained is a pale yellow liquid of the formula

C ₃₄ H ₂₆ Cl ₉ N ₆ O ₁₁ P

Analysis values calculated: Cl / P = 10.30 found: Cl / P = 9.90

Example 27

For the preparation of 1-bis (ßßß-trihaloäthylen- Q £ -urylenphenylisocyanat) -oxy-diethyleneglycol-2-tetrachlorethylene phosphate the formula

0
I.

CCl ₃ CHO - P - (OCH ₂ CH ₂ OCH ₂ CH ₂ OCHCx ₃ ) 2

Cl O = C NH r ^ NCO

CH ₃ -A = /

a device according to Example 1 was used, which was charged with 1 mol of tetrachlorethylene-phosphorus dichloride (Example 6) and 2 mol of diethylene glycol under nitrogen. The reaction mixture was heated to 50 ° C. and 2 moles of triethylamine were added. After purification, the solution obtained was ^{treated with 2 mol of chloral at 50 °} C. and left to stand for 40 minutes. Then 2 mol of toluene diisocyanate with 25% NCO residues were added at 90 ° C. and the mixture was left at this temperature for a further 25 to 35 minutes. There was obtained a pale yellow liquid having the following formula:

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Analysis values C ^ ₃ H _{1 -.Cl 10} N .O. 2 ^p
calculated: Cl / P = 11.44
found: Cl / P = 11.36

Example 28

For the production of o ^ -Tetrahalo-ethylene-o ^ ¹ -polyhalophenyl-Me-phosphate and c ^ -Tetrahalo-ethylene - * ^ - ¹ -polyhalo-cycloalkyl-Me-phosphate of the formulas

0 0

I! B.

CX -, CHO - P - 0 - Me CX3CHO - P - 0 - Me

"Ί I Cl

in which X = Cl or Br and Me = Na, K, Li, Zn, Mg, Ni, Ca, Ba, Sb, Ti, V, Sn are salts, a device analogous to Example 1 with 0.2 mol of tetrachlorethylene phosphorus dichloridate was used or phosphorothiochloridate (Example 6 or 8) and 0.2 mol of polyhalocycloalkyl or polyhaloaryl alcohol such as 2,4,6-tribromophenol and 100 ml of dried benzene are added. To the reaction mixture were not added dropwise while maintaining a temperature of about 25 to 30 ⁰ C 0.2 moles of triethylamine. The mixture was stirred at 50 ° C. for two hours. It was then filtered and washed with benzene. The resulting solution was at 40 to 50 C in the presence of triethylamine on addition

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of 18 g of H-O heated in 12 minutes after cleaning, whereby the following product B was obtained:

CCl-CHO - P

³ I.

Cl

0.5 g of potassium salt was added to the resulting solution and the mixture was heated to 50 ° C. for a further 20 minutes. The unreacted product was distilled off, whereby CgH ₃ Br ₃ Cl ₄ O ₄ PK was obtained. Analysis values calculated: Br / P = 7.74 found: Br / P = 7.64

Example 29

For the preparation of o ^ -Tetrahalo-ethylene-c *: ¹ -phosphate (metha) acrylate of the formula

0
I.

CX-, CHO-P-0-Q Cl 0

in which X = Cl or bromine and Q = H or an alkyl, alkenyl, cycloalkyl, aryl or heterocyclic epoxy ester of the acrylic

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or methacrylic acid, was analogous to Example 28, replacing 2,4,6-tribromophenol with tetrachlorocyclohexanol and under Replacement of the metal salts by 1 mol of the corresponding epoxy acrylate or methacrylate derivatives, such as cycloalkyl / or aryl / or heterocyclic derivatives such as hydantoin derivatives, worked.

The following formula shows the reaction with 1 mol of glycidol methacrylate at 50 C in the presence of TMAC as a catalyst when heated to 60 ⁰ C for a period of 10 to 120 minutes. The unreacted product was distilled off to obtain a compound represented by the following formula:

0 CH-,

Il I ^J

CCl ₃ - CHO - P - 0 - CHp - CH - CO-, -C = CH-,

Il I ^{l 2}

Cl 0 OH

Analysis values calculated: Cl / P = 9.15
found: Cl / P = 9.09

Example 30

For the production of Qei-Tetrahaloäthylen- Qt ' -bis- (polyhalo cyclohexane) phosphate of the formula

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in the X is chlorine or bromine, with a device according to Example 1 and 0.2 mol of tetrachlorethylene phosphorus dichloride (Example 6) or phosphorothiochloridate (Example 8) and 0.4 mol of polyhalocyclohexanol such as tetrachlorocyclohexanol or its isomers or polyhaloaryl alcohol and 1OO ml dry benzene worked under nitrogen. 0.6 moles of triethylamine were added in such a way that the temperature of the reaction mixture did not rise above 25.degree. To 30.degree. The mixture was then stirred for 2 hours at 50 ° C. under nitrogen and purified. Analysis values of C ₁₄ H ₁₃ Cl ₁₂ O ₄ P calculated: Cl / P = 6.87 found: Cl / P = 6.80

Example 31

To produce poly (halo-hydroxy-phosphate) carbohydrate , a device according to Example 1 and 41.13 g of carbohydrate (sucrose, fructose, glucose, sorbitol, soforose) such as glucosan, 165 ml of dioxane and 40 g of triethylamine were used. These

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The mixture was heated to 65 ° C. under nitrogen and then treated with 52 cJ tetrachloroethylphosphorus dichloride and more Leave at this temperature for 1.5 hours. The reaction mixture was cooled to room temperature and filtered, whereby a compound of the following formula was obtained

Il

c ei -cii-op (° - ^R ) _m

³ II
Cl OH

in which R denotes the corresponding carbohydrate polymer residue. The reaction mixture was heated to 50.degree. C. for 20 minutes, and 171 g of epichlorohydrin were added so slowly that the temperature did not rise above 80 to 90.degree. The resulting solution was left at this temperature for a further 360 minutes. The unreacted compounds were isolated at 80 ° C / 8 mm Hg to give a viscous polymeric material. Analysis values of C ₃₀ II ₃₆ Cl ₁₈ O ₁₈ P ₃
calculated: Cl / P = 6.87
found: Cl / P = 6.77

Example 32

For the production of bis (ßßß-trihalo-ocr-hydroxyethylene-oxyethane-aminoethoxy-2-bis (polyhalopropane) phosphate the formula

Br Br I I

CH-C- CH ₂ OIIX ¹ X '

0 O »

1 I.

P- _{O CH 2} CII ₂ -N (CH ₂ CH ₂ -O-CH-CX ₃ J ₂

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in which X = Cl or Br and X ¹ = H or Br, a device according to Example 1 with 0.37 mol of triethanolamine in 100 ml of 1,1-dichloroethylene and 102 g of triethylamine and from a dropping funnel with 0.123 mol of bis ( ^, ß-dibromopropane) phosphorochloridate or bis (C ^ ", o«: ¹ , ß, ß'-tetrabromopropane) phosphorochloridate in 50 ml of 1,1-dichloroethylene. The reaction temperature was below 15 ° C to 20 ° C The reaction mixture was then allowed to warm to room temperature, after 10 hours the solution was evaporated in vacuo to give a viscous oil as a residue and dried over sodium sulfate and filtered to give the following compounds.

Br
I. Br
I. - CH ₂ O - CH ₂ O 2 2 - CH ₂ - CH 0
I. Br
I. Br
I. P. CH
I.
Br I.
Br

-P- OCH CH ^ H

- O -CH ₂ CH - N - (CH ₂ CH ₂ OH) ₂

A neutral sample of 1 mol of the product Λ or B was heated to 40 to 45 ° C. under nitrogen. 2 moles of chloral or bromal or β-β-trihalo-1,2-epoxypropane were slowly added dropwise to this solution in the course of 30 to 40 minutes. After the exothermic reaction had ended, the mixture was left at 50 to 60 ° C. for 80 minutes.

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Analysis values of the product obtained with chloral: calculated: bromine / P = 10.32 (A)

Bromine / P = 20.64 (B)
found: bromine / P = 10.28 (A)

Bromine / P = 20.61 (B)

Example 33

For the production of bis (tetrachlorethylene-phosphorus chloride-ßchlorpropion-Q ^ -hydroxymethyl-ß-methoxyimine) the following formula

0 CH ₉ OH CH-, ΟΗ O

1 \ ^l I ^Z I

CCl-CHO - P - CH-CHCO-N-Ch ₉ OCH ₇ -N- COCHCH-, - P - OCHCCl, ³ I. I ² I ^ά I ^λ II ³

Cl Cl Cl Cl Cl Cl

was carried out with a device according to Example 1 and 2 mol of tetrachlorethylene phosphorus chloride-ß-chloropropionamide, 100 g of dioxane and 15.75 g of p-toluenesulfonic acid at 40.degree. 4.75 mol of formaldehyde were slowly added dropwise to the reaction mixture so that the temperature did not rise above 65.degree. The reaction mixture was left at 65 ° C. for 80 minutes with further stirring, cooled to room temperature and purified analogously to Example 1.
Analysis values for C _{1 .H 1} ^ Cl ₁ »N_0-P _?
calculated: Cl / P = 6.87
found: Cl / P = 6.79

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Example 34

For the production of tetrahaloethylene-ß-chlorophosphate-ß ¹ -hydrogen-oxymethylphosphite of the formula

0 O t I

CX ₃ -CH-OP-0-P-OCH, III ^J Cl Cl H

in which X = chlorine or bromine, a device analogous to Example 1 and 0.1 mol of tetrachlorethylene phosphorus dichloride (Example 6) or tetrachlorethylene phosphorothiodichloride (Example 8) and 102 ml of triethylamine and 100 ml of inert solvent were used. There was 0.1 mole of monoalkyl / or cycloalkyl / or aryl hydrogen phosphite such as ß-oxymethyl hydrogen phosphite of the formula

CH, O-P.T added so that the temperature does not

rose above 10 C. The mixture was then stirred at room temperature for 30 minutes and slowly heated to the boiling point of the solvent for 20 to 12Ο minutes and preferably 40 minutes before. It was then filtered and the solvent was distilled off. Analysis values of C _{3 HcCl 5} O ₁ -P ₂ calculated: Cl / P = 2.86 found: Cl / P = 2.77

709850/0967

Example 35

For the preparation of tetrahaloethylene-ß-chlorophosphate-1,4,5,6,7,7-hexachlorobicyclo- (2,2,1) -5-heptane-2,3-carboxy-ß'-cyclohexanol the formula

0 cl
1

CXo-CH-O-P-O-C

Cl

I Cl

was with a device according to Example 1 and 1 mol
1,4,5,6,7,7-hexachlorobicyclo- (2,2,1) -5-heptane-2,3-acid anhydride, 200 ml benzene and 1 ml (η-benzyl) -dimethylamine worked. The reaction mixture was left under a nitrogen blanket at 45 to 55 ° C. until it dissolved, whereupon 1 mol (+ 10% excess) cyclohexene oxide was added dropwise within 40 to 60 minutes at the same temperature. Then 102 g of triethylamine were slowly added dropwise.

The dropping funnel contained 1 mole of tetrachlorethylene-phosphorus dichloride (Example 6); Instead, tetrahaloethylene-ß-chlorophosphate OL ' -chloroethylphosphorus dichloride (Example 7) or tetrahaloethylene-phosphorothiodichloride can be used

709850/0967

(Example 8) can be used. The addition was carried out so uniformly that the temperature did not rise above 5 to 15, preferably 10 C. The mixture was stirred for 30 to 80 minutes, preferably 30 minutes, heated gently to the boiling point of the solvent for 20 to 120 minutes, and preferably 40 minutes, after which the product was filtered off and concentrated. Analysis values for C ₁₇ H ₁ -Cl ₁₁ O ₇ P calculated: Cl / P = 12.59
found: Cl / P = 12.47

Use of the compounds according to the invention in resins and other materials

Example 36

For use with thermoplastic / thermosetting acrylic resins, a suitable reaction vessel with stirrer, temperature controller, condenser and dropping funnel with drying tubes with pyrophosphoric acid, such as chloropyrophosphoric acid, namely 21.84 parts by weight of Cl (OH) (O) POP (O) (OH) ₂ and 58 , 84 parts by weight of urea or urea derivatives charged. The mixture was left at 50 ° C. for 20 minutes to 2 hours and then cooled to room temperature, whereupon 8 parts by weight of urea and 18 parts by weight of FR from Example 4 were added. The dropping funnel contained acrylic

709850/0967

alkyl esters or metha- (acrylic) alkyl esters such as 50.8 parts by weight of methyl methacrylate and, as a vinyl nitrile derivative, 127 parts by weight of acrylonitrile. These ingredients were stirred to obtain a clear solution.

The solution obtained can be polymerized by UV light, by electronic radiation or by a redox system .

1 part by weight of an organic peroxide such as 2,4-dichlorobenzoyl peroxide and N, N-di- (2-hydroxy- ethyl) -p-toluidine was added to this solution. The solution was heated to 40 ° C. under nitrogen to a viscous mass, whereupon the reaction was complete. The cast body was then cured for several hours at 70 ° C. in order to ensure complete polymerization. The product obtained was a refractory thermoplastic. When the product is heated to 200 ° C for 35 to 40 minutes , the acrylic copolymer becomes a fire-resistant thermosetting resin.

Example 37

The procedure was analogous to Example 36, but now in the presence of vinylamide derivatives such as 25.4 parts by weight of acrylamide and a metal oxalic acid complex , namely K_ [T JO (C ₃ O ₄ ) _{_J2H 2} O , a fire-resistant copolymer being obtained .

709850/0967

Example 38

The following components were used analogously to Example 36:

Methacrylic acid 58.42 parts by weight

Methacrylonitrile 68.58 parts by weight

Urea 8.89 parts by weight

4-Amino-2,5-imino-amido-s-triazine 0.8 parts by weight

QC-tetrachlorethylene-ß-chloropropionamide phosphorochloridate
(Example 22) 15 parts by weight

Azoisobutyronitrile as a stimulator 0.8 parts by weight

These ingredients were stored for 48 hours at 50 ° C. under nitrogen heated and then 4 to 10 minutes at 90 ° C. The deformable thermoplastic copolymer obtained was fire resistant.

Example 39

Analogously to Example 36, a device with methyl meth-

charged acrylate monomer and / or other acrylic or vinyl monomer, as described, for example, in US Pat. No. 3,847,865,

3 843 612, 2 750 320 and 2 367 661, namely for example:

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Methyl methacrylate
Methacrylic acid

3,4-epoxycyclohexanecarboxylate

2- (2'-Hydroxy-50 ¹ -methylphenyl) benzotriazole

0.4 NaOH

75 % solution of t-butyl peroxypivalate

O-Ethyl-C *: - (ßßß-trichioräthyLenoxy- ⁰ ^ ¹ -hydroxy-ßßß-trichlorethylene phosphonate (as Example 4)

hydrophobic Si 1 Lcium dioxide

49 parts by weight 21 parts by weight

29.4 parts by weight

0.1 part by weight 0.4 part by weight

2 parts by weight

17 parts by weight 6% by weight in MMA base 0.1% by weight in MMA base

The polymerization was carried out analogously to the process in US Pat. No. 3,843,612. A fire-resistant polymer was obtained obtain.

EXAMPLE 4P

It was with a device according to Example 36 with mixtures

anaLog US-PS 3 843 594 worked, such as:

Methyl methacrylate
Glycidol methacrylate
Methacrylonitr i L.

435 parts by weight 266 parts by weight 159 parts by weight

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hydrophobic silicon dioxide 0.8 wt.% in MMA base

5,5-bis (chloromethyl) -o ^ -oxy-tetrachlorethylene-Ö ^ ¹ -chloro-1-hydantoinphosphonate (Example 16) 20 parts by weight

ßßß-Trichlor- o ^ -hydroxäthyl-ß-ethoxy-

phosphonate (Example 1) 5 parts by weight

MoO ₃ -Cu ₂ O 5% by weight in MMA base

The thermosetting molding powder obtained was fire-resistant.

Example 41

Mixtures as described in US Pat. No. 3,033,813, 3,104,154 or 3,736,241 were used in an apparatus according to Example 36 are used such as:

5 g were added to 100 g of a 50% strength aqueous ZnCl ^ solution homopolymer acrylonitrile and 1 g polypyrrolidone (analog US-PS 3,033,813) and bis (2,3-dibromo-2-propen-1-oxy-ßßßtribrom-ethylene-Qo-oxy) -phosphate-bis- (ß-chloromethyl-propane glycol) according to Example 24 was added. The obtained acrylic fiber was fire resistant.

Example 42

A homogeneous mixture of the following ingredients was made in a shaker:

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- 6O 272A2A3

Polypropylene powder with a melt index of 10

OcT-Te t räch 1 orä thy 1 en -bis- ( & c ' -polychlorocyclohexane) -phosphate (Example 30)

Bis (ß-chloromethyl) vinyl phosphate zinc (Salt)

UV stabilizer (Tinuvin P) 90 parts by weight

10 parts by weight

0.5% by weight of PP
0.08% by weight of PP

A sample was rolled out at 100 to 135 C and between Aluminum surfaces are pressed at 170 to 2OO C for one minute. the The polypropylene film obtained is fire-resistant.

Example 43

A mixture of the following ingredients was made:

Polypropylene powder with a melt index of 10

C \ i-Te t räch lorä thy len-bis-fpoly- (halocylcohexane) J phosphate (example 30)

Tetrachlorethylene-ce ¹ -2,4,6-tribromophenol-K-phosphate (Example 28)

Cadmium-ß-chloroethyl vinyl phosphate UV stabilizer 90 parts by weight

7 parts by weight

3 parts by weight 0.05% by weight of PP
0.01% by weight of PP

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A sample was rolled out at 10 to 135 ° C and between Aluminum surfaces pressed for 1 minute at 170 to 2OO ° C. the The polypropylene film obtained was fire resistant.

Example 44

A mixture of the following ingredients was made:

Polypropylene powder with a melt index of 10

o ^ -Tetrachlorethylene-bis-L ⁰ ^ '- poly (halocyclohexane) J phosphate (Example 30)

ZnCl ₂ -2DMF Sb ₂ O ₃

9O parts by weight

7 parts by weight 0.5 to 5 parts by weight 2.7 parts by weight

A sample was rolled out at 100-135 ° C and between Aluminum surfaces for 1 minute at 170 to 2OO ° C ./pressed. the obtained polypropylene film was fire resistant.

Example 45

A mixture of the following ingredients was made:

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Polyvinyl chloride resin (PLiovic S-51 der

Goodyear Rubber Co.) 90 parts by weight

«V-Tetrach Lorethylene- <V -2, 4, 6-

tribromophenol-K-phosphate (Example 28) 7 parts by weight

A sample was rolled out at 80 to 125 C and between Aluininiumf puddles pressed for 15 to 25 minutes at 120 ° C. the The PVC film obtained could be colored and was fire-resistant. Instead of the PVC resin Pliovic, the same result could also be carried out with another PVC resin SM-250 from ETHYL Co. will.

Example 46

A polyester plate was produced by mixing the following ingredients and then hot pressing:

Polyester resin Hetron 23925 (made by Hooker ChemicaL Co.)

Qdf-Tetrachlorethylene- <*: '-2, 4, 6-tribromophenoxy-ß- Q ^ -hydroxyethyl methacrylate (Example 29)

il

9O parts by weight 8 parts by weight

CCl -.- CH-OPO-CH ₀ CH-CO ₉ -C = CIU

7098 5 0/0967

Benzoy! Peroxide

Sb ₂ O ₃

1.2% weight percent in the resin

1.68 parts by weight

The procedure was analogous to Example 45, a fire-resistant and dyeable product being obtained.

Example 47

It became a polyester plate by mixing and hot pressing

made of the following components:

unsaturated polyester resin according to

U.S. Patent 3,372,176 (Diamond Shamrock Co.) 90 parts by weight

Bis- (2,3-dibromo-2-propen-1-oxy-ßßßtribromäthylencs ^ -oxy-phosphate-bis- (ß-chloromethyl-propane-glycol) (Example 24)

ZnCl ₂ .2DMF
Benzoyl peroxide

5 parts by weight of 0.5 to 2 parts by weight

1.06% weight percent in the resin

The procedure is analogous to Example 45 and gives a dyeable, fire-resistant product.

Example 48

A polyester plate was made by mixing the following ingredients and then hot pressing:

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Polyester resin PBT VERSEL-1200 from Allied Chem. Co.

O-ethyl bis (O ^ -oxy- οέ ' -hydroxyethyl-ßßß-trichloro) phosphate (Example 4)

ZnCl ₂ -2DMF
Sb ₃ O ₃

90 parts by weight

8 parts by weight 0.5 to 5 parts by weight 1.5 parts by weight

The procedure is the same as that of Example 45, whereby a fire-resistant product was obtained.

Example 49

It became a polyester plate by mixing the following

Components manufactured:

Polyester resin PBT-VERSEL-11OO (Allied Chem. Co.)

cv-tetrachlorethylene-ß-chloropropionamide phosphorochloridate (according to example 22)

SbCl ₃ DMF (or ZnCl ₂ 2DMF)

90 parts by weight

8 parts by weight 2 parts by weight

After mixing the ingredients and hot pressing Analogously to Example 45, a fire-resistant and dyeable product was obtained.

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Example 50

A polyurethane foam was produced by known methods using the following components:

8.89 g of a starch-glucoside polyalkylene ether (with OH 450 to 560) were mixed with 4.40 g of bis- (β-β-trichloro-oe-hydroxyethylene) -β-oxy-diethyl glycol-2-tetra-chloroethylene phosphate (according to Example 19) and 8.89 g of toluene diisocyanate mixed and heated for 1 to 0 minutes. You can also use 50 to 70% TDI with bis (ßßß-trihalo-o ^ -urylene-phenyl isocyanate-ß'-oxy-diethylene glycol tetrachlorethylene phosphate) from Example 27. A nonionic emulsifier based on vegetable oil (0.50 g) and 0.5 g HO with a content of 0.17 g triethylenediamine were slowly added dropwise with stirring over the course of 20 to 30 seconds. The reaction mixture was poured into a wax-lined box to allow it to foam at room temperature. A fire-resistant polyurethane foam was obtained.

Example 51

The procedure was analogous to Example 50 with 2.0 g of tetrachloroethylene phosphate bis (methoxyisocyanate) (from Example 7) and 6.8 g of silicone tetra (methoxy isocyanate) instead of 8.89 g of TDI.

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The foam obtained was UV-resistant and fire-resistant.

Example 52

In this example the compound of formula A is used:

N-ethylmorpholine 0.12 part by weight

Silicone oil O, O3 parts by weight

Dibutyltin 0.08 part by weight

Water 0.46 parts by weight

Polyol as in Example 32, namely bis (ßßß-tribromo- Q ^ -hydroxy ethylene) -oxy-ethane-amino-ethoxy-2-bis (tetrabromopropane) phosphate, 139 parts by weight, mixed with 8.89 parts by weight of polypropylene glycol. After the addition of 3.33 g of bis (ßßßtrihaloäthylen-O ^ -urylen-phenyl-isocyanate) -oxy-diethyleneglycol-2-tetrachlorethylene phosphate (as in Example 27) 4.57 g of toluene diisocyanate were added.

The polyurethane foam obtained is fire-resistant.

Example 53

Wood, such as Douglas fir or wood shavings, redwood, white spruce, western hemlock, western pine, southern pine or other types of wood, as well as plywood and cardboard, were used as the material. A 1/8 inch plate was made with

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- D / -

ßßß-Trichlor-Ocr-hydroxyethyl-ß-ethoxy-phosphonate (Example 1) or Ο, Ο-dimethyl bis (CVf-oxy- cyr '-hydroxyethyl-ßßß-trichloro) phosphonate (Example 3) in amounts of 70 to 80% parts by weight and tris (haloaliphatic) phosphites such as tri- (ß-chloropropyl) phosphite diluted in amounts of 30 to 20% parts by weight with methylene chloride or chloroethylene derivatives impregnated with a boiling point below 100 ° C with 15 to 70% parts by weight of the materials. The materials were at room temperature Impregnated for 80 to 100 minutes at a pressure of 2.5 to 50 atmospheres. Subsequently, the solvent removed by heat, taking fire-resistant materials, namely wood, wood chips, panels or cardboard without modification physical properties with good moisture resistance were obtained.

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Claims (1)

UtXKÜLLS SrOLBERU PATENTANWÄLTE HAMBURG 52 BESELERSTRASSE 4 DR. JD FRHR. by UEXKÜLL DR. ULRICH GRAF STOLBERG 2 / Z 4 t 4 J DIPL.-ING. JÜRGEN SUCHANTKE John Joseph Waldmann (Prio: May 28, 1976 US 691 017 - 13999) Monroe Road, Apartment 3,
Charlotte, NC / V.St.A. Hamburg, May 12, 1977 Halogen-containing organic phosphorus compounds and their use as flame retardants especially in plastics Claims Halogen-containing organic phosphorus compounds of the general formula R'I! ^ p (A - CHCX ₃ J _n (Ri). ^B. 2-n in the η the number 1 or 2,
X chlorine or bromine, 709R ^f .i _i / 0967 Z oxygen or sulfur, Λ a divalent radical with one or more oxygen bonds, B a chlorine, bromine, hydroxy, alkoxy, alkenyloxy or ureido hydrocarbyl isocyanate radical, R. a bromine, chlorine, hydroxy, hydrocarbyl or hydrocarbyl oxy radical, R _{2 is} a bromine, chlorine, amino, hydrazino, hydroxy, -R - radical or an -OMe radical, in which Me is the salt of a metal from the group Na, K, Li, Zn, Mg, Ni, Ca, Ba, Sb, Ti, V, Sn, or an -OQ- radical in which Q is an epoxy ester derivative of an acrylic or methacrylic acid and where In _{the case of η = 1, R 1} and R "together represent a divalent arylenedioxy radical mean. 2. An organic phosphorus compound according to claim 1 of the following formula (R ₁ ) - ρ - ACHCX, ² I ³ 3. An organic phosphorus compound according to claim 2, characterized in that the radical R is a lower (C to C.) Aikoxy radical and B denotes a hydroxy, chlorine or bromine radical. 7 09 f »'■■' ■■ '096 7 - 3 - 272Λ243 4. Organic phosphorus compound according to claim 2, characterized in that R is a radical of the following general Formula in which u has the value from 1 to 2 and B is a chlorine or bromine radical: -0 (CH ₂ CH ₂ O) _U ^{C. HCX} 3 OH 5. Organic phosphorus compound according to claim 2, characterized in that the radical R has the following formula in which u has a value from 1 to 2 and B is a halogenated substituted alkoxy radical: -O (CH ₂ CHO) _U H CH ₂ X 6. Organic phosphorus compound according to claim 2, characterized in that R. is a radical of the following general formula Ii JnICO and B is a residue of the following general formula nco 709850/0967 7. Organic phosphorus compound according to claim 2, characterized in that it has the following general formula owns: ^ ₁ λ CHCX ₃ Y ^Y in which Y, regardless of the meaning of X, is chlorine or bromine. 8. An organic phosphorus compound according to claim 2, characterized in that it has the following formula: HC. Il \ P Λ CHCX ₃ HO ^X 9. An organic phosphorus compound according to claim 1, characterized in that it has the following general Formula has: Il R ₁ -P (ACHCX ₃ ) 709850/0967 TO. An organic phosphorus compound according to claim 1, characterized by having the following general
Formula has: ACHCX. I ³ 11. An organic phosphorus compound according to claim 1, characterized in that it has the following general
Formula has: R. ^ I! ^ PA CUCX ₃ R * X in the row a chlorine, bromine, amino, hydrazino,
Hydroxy, -OMe- or -OQ radical. 12. Organic phosphorus compound according to claim 11, characterized in that R. is a chlorine, bromine, amino,
Is hydrazino or hydroxy. 13. Organic phosphorus compound according to claim 11, characterized in that A is an oxy radical and B is chlorine or bromine is. 709860/0967 14. Organic phosphorus compound represented by the following general formula Λ ¹ CHCX, I ³ OH where X is chlorine or bromine, Z is oxygen or sulfur, A 'is a direct bond or a bivalent PC radical having one or more oxygen linkages, R is a hydro carbyl or hydrocarbyloxy group. 15. Organic phosphorus compound according to claim 14, characterized in that R is a lower (C. to C.) alkoxy radical and A ^{1 is} the radical -CHO- and / or a direct PC- CX ₃ Bond is. That it contains 16 to Claim 1 polymer blend, characterized in that a reactive Fiammverhinderungsmittel according to 15th 17. Use of organic phosphorus compounds according to claims 1 to 15 as flame inhibitors, in particular for polymers. 70985 0/0967