DE2036595C3 - Phosphorus and halogen-containing polyols and processes for their production - Google Patents

Description

R ₁ OPR ₁ -O

OR,

-PR ₁ -O

OR,

IO

P-OR,

/ η

OR,

(I)

in which a = 1 or O and 1, η = O to 4, R ₁ at least one singly or multiply halogen-substituted alkyl radical or one singly or multiply halogen-substituted aryl radical with at most 8 carbon atoms, where halogen is chlorine or bromine, and at least one bydroxyl-containing Remainder of the general formula (II)

25th

CH - CH - O

I!

R ₃ R ₄

-H

(ID

30th

and Ri is a radical of the general formula (III)

J. A connection was made in a first stage of the process of the general formula (IV)

OR ₅

R ₅ OP-OR ₅

in which R _{5 is} a singly or multiply halogen-substituted alkyl radical or a singly or multiply halogen-substituted aryl radical with a maximum of 8 carbon atoms, where halogen is chlorine or bromine, and b is zero or 1, with polyphosphoric acid or a mixture of polyphosphoric acid with P ₂ O _{5 is} reacted at a temperature of 20 to 180 ° C within about 0.5 to 5 hours and the partially esterified reaction mixture obtained then in a second process stage with an epoxide of the general formula (V)

i CH CH R ₄

(V)

in which R ₃ and R _{4 have} the meaning given in claim 1.

3. The method according to claim 2, characterized in that the reaction is carried out in the presence of phosphorous acid as a stabilizer and disodium phosphate as a regulator.

O-CH-CH

(III)

means, where in the formulas (II and III) R ₃ and R ₄ . a hydrogen atom or an optionally chlorine-substituted alkyl radical having 1 to 6 carbon atoms and m is a number from 1 to 4, and B) the product of the general formula (VI)

R ₁ OP-OR ₁ OR ₁

45

(VI)

in which a = O or 1 and R _{1 has} the meaning given above.

2. Process for the preparation of a mixture containing phosphorus- and halogen-containing polyols according to claim 1, characterized in, The invention relates to phosphorus and halogen-containing Polyols based on mixed polymeric phosphoric acid esters of those specified below Art and a process for making these compounds. Such connections are so far not known.

US Pat. No. 2,402,703 describes a process for the preparation of neutral alkyl polyphosphate by reacting an alkyl orthophosphorate with P ₂ O ₅ . This process does not enable the preparation of compounds of the constitution according to the invention.

It is also known from US Pat. No. 256,240, triester of orthophosphoric acid, which are substituted in the ester group by a halogen atom and a hydroxyl radical, by orthophosphoric acid with an epichlorohydrin, for example according to the following reaction equation is condensed.

C ₂ H ₅

O
H f O- C. C ₂ H ₅ ' OH Il
ρ : ₃ h ₇ I.
C.
I. X -C CH ₂ Cl _; I. i

P - (OH) ₃ + 3 A-CH ₃ - CH ₂ - CH ₂ - CH - C - CH ₂ - Cl

Finally, the United States patent describes compounds of the composition described above

i. Korinen z. B. used as a flame retardant, 65 3 099 676 the use of hydroxialkylsubstitu-

however, their use for this purpose is due to the. ated polyphosphates, which may be used in the hydro

Expensiveness of the xialkylrest necessary as a starting product can contain a halogen atom than

Epoxy compound uneconomical. Flame retardants for flammable substances, where

substituted Polyphosphorsäurealkylest.er by reaction of polyphosphoric acid with a vicinalen.epoxid can be obtained. It has been shown that these compounds are not sufficient Flammschutzffeki result and are therefore only conditionally usable as flame retardants.

The invention now relates to inexpensive and, for example, flame retardants effective phosphorus- and halogen-containing polyols based on mixed polymeric phosphoric acid esters,

The phosphorus- and halogen-containing polyols according to the invention are characterized by a mixture consisting of

A) the product according to the general formula (I)

Ii
R ₁ OPR, -

OR ₁

-O

-PR ₂ -OR.

-O

? ■

-P-OR ₁

OR ₁

(D

in which a = 1 or O and 1, η = O to 4, Rj at least one singly or multiply halogen-substituted alkyl radical or a singly or multiply halogen-substituted aryl radical with at most 8 carbon atoms, where halogen is chlorine or bromine, and at least one hydroxyl-containing radical of the general formula (II)

CH-CH
R ₃ R ₄

- H

(II)

and R _{2 is} a radical of the general formula (III)

0-CH-CH

I I

R ₃ R ₄

35

(III)

denotes, where in the formulas (II and III) R ₃ or R _{+ is} a hydrogen atom or an optionally chlorine-substituted alkyl radical having I to 6 carbon atoms and m is a number from 1 to 4, and

B) the product of the general formula (VI)

R ₁ OP-OR ₁

(Vl)

R ₅ O

OR ₅
P-OR ₅

45

₅ o

in which a = O or 1 and R _{1 has} the meaning given above.

In the general formula (I), R _{1 can} in particular mean a 2-chloroethyl radical or 2,3-dibromopropyl radical, while R ₃ , R _{4 can be} a Η atom, a methyl or chloromethyl radical.

Another object of the invention is the process for producing the phosphorus- and halogen-containing Mixture containing polyols, which consists in that in a first process stage a compound of the general formula (IV)

substituted alkyl radical or a singly or multiply halogen-substituted aryl radical with a maximum of 8 carbon atoms, where halogen is chlorine or bromine, and b is O or 1, with polyphosphoric acid or a mixture of polyphosphoric acid with P ₂ O ₅ at a temperature of 20 to 180 "C within about 0.5 to 5 hours and the partially esterified reaction mixture obtained then in a second process stage with an epoxide of the general formula (V)

'■ 5

R ₃ -CH CH-R ₄

(V)

in which R ₅ converts a single or multiple halogen in which R ₃ and R _{4 have} the aforementioned meaning.

In a preferred embodiment of the process according to the invention, the reaction is carried out in the presence of phosphorous acid as a stabilizer and disodium phosphate as a regulator.

According to a further preferred feature of the process of the invention, R _{5 is} a chloroethyl radical or 2,3-dibromopropy radical. Starting products that have proven themselves in practice are, for example, tris-2-chloroethyl phosphate or tris-2-chloroethyl phosphite.

The phosphorous acid used as a stabilizer is intended to cause a thermal change in the resulting Prevent polyol so that the latter can be obtained as a colorless product. It has been found to be functional proven to add the phosphorous acid to the starting mixture in an amount of about 0.1 to 2 percent by weight, based on the end product. The effect of the disodium phosphate is on the process sequence in the 2nd process stage limited, with the disodium phosphate a complete implementation of the "epoxide with the intermediate product produced in the first process stage is favored. Optimal sales are achieved if the concentration of disodium phosphate in the reaction mixture is about 0.1 to 2 percent by weight, based on the intermediate product of the first process stage.

The epoxide characterized by the general formula (V) as a reaction component can preferably have the following radicals _{with regard to the substituents R 3} , R _4; a Η atom, a methyl or chloromethyl radical. Ethylene oxide, propylene oxide or epichlorohydrin, for example, are suitable as reaction components. Almost complete conversion of the acid groups with the epoxide is ensured if a reaction temperature of about 60 to 120 ° C. is maintained in the second process stage. After the reaction has ended, unreacted epoxide is removed from the reaction mixture by blowing it out with, for example, nitrogen at a temperature of about 80 to 120.degree.

In detail, the following should be noted about the present invention:

The products of the first process stage obtained by the process described above generally represent mixtures of different esters of polyphosphoric acids with different degrees of condensation, which are in equilibrium with one another. The establishment of the equilibrium can be followed by CMR measurement of the contents of isolated or terminal and intermediate P0 ₄ groups.

The qualifying process products are of technical interest because they are used, for example, as flame retardants with a high flame retardant effect can be used for flammable substances. They exceed known flame retardants in terms of effectiveness, such as That described in U.S. Patent 3,256,240 or that which is commercially available Flame retardant of the formula

(C, H ₅ O), P (O) CH, N (C ₂ H ₄ OH),

IO

The statute of limitations according to the invention itself permits numerous possibilities of variation with regard to the constitution of the manufacturable Poljole. By choosing the proportions and the type of Starting components in the first process stage both the ratio of ha! Ogensubstituted to hydroxyl-substituted ester groups and the average chain length of the product obtained varies graze. Finally, there are also the possibilities for variation through the use of mixtures various phosphoric acid esters, mixtures of phosphoric acid and phosphorous acid esters, as well as different epoxides called Due to the flexibility of the method according to the invention, it is possible the diverse requirements of practice through the targeted manufacture of products with special Properties to accommodate.

example 1

In one with a stirrer. Thermometer. Gas inlet tube and reflux condenser equipped reaction vessel 2950 g of tris-2-chloroethyl phosphate (10.3 mol) and with the exclusion of air and moisture and maintaining a temperature of 25 C 294 g of phosphorus pentoxide (2.06 mol) and 349 g of polyphosphoric acid with a P ₂ O ₅ content of 84 weight percent (1.03MoI) was added. By heating the mixture to 60 ⁵ C, the P ₂ O _{5 was dissolved} in the mixture. After adding 32 g of H ₃ PO ₃ and 10 g of Na ₂ HPO ₄ , the mixture was ^{heated to 90 °} C. and kept at this temperature for 3 hours. Ethylene oxide was then passed into the mixture at 60 to 80 C until a strong reflux in the condenser charged with methanol and dry ice indicated the end of the oxalkylation reaction. After blowing out the excess ethylene oxide with nitrogen from the reaction mixture at 90 ¹ "C, 4608 g of an almost colorless liquid with a density of Df = 1.44 g cm ^{3 were} obtained. The product had a P ₂ O ₅ content of 29.5 Weight percent, a chlorine content of 23.7 weight percent, a hydroxyl number of 114 mg KOH g and an acid number of 2.5 mg KOH g.

Example 2

55

A mixture of 1863 g of tris-2-chloroethyl phosphate (6.5 mol), 737 g of polyphosphoric acid (84 percent by weight P ₂ O ₅ , 2.17MoI), 26 g of phosphorous acid and 8 g of Na ₂ HPO ₄ was in the im The reaction vessel described in Example 1 was heated to 150.degree. C. for 1 hour and then cooled to 80.degree. At this temperature, ethylene oxide was passed into the reaction mixture until a strong reflux occurred. After the unreacted ethylene oxide had been removed from the reaction mixture by purging with nitrogen at 90 ^° C., 4426 g of a pale yellowish liquid with a density of Df - 1.35 g / cm ³ , a P ₂ O ₅ content of 24, p Weight percent, a chlorine content of 15.5 percent by weight and a hydroxyl number of 212 mg KOH g.

Example 3

A mixture of 190 g of tris-2-chloroethyl phosphate (0.67 mol), H3 g of polyphosphoric acid (84 percent by weight of P ₂ O _5, 0.33 mol), 3 g of phosphorous acid and 0.9 g of Na ₂ HPO ₄ was analogous Example 1 ^{heated to 150 1} C for 1 hour. After the mixture had cooled to 50 ° C., 289 g of propylene oxide were added dropwise over the course of 3 hours. After blowing out the excess unreacted propylene oxide, 581 g of a slightly yellowish liquid remained with a P ₂ O ₅ content of 25.2 percent by weight, a chlorine content of 11.3 percent by weight and a hydroxyl number of 224 mg KOH g.

Example 4

404 g of tris-2-chlorathyI-phosphite (1.5 moles). 169 g of polyphosphoric acid with 84 percent by weight of P ₂ O ₅ (0.5 mol) and 2 g of Na-HPO ₄ were mixed at 60 ° C. in the reaction vessel described in Example 1 and heated to 90 to 95 ° C. for 1 hour. After cooling the mixture to 60 ° C., ethylene oxide was introduced until a strong reflux occurred and the unreacted epoxide was blown out with nitrogen at 90 _{° C. 768 g of a slightly colored liquid with a P 2} O ₅ content of 25.2 percent by weight, a Chlorine content of 11.3 percent by weight and a hydroxyl number of 146 mg KOH.

Example 5

In a reaction vessel analogous to Example 1, 105 g of tris (2,3-dibromopropyl) phosphate and 51 g of polyphosphoric acid with a P ₂ O ₅ content of 84 percent by weight with the addition of 0.7 g of H ₃ PO _{3 were} mixed and then for 1 hour heated to 90 C. After the mixture had cooled to 30 ° C., 86 g of tris (2-ch! Oräthy]) phosphate, 0.6 g of H ₃ PO ₃ and 0.6 g of Na ₂ HPO _{4 were} added and the mixture was again at 90 "for 1 hour. stirred C. the mixture was then introduced at a temperature of 60 to 80 ^c C ethylene oxide, to a strong reflux, the end of ethylene oxide addition indicated. Following stripping of the excess ethylene oxide by a stream of nitrogen at 80 to 90 ^c C were 347 g of a pale brownish obtained colored product which had a P ₂ O ₅ content of 21.9 percent by weight, a bromine content of 19.0 percent by weight, a chlorine content of 9.0 percent by weight and a hydroxyl number of 161 mg KOH / g.

Testing of the flame retardant effect of the polyol produced according to Example 2 by incorporation in a polyurethane foam A or B.

To produce the foam A, 49.1 g of the phosphorus and produced according to Example 2 were chlorine-containing polyol mixed with the following substances at room temperature:

80 grams of hydroxyl number polyether polyol
520 mg KOH / g,

1 g water,

1 g silicone oil SF 1066® (General Electric),

3 g triethylamine,
24 g trichlorofluoromethane.

150 g of methylenediphenyl-4,4'-diisocyanate were quickly stirred into this mixture. After a standing time of 30 seconds and a rise time of 120 seconds, the flame-retardant rigid polyurethane foam with a density of 34 g / l cured within 5 minutes at 20 ³ C. The foam had a phosphorus content of ■ 1.7 percent by weight and a chlorine content of 2,5 '■' - weight percent. ,

For producing a foam B was 23.2 g of phosphorus prepared according to Example 2 j ₀ and chlorine-containing polyol with the following substances are mixed:

90 g of polyether polyol with a hydroxyl number

from 520 mg / KOH / g, ''

1 g silicone oil SF 1066® (General Electric). ' ⁵

3.5 g triethylamine,
26.0 g trichlorofluoromethane.

150 g of methylenediphenyl-4,4'-diisocyanate were added to this mixture with rapid stirring. It arose after a standing time of 25 seconds, a rise time of 75 seconds and a curing time of 2.5 minutes at 20 C a flame-retardant rigid polyurethane foam with a density of 35 g / l. Foam B had a phosphorus content of 0.86 percent by weight and a chlorine content of 1.2 Percent by weight.

Testing of the flame retardant effect of known flame retardants in the polyurethane foams C or D.

The foam was produced by mixing the following substances:

49.1 g of a halogen-free, but phosphorus-containing polyol of the formula (C ₂ H ₅ O) ₂ P (O) CH ₂ N (C ₂ H ₄ OH) ₂ , 60.4 g of polyether polyol with an OH number of

520mgKOH / g,
1 g of water.

1 g silicone oil SF 1066® (General Electric), 3 g triethylamine and
24 g trichlorofluoromethane.

The mixture was quickly stirred into 150 g of methylenediphenyl-4,4'-diisocyanate. After 25 seconds A flame-retardant foam became a standing time, 100 seconds rise time and 4 minutes curing time obtained with a density of 35 g / l. The phosphorus content of foam C was 2.1 percent by weight.

To produce the rigid polyurethane foam D, a phosphorus- and halogen-containing polyol described in US Pat. No. 3,256,240 was used as the starting product. The polyol was prepared by reacting phosphoric acid with epichlorohydrin and had a hydroxyl number of 201 mg KOH / g, a phosphorus content of 8 percent by weight P ₂ O ₅ and a chlorine content of 18.7 percent by weight. To produce the foam, the following substances were first mixed:

49.1 g of the phosphorus and chlorine containing polyol

with an OH number of 201 mg KOH / g, 81.4 g of polyether polyol with an OH number of 520 mg

KOH / g,
1 g water,

1 g silicone oil SK 1066® (General Electric), 3 g triethylamine,
24 g trichlorofluoromethane

and then 150 g of methylenediphenyl-4,4'-diisocyanate into the mixture with rapid stirring carried. After a standing time of 35 seconds and a rise time of 130 seconds, a flame-proof poly was created Urethane hard foam with a density of 34 g / l. The curing time was 6.5 minutes. De The phosphorus content of foam D was 0.55 percent by weight and the chlorine content was 3.0 percent by weight percent.

The polyurethane foams A, B, C and P produced were tested for their properties and unc . the "test results in the following table recorded. In the table means

J is the density of the foam in (g / l),

K is the amount of phosphorus and halogens Polyols mixed with known polyols ii (percent by weight),

L Burning test according to ASTM-D 1692-59 T. The test was carried out immediately after completion de: Foam. L means the burn length (in millimeters) up to self-extinguishing;

M Abbrandtest ASTMD 1692-59 T. Dei foam was 4 weeks at 90 ^r 'C M denotes the stored Abbrandstrecke (in millimeters to self verlöschung;

N Burn test according to ASTMD 1692-59 T. Dei Foam was exposed to weathering for 7 months prior to the test. N means the burn distance (in millimeters) up to self-extinction;

P dimensional stability or change in volume de: foam (in percent) after a storage period of 4 weeks at 70 ^° C. and 95% relative humidity;

Q Compression test according to DIN regulation 53 421 in (Kp./cm ² ),

R Compression test according to DIN regulation 53 421 with 10% compression in (Kp./cm ² ).

S bending test according to DIN regulation 53 423 in (Kp./cm ² ),

T shear test according to DIN regulation 53 422 in (Kp./cm ² ),

U phosphorus content of the foam in percent by weight,

V Chlorine content of the foam in percent by weight

From the ones listed in the table. Test results can be seen that the invention Polyurethane foams are essentially the comparison products in terms of flame resistance surpass. On the other hand, despite the phosphorus and halogen content in the polyurethane molecule, its physical properties compared to phosphorus-containing but halogen-free polyurethane not disadvantageously changed also compared to known phosphorus- and halogen-containing polyurethanes, such as. B. the foam D, the foams according to the invention withstand any critical comparison or are characterized by a higher flame resistance.

609 634/348

f * 1 '

foam J κ L. M. N P. Q R. S. T U 25; l ^f material 34 38.0 not not not + 6.1 3.76 3.68 2.85 ¹ 57 IJ A. flammable flammable flammable 1 * 2 if 35 17.6 3.1 3.7 3.5 - 3.2 3.72 3.80 2.77 2.49 0.86 . ^: i
* - £ + ■ B. 35 44.8 20.5 20.3 21.1 + 6.2 3.81 3.69 2.80 2.58 ? 1 30th C. 34 37.6 28.0 32.0 31.5 + 8.6 3.70 3.63 2.71 2.49 0.55 D.

Foams A and B contain flame retardants according to the invention. Foams C and D contain known flame retardants!

J- J. · '

Claims (1)

Patent claims: I. Phosphorus and halogen-containing polyols, characterized by a mixture consisting of out A) the product according to general formula (I)