DE1518747A1 - New phosphoric acid ester polyols and processes for their preparation - Google Patents

Description

DR.-ING. BY KREISLER DR.-ING. SCHDNWALD DR.-ING. TH. MEYER DR. FUES DIPL-CHEM. ALEK VON KREISLER DIPL-CHEM. CAROLA KELLER DR.-ING. KLOPSCH

COLOGNE 1, DEIGHMANNHAUS

December 17, 1968 Ke / Ki

Establishments Kuhlmann,

25 Boulevard de l'Amiral Bruix, Paris (France)

New Phosphoric Ester Polyols and Processes for Their

Manufacturing

The process for the preparation of the new polyols is characterized in that at least one compound the general formula

O = P /

in which Y is an alkylene group and η is an integer between about 1 and 10 is heated under a pressure of less than 50 mm Hg at a temperature of about 80 ° to 250 ⁰ C and a distillation Phosphorsäureesterpolyol of the general formula

H (OY)

(OY) _n OH

0-P- (OY) _n 0

OH

separates, in which Y and η have the meaning already mentioned and χ is an integer of more than 1, preferably is from 1 to 20.

The process according to the invention can be carried out with the greatest advantage when the starting compound is an alkylene radical Y of the formula

2Q9816 / 1S10

CH - CH ₀

contains, wherein R is a hydrogen atom, an alkyl or haloalkyl radical and is advantageously a methyl radical, ethyl radical or halomethyl radical. If η in the formula is greater , 5 is than 1, the radicals Y can be identical or different

, i.e. R can have a different meaning in each of the radicals Y. For example, the group (OY) fe be formed by linking different alkylene oxides, for example from ethylene oxide and propylene oxide or from propylene oxide and epichlorohydrin.

According to the invention, the best results are achieved when the process is carried out under the following conditions is carried out: During the heating, the pressure is below 20 mm Hg, preferably at about 1 mm Hg, and the The temperature is advantageously kept between 120 and 170 ° C. In addition, it is advisable to also Remove volatile products formed in the reaction with the aid of an inert gas such as nitrogen.

W It has been surprisingly found that under the above conditions, the Phosphorsäureestertriol condensation experienced by alcoholysis between an alcohol function of a molecule and a Phosphorsäureesterfunktion of another molecule. Theoretically, this can be represented by the following reaction scheme:

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P - (OY) OH + HO (YOL -P-

y Il Il 4 |

P - (OY) _n O - P - + HQ - (YO) _n H OO

In general, the condensation according to the invention proceeds without the use of a catalyst, but in In certain cases the addition of an acidic catalyst is two-fold. Phosphoric acid or a are suitable for this purpose Friedel-Crafts catalyst, such as aluminum chloride, tin (II) chloride, Dibutyltin dichloride, titanium tetrachloride or boron trifluoride.

The polycondensation between several molecules results in a phosphoric acid polyester polyol, where a diol which is removed by distillation under reduced pressure as it is formed. the Response can be written as follows:

(OY) _n OH

H (O-Y)

(0-Y) _n OH 0 -P - (OY) J OH

+ (χ - 1) HO (YO) _n H

It is thus possible to regulate the average degree of polycondensation by changing the amount of diol withdrawn, that is, practically by considering the conditions of heating under reduced pressure, especially the duration of heating varies.

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It should be noted that a small proportion of the distill / beforehand in the phosphoric acid ester triol used may exist. This diol is formed during the preparation of the phosphoric acid ester triol Addition of alkylene oxide to the water, which in small quantities in the lOO ^ igen phosphoric acid is in equilibrium with of pyrophosphoric acid can be present according to the known equation:

In the known method, for example the U.S.A. patent 2 909 559, the alcoholysis of the hydroxyalkyl dialkyl phosphates takes place exclusively according to the following Reaction scheme:

RO I

- (0Y) _n OH

OR
■ P

- (OY) --OH + (x-1) RAW

It was thus believed that such a reaction would never lead to the formation of a diol even if the group R is derived from an alcohol or phenol whose boiling point is higher than the boiling point of the diol in which it is could have formed.

The phosphoric ester polyether triols used as starting compounds can in a known manner by reacting oxirane compounds such as ethylene oxide, propylene oxide, Butylene-1,2-oxide, epichlorohydrin or epibromohydrin of glycerine or mixtures of these compounds with anhydrous phosphoric acid. This reaction has the following well-known scheme:

2 0 9 8 1 6/1 B 1 Q

= P (OH), + 3n R - CH '- CH ₀

->

(OCH-CHg) _n OH -R

In the preparation of these Phosphorsaureestertriols oxyalkylation reaction is carried out at temperatures between about 0 ° and 120 ⁰ C, preferably between 20 ° and 80 ° C, and at normal pressure or elevated pressure. The alkylene oxide of the phosphoric acid can be gradually added, the acid can be added to the epoxide or both reactants can be added to the vessel at the same time. In certain cases it can be advantageous to carry out the reaction in the presence of an inert solvent such as ethyl acetate. Depending on the type of epoxide, the reaction temperature and the working conditions, 3 to 50 molecules of epoxide can be converted per molecule of phosphoric acid.

The oxyalkylation of phosphoric acid is autocatalyzed Reaction. The free acid functions of a molecule first catalyze the polyaddition, whereupon the last grouping P-OH is neutralized by adding a single molecule of the alkylene oxide, forming a compound the formula

(0 - CH - CHg) _a - OH

R.
(O-CH-CH ₂ ) _b -OH

R 0 - CH - CH ₂ OH

is obtained in which a + b + 1 «= j5n and a, b and η are integers.

Contrary to previous assumptions, it has been found that the ester bond of the hydroxyalkyl phosphate group, in particular

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the group of the 2-hydroxyalkyl phosphate, relative easily enters into alcoholysis reactions. Without the invention through a theoretical interpretation of the chemical taking place or to limit physicochemical phenomena, it can be assumed that the ability to alcoholysis very likely to the destabilizing effect of the terminal and especially adjacent hydroxyl group is due to the C-O-P bond. The polycondensation according to the invention thus essentially takes place from a 1,2-diol.

The condensed novel phosphoric ester polyols prepared according to the invention are generally of the form of viscous, colorless liquids and can be used, among other things, as polyols for the production of polyurethane foams be used. Due to the presence of the phosphorus components and optionally the halogenated components they are particularly suitable for the production of sohwer flammable foams and resins. Because of their polyfunctional nature, they are particularly advantageous for the production of rigid foams. Compared to the triplets they come from, their P content per OH group is higher, so it is possible to a higher amount of phosphorus per urethane function in the Introduce foams.

The compounds produced according to the invention have also been found to be advantageous components of heat transfer fluids, hydraulic fluids and lubricants.

example 1

In a 1 liter flask with 4 side ports, one Stirrer, a reflux condenser, a separating funnel, a thermometer and a capillary

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NEN dip tube is provided, one gives dropwise ^ 48 g (6.0 mol) of propylene oxide in 98 g (1.0 mol) of anhydrous phosphoric acid. At the beginning, the temperature is kept between 20 ° and 40 ° C. by cooling with an ice bath. After the first third of the Propylenoxyds is added, the temperature allowed to rise gradually to 8O ⁰ C. The addition of propylene oxide is stopped when its reflux is steady. The reaction mixture is then kept at 80 ° C. for 1 hour and the excess propylene oxide is then driven off by introducing nitrogen at 80 ° C. under a pressure of 20 mm Hg, which is then lowered to 1 mm Hg.

The product obtained is 429 g of phosphoric ester polyether triol the formula

15 O = P

CH ₃

(OCH-CH ₂ ) _n OH

obtained in which η has a value of about 1.90. On average, this corresponds to the binding of 531 g «5 * 70 mol Propylene oxide per mole of phosphoric acid.

The product is in the form of a neutral and colorless liquid containing 7.00 hydroxyl functions per kg and 7.20 % phosphorus.

For the preparation of the condensed polyol of the invention, the reflux condenser is then replaced by a descending cooler, which is connected to a Kondensationsgefaß, followed by heating the triol under a pressure of 0.7 mm Hg, while nitrogen is passed through at I50 ⁰ 170 ⁰ C. The propylene glycols formed during the condensation are distilled off. Within

2 0 9 8 16/1610

2 hours, a total of 57 g of volatile compounds are removed from a mixture of 38 g (0.50 mol) of monopropylene glycol and 19 g (0.14 mol) of dipropylene glycol. hen. 372 g of phosphorus-containing polyol are the residue which is in the form of a colorless, viscous liquid and has the following formula:

CH,

H (OCH ₂ -CH) _n

0 -

(OCH - g _n P - (OCH-CH ₂ ) _n

CH,

OH

This polyol has the following key figures: acidity = 0.065 ml / g in NaOH solution; OH number, calculated from the amount of diol removed »4.62 / kg; n? P »1.4578; medium poly

x-1 degree of condensation (calculated according to the formula ——— = moles removed Diol per mole of triol) χ = 2.78.

It is possible to obtain a practically neutral polyol by re-treating the above product with propylene oxide. For this purpose, 1.6 g of propylene oxide are added and the mixture is heated to 100 ^° C. for 1 hour.

Example 2

The same experiment as in Example 1 is carried out, but the polycondensation time is extended from 2 to 3 hours. 43 g (0.58 mol) of propylene glycol, 23 g (0.17 mol) of dipropylene glycol and 362 g of phosphoric ester polyol are obtained with the following properties: colorless, very viscous liquid; Acidity 0.100 ml / g in NaOH solution; calculated OH number 4.10 / kg; average degree of polycondensation χ = 4.00; nf ^u = 1.4570; Viscosity 885 cS at 37.8 ⁰ C.

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Example 3

174-0 g (30 mol) of propylene oxide in 490 g (5 mol) of anhydrous are added at a temperature between 20 ° and 80 ° C. Phosphoric acid diluted with 260 g of ethyl acetate. The temperature is then kept at 80 ° C. for 1 hour the excess propylene oxide and ethyl acetate first at a pressure of 20 mm and then at a pressure of 0.2 mm Hg from. 2071 g of phosphoric acid ester triol are obtained. This corresponds to the binding of 5 * 4-5 moles of propylene oxide per mole Phosphoric acid. Calculated OH number = 7.24.

For the polycondensation the product is heated under a pressure of 0.8 mm Hg at 105 ° to 150 ⁰ C. 2.5 hours removed 332 S propylene glycols, consisting of a mixture of 200 g (2.62 mol) of propylene glycol mono and 132 grams (1.00 mole) of dipropylene glycol. The residue weighs 1739 g. Calculated OH number = 4.45 hydroxyl functions / kg.

Example 4

374 g (8.5 mol) of ethylene oxide are added to 98 g (1.0 mol) of anhydrous phosphoric acid which is dissolved in 90 g of ethyl acetate, cooling with an ice bath. During the addition the temperature is allowed to gradually rise from 20 ° to 85 ⁰ C. Subsequently, the temperature is maintained for 1 hour at 80 ⁰ C. Then it drives the excess ethylene oxide and ethyl acetate at 8o ° C under a pressure, the first 20 mm and then 0.2 mm Hg, under nitrogen from.

450 g of polyether phosphoric acid ester triol of the formula are obtained

O = P

(0CH ₂ -CH ₂ ) _n OH

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- ίο -

This corresponds to the binding of 352 g (8.0 mol) of ethylene oxide per mole of phosphoric acid. This triol contains 6.7 hydroxyl functions / kg. *

This triol is heated for the purpose of polycondensation a pressure of 0.5 ram Hg to 105 ° to 150 ° C, while one Nitrogen. The ethylene glycols formed during the condensation are distilled off. Within 58 g of glycols are removed from 2 hours, which are obtained from a mixture of 33 g (0.53 mol) of ethylene glycol, 19 g (0.18 mol) "10 diethylene glycol and 6 g (0.04 mol) of triethylene glycol consist. 392 g of phosphoric ester polyol of the following formula are obtained as residue:

H (OCH ₂ -CH ₂ ) _n

(OCH ₂ -CHg) _n OH 0 - P - (OCH ₂ -CH ,,) ,,

Jx

Calculated OH number - 3.83 hydroxyl functions / kg.

Example 5

Using the apparatus described in Example 1, 509 g (5 * 5 moles) of the epichlorohydrin of glycerol are added dropwise to 98 g (1 * 0 moles) of anhydrous phosphoric acid while cooling with an ice bath. During the addition, the temperature is allowed to rise gradually to 20.degree. To 75.degree. This temperature is then maintained for 1 hour. The excess epichlorohydrin is removed by increasing the temperature of the liquid to 100 ^° C. under a pressure of 10 mm Hg. This gives 5 ^ 5 g of a residue which consists of a phosphoric acid ester triol of the following formula:

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- li -

(OCH ₂ -CH) _n OH

This triol had the following properties: light yellow, viscous liquid; Acidity 0.006 ml / g in 1N solution of sodium phenolate in acetone-phenol; calculated OH number = 5.50 / kg; P = 5.68 %; Cl = 31.42 #. The product corresponded to the binding of 4.83 moles of epoxy compound per mole of phosphoric acid.

The polycondensation is carried out under the conditions mentioned in Example 1. Will be within 3 hours 111 g (1.01 moles) of monochlorohydrin were withdrawn from glycerol which passed over at 80 ° C / 0.7 mm Hg. The extremely viscous one The residue weighed 434 g and consisted of a phosphoric acid ester polyol of the following formula:

CH ₀ Cl

H (OCH-CH ₂ -) _n

Cl

_n OP- (OCH ₃ -CH) ₁ ,

Il I

CH ₂ Cl

Acidity: 0.0103 ml / g in normal solution of sodium phenolate; calculated OH number = 2.30 / kg; P = 7.15 %; Cl = 31.21 %.

Example 6

At a temperature between 15.degree. And 70.degree. C., 463 g (5,000 mol) of epichlorohydrin in 98 g (1.0 mol) of anhydrous are added Phosphoric acid dissolved in 106 g of ethyl acetate. The reaction mixture is then kept for 2 hours

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80 ° C. The unreacted ethyl acetate and epichlorohydrin are removed at 50 to 0.5 mm Hg by heating to 95 ⁰ C. This gives 66 g (0.7 mol) of epichlorohydrin and, as a residue, 495 g of triol of the following formula

CH ₂ Cl

- (OCH-CHg) _n OH

This triol is a light yellow, viscous liquid. It corresponds to the binding of 4.3 moles of epichlorohydrin per mole Phosphoric acid.

During the polycondensation, this triol is heated to 100 ° to 150 ° C. under a pressure of 0.3 mm Hg, while Nitrogen is passed through. 10J g of volatile compounds are drawn off within 2.25 hours, the 1.32 OH functions included. The residue weighed 392 g. Calculated OH number 4.28 / kg.

Example 7

102 g (1.2 mol) of epichlorohydrin from glycerine are added strength in 98 g (1.0 mol) of lOO ^ phosphoric acid, which is dissolved in 83 g ethyl acetate at 20 ° to 40 ⁰ C. This temperature is then maintained for a further 3 hours.

Then 266 g (4.58 mol) of propylene oxide are first added at 4o C, after which the temperature spontaneously rises to 7O ⁰ C. The reflux is maintained for 1 hour. The excess propylene oxide, the ethyl acetate and the unreacted epichlorohydrin are removed by gradually heating the liquid to 80 ° C. under a pressure which is initially 100 mm Hg and finally 0.2 mm Hg. The product obtained is 433 g of a triol of the following formula:

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O = P

- 13 -

CH ₂ Cl CH,

(OCH ₀ -CH-) _β (-OCH-CH ₀ ) OH γ d a cL χα

CH ₂ Cl CH,
■ (OCH ₂ -CH-) _b (OCH-CHg) _n OH

₅
(OCH-CHp-) OH

a + b = 1.1; m + n + p = 3.93; calculated OH number = 6.93 / kg

The polycondensation was carried out at 100 ° to 150 ° C under a pressure of 0.4 mm Hg. 76 g were obtained a mixture of mono-, di- and tripropylene glycols and monochlorohydrin of glycerol with 1.10 OH punctures.

The residue weighed 350 g and was in the form of a very viscous, light yellow liquid. Calculated OH number = 5.42.

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Claims (1)

Claims 1.) Phosphoric ester polyols of the general formula H (OY) (OY) _n OH 0 - P - (OY) OH in which χ is an integer greater than 1, preferably in the range up to 20, η is an integer between 1 and 10 and Y is an alkenyl radical. 2.) Compound of the formula CH-. H (OCH ₂ -CH) _n (OCH-CH ₀ ) OH I.
0 - P - (OCH-CH ₀ ) Il! ²ⁿ with the key figures; Acidity = 0.065 ml / g, OH number = 4.62 / kg, n ^ ° «1.4578 and χ = 2.78. ~) Compound j of the formula according to claim 2 having the characteristics: Aoidität = 0.1 ml / g, OH value = 4, l / kg, n ^ ° = 1.4570, viscosity at 37.8 ⁰ C - 885th cS and χ «4. 209816/1610 4.) - Compound of the formula H (OCH ₂ -CH ₂ ) _n (0CH ₂ -CH ₂ ) _n 0H 0 - P - (0CH ₂ -CH ₂ ) _n -f- Il L- 0 with an OH number of »3.83 / kg. OH 5.) Compound of the formula CH ₂ Cl CH ₂ Cl (OCH-CH) _n OH H (OCH-CH ₂ ) _n O - P - (OCH ₂ -CH) _n OH CH ₂ Cl with the key figures: acidity = 0.0103 ml / g * OH number =
2.3 / kg and with 7.15 % P and 31.21 % Cl. 6.) Phosphoric acid ester polyol from the phosphoric acid triester of propylene oxide with an OH number = 4.45 / kg. 7.) Phosphoric acid ester polyol from the phosphoric acid triester of epichlorohydrin with an OH number = 4.28 / kg. » 8.) Phosphoric acid ester polyol from the phosphoric acid triester of glycerine epichlorohydrin with an OH number = 5.42 / kg. 9 ·) Process for the preparation of phosphoric ester polyols according to claim 1 to 8, characterized in that phosphoric acid triesters of polyglycols of the general formula O = P ^ TOY) _n OHj ₃ 209816/1610 in the η is an integer between 1 to 10 and Y is an alkylene radical, is polycondensed by heating at 80 ° to 250 ⁰ C, at pressures below 50 mm Hg, and separating the resulting Phosphorsäureesterpolyol by distillation. 10.) The method according to claim 9 » characterized in that the starting material is a phosphoric acid triglycol ester of the formula O = P "i ^z (O-CH-CH _2. ) _Η -ΟΗ_ R used, in which R represents the same or different radicals within the molecule and hydrogen, a Alkyl or haloalkyl radical, in particular a methyl, Means ethyl or halomethyl radical and in which η has the meaning given above. 11.) Method according to claim 9 or 10, characterized in that that the polycondensation is carried out in the presence of a catalyst. 12.) Process according to claim 9 to 11, characterized in that the catalysts used are phosphoric acid, Friedel-Crafts catalysts or boron trifluoride is used. 15.) Process according to claim 9 to 12, characterized in that the polycondensation is carried out at temperatures of 120 ° to 170 ^o c. 14.) The method according to claim 9 to 13, characterized in that that the polycondensation is carried out at pressures below 20 mm Hg, preferably at about 1 mm Hg. 209816/1610 15.) The method according to claim 9 to 14, characterized in that volatile constituents with the aid of an inert gas leads away. 209816/1610