DE2365360A1 - Non-inflammable polyurethane moulding compsns. - contg. polyol and chemically combined chlorinated polyhydroxy phosphate ester, avoiding migration from polymer - Google Patents

Abstract

A polyurethane moulding compsn. with reduced inflammability is prepd. by condensing an organic polyol and a flame-repellent of formula (I) where R is (halogenated) 2-6C alkyl, -CH2CH2-O-CH2CH2-, phenylene or a diphenylmethane radical opt. substd. by alkyl or haloalkyl, R1 and R2 are H or (halogenated) 1-4C alkyl, x + y = 0-3 and n = 1 or 2, with an isocyanate, opt. with activators, blowing agents and/or cell regulators. (I) is chemically combined and does not migrate from the polymer.

Description

KNAPSACK AKTIENGESELLSCHAFT
K 1o86 II

Process for the production of polyurethane molding compounds with reduced flammability

(Exclusion from patent application P 23 56 o33.o)

The invention relates to polyurethane molding compositions, their flammability is reduced by adding certain flame retardants.

Polyurethanes, especially polyurethane foams, have been used in the industry found a wide field of application in a wide variety of sectors. Their importance is constantly increasing. Because Due to their excellent heat and sound insulating properties, polyurethane foams are widely used e.g. in the construction industry, Used as thermal insulators for refrigerators and trucks, pipes, tanks, tank trucks and for many other purposes. Their ease of manufacture on site is felt to be particularly favorable. Flexible polyurethane foams are used in large quantities for the production of mattresses, upholstery for furniture and automobile seats as well as in many other fields of application used industrially. ■

Sufficient flame protection is often required in these areas of application either mandatory or at least desirable.

Various attempts have therefore been made to produce flame retardant polyurethanes, mostly by any Phosphorus-containing substances as a flame retardant component

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were added. However, these substances are only used as additives embedded in the plastic, there is a risk, especially in the case of polyurethane foam, that it will with the Time to migrate out of the plastic or be leached out during weathering. Well-known representatives of such additives are for example tris (dichloropropyl) phosphate, iris (dibromopropyl) phosphate or the ethylene bis (2-chloroethyl) phosphonate described in US Pat. No. 3,147,299, Example 2 following formula *

0 0

, _0-P-0- (
H

CI-CH ₂ -CH ₂ -OPO-CH ₀ -CH ₀ -OPO-CH ₀ -Ch ₀ -CI

The risk of the flame retardant migrating out of the plastic is avoided if one is reactive Flame retardant that is chemically bonded to the plastic. In the case of flame retardant polyurethane foams In particular, phosphorus-containing polyols, such as those in the USA patent, have proven useful for this purpose 3 22o 961. According to Example 4 of this patent specification can be used as a reactive flame retardant for polyurethane foams a compound of the following constitution can be used. ·

DPG DPG

P-CH ₂ -CH-CH-

fin rtrr rtjj T) s

LL Y \

DPG 0 Br Br 0 DPG

DPG = dipropylene glycol

509 820/0957

It has now been found that the flame retardant effect that can be achieved with the above reactive flame retardant in polyurethane foams can be exceeded if a flame retardant is used which is obtained by modifying the constitution of the product described in US Pat. No. 3,147,299, Example 2, in such a way that one to the
the phosphorus atoms bound Η atoms are replaced by an organic radical containing hydroxyl groups. The invention thus provides a process for the production of polyurethane molding compositions with reduced flammability due to condensation
an organic polyol and a flame retardant containing alcoholic hydroxyl groups with equivalent amounts of an organic isocyanate compound, optionally in
Presence of activators, propellants and / or cell regulators, which is characterized in that the flame retardant is a compound of the general formula (i),

0 0

1 ii
Ci-CH ₂ -CH ₂ -OPOROPO-CH ₂ -CH ₂ -CI (I)

H- (O-CH-CH) _x - _{(O-CH 2} -CH ₂ ) _n -0 0- (CH ₂ -CH ₂ -O) - (CH-CH-O) -H R ₂ Rt R ^

in which R is an optionally halogen-substituted alkylene radical with 2-6 carbon atoms, a -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ radical, a -Pheriylen- or an alkyl- or haloalkyl- substituted
Diphenylenemethane radical, R. or R _{2 is} a Η atom, an alkyl radical or a halogen-substituted alkyl radical with 1-4 carbon atoms

χ -f y equal to 0.1 to 3 and

η denote the number 1 or 2.

In the formula (I), the substituent R is preferably a
Ethylene or hexamethylene radical, a radical of the formula

CH ₂ Br
- CH ₂ - C - CH ₂ -

^CH p.Br 509820/0957 ₄

or a radical of the formula

The compounds a) -k) recorded below, which are highly viscous, colorless and non-distillable, are preferably used Liquids are used as flame retardants containing alcoholic hydroxyl groups:

Cl-CH ₂ -CH ₂ ,

0-Ρ-Ό-

CH ₂ -

D) r-

Cl-CH ₂ -CH ₂ -O-

H- ■

P-O-CH ^ -

Cl-CHo-CH ₀ OP-OCH ₀ -

H- (O-CH-CH ₂ ) ₀ ^.

0-P- (

Xq VXJ-Av / -L · WHa

CH.

Cl-CH ₂ -CH ₂ OP-OCH ₂ -

H- (0CH-CH ₀ ) _{n of} -

CH ₂ Cl

509820/0957

JL

Cl-CH ₂ -CH ₂ -OP-OCH ₂ H- (OCH-CH ₂ ) _{1 5} -OCH ₂ -CH ₂ -0-CH ₂ -CH ₂ 0

_

-0-P-0-

-CH ₂ -CH ₂ -OPO-CH ₂ -CH ₂ -Cl

CI-CH ₂ -CH ₂ -OPO-Ch ₂ -CH ₂ -CH ₂ -

BrCH,

BrCH,

CH ₂ OP-OCH ₂ -CH ₂ -Cl O

OCH ₂ -CH ₂ O- (CH ₂ -CH ₂ O) ₀

f ^H 3

c—

OCH ₂ -CH ₂ O- (CH ₂ -CH ₂ O) _Q ^ ₅ -

-ir

V? "

O-PO-CH ₂ -CH ₂ Cl

B09820 / 0957

The proportion of the flame retardant in the polyurethane molding compound is about 3 to 40% by weight, in particular 5-15% by weight, based on the amounts of the organic polyol. The latter can be a halogen- and phosphorus-free polyether polyol or polyester polyol be. For example, a partially branched polyether polyol based on propylene oxide with a hydroxyl number of 46 mg KOH / g, a molecular weight of 35oo and a viscosity 25 ° C of 575 cP can be used.

The polyurethane molding compositions according to the invention are the isocyanate component in particular 2,4- and / or 2,6-tolylene diisocyanate or diphenylmethane-4,4-diisocyanate. The for the production of the polyurethane molding compounds required additives such as activators, propellants and cell regulators are known as such. As activators, Sp are tertiary amines and / or organotin compounds, chlorofluoroalkanes as propellants and / or water and, as cell regulators, polysiloxanes, in particular polyethylene-poly-dimethylsiloxane block copolymer, suitable.

The flame retardants containing alcoholic hydroxyl groups can be prepared by a process which consists in that a compound of the general formula (IJ)

i Ii, _%

GI-CH ₂ -Ch ₂ -OPOR ₃ -OPO-CH ₂ -CH ₂ -CI (II). H 'H

in which IL. an optionally halogen-substituted alkylene radical with 2-6 carbon atoms, means a -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ radical, a phenylene or an alkyl or haloalkyl-substituted diphenylenemethane radical, by reaction in at least stoichiometric amounts of chlorine gas at a temperature of about 0 to 5 ° C in the presence of a difficult for hydrogen chloride.

509820/0957

soluble solvent in a compound of general Formula (III)

0 0

CI-CH ₂ -CH ₂ OPOR ₃ -OPO-GH ₂ -CH ₂ Ci (III)

Cl Cl

transferred and excess after the reaction has ended Chlorine gas or hydrogen chloride formed is removed by introducing an inert gas into the reaction solution, whereupon one in the reaction solution with further introduction of the inert gas at a temperature of about 15-4o ° C stoichiometrisehe Amounts of a diol of the general formula (IV)

HO (-CH ₂ -CH ₂ O) _n -H (IV)

in which η denotes the number 1 or 2, is added dropwise after completion the reaction is distilled off the solvent and the resulting product of the general formula (V)

C1-CH ₀ -CH ₀ -Ö-P-0-R, -0-P-0-CH ₀ ~ CH ₀ C1

-PH (OCH ₂ -CH ₂ ) _n -b O (-CH ₂ -CH ₂ O) -I

in which η and R ₃ . have the above meaning, with at least stoichiometric amounts of a compound of the general formula (VI)

• HH

R ₅ - CC - R ₄ (VI)

509820/0957

in which R ^ or R _{5 is} a Η atom, an alkyl radical or a halogen-substituted alkyl radical with 1-4 C atoms, epoxidized at a temperature of about 6o-14o ° C until a permanent epoxide reflux occurs and then excess epoxide through Separated by distillation or by passing in an inert gas stream.

The production of the intermediate product is correspondingly more general Formula (III) is advantageously carried out in the presence of methylene chloride or dichloroethane as a solvent, since these solvents have relatively little of the by-product Absorb hydrogen chloride gas. The hydrogen chloride components dissolved in the solvent can, for example, by passing in Nitrogen can be removed.

The compound required as the starting product according to the general Formula (II) is known and can be prepared by the method of U.S. Patent 3,147,299, Examples 1 and 2.

The reactive flame retardants used according to the invention for polyurethane foams represent similarly constituted compounds, such as the brominated diphosphenate of the formula below described in U.S. Patent 3,220,961, Example 24

(HO-CH-CH ₂ -O-CH-CH ₂ O) ₂ -P-Ch ₂ -CH -

CH

CH

Br

are, but have the polyurethane foams of the invention compared to the products described in the USA patent 3.22o.96i an improved flame resistance.

509820/0 9 57

The following examples serve to explain the subject matter of the invention in more detail without, however, referring to it limit, with Examples 1-4 demonstrating the preparation of the agents used according to the invention, while Example 5 the effectiveness of the agents in molding compositions made from polyurethane foams explained.

example 1

Il

Cl-CH ₂ -CH ₂ OP-OCH ₂ -

H- (O-CH-CH ₀ ) _n CH ,.

J »'

A solution of 2720 g of PCI (19.8 mol) and 4 l of methylene chloride was placed in a reaction vessel equipped with a reflux condenser and stirrer, and 1224 g of ethylene glycol (19.8 mol) were added dropwise to this solution at room temperature with stirring The reaction was over for about 2 hours. A further 9.9 mol of ethylene glycol were then added in such a way that the reaction temperature did not exceed 20-25.degree. Chlorine was then passed into this solution at a temperature of 0-5 ° C. until the appearance of a yellow-green colored solution indicated the end of the reaction. The excess chlorine and the hydrogen chloride formed were expelled by passing nitrogen into the solution. With further introduction of nitrogen, 1175 g of "ethylene glycol at room temperature were then added dropwise". After the HC! Evolution had ended, the solvent was distilled off from the solution, the residue being a highly viscous colorless liquid in a yield of 94.5 % of theory was received "

509820/0957

- 1ο -

1οοο g of colorless liquid was mixed with 2 g NaJfflPO, was added and charged so long as at 8o C ^o-1oo ° C with propylene oxide until a constant reflux, the end of the propylene oxide receiving indicated. After the volatile constituents had been distilled off from the reaction mixture, 110 g of a colorless product with an acid number of less than 1 mg KOH / g substance were obtained. This corresponds to an uptake of about 0.6 moles of propylene oxide per mole of substance.

The analysis of the product resulted in the following values:

found

P 12.4% OH 6.5 %

theoretically

13.1 % 7.5 %

Example 2

CI-CH ₀ -CHoO-P-OCH ₀ -

H- (OCH-CH ₂ ) _{0 25} -

CH ₂ Cl

The procedure was analogous to Example 1, except that 1 g of Na ₂ HPO ^ was added to 600 g of the intermediate product produced and 65 g of epichlorohydrin were reacted at 12o-135 ° C. After distilling off the volatile constituents from the reaction mixture remained 66o g of a colorless oil back ₅ which corresponds to a recording YonQ, 5 moles of epichlorohydrin per mole of substance Säurezakl of the product was 1 mg KOH / g of substance and

- 11 -

S09820 / 09

Analysis showed the following values:

found

P 12.6% Cl 18.2 % OH 8.2 %

theoretically 9 % 12, 2 % 18 2 % 7,

Example 3

BrCH ₂

rt __

BrCH.

CH ₀ OP-OCH ₀ -CH ₀ -Ci

2 ι 2 2

CH ₂ -CH ₂ O- (CH ₂ -CH ₂ O) ₀ ^ -

To a solution of 1o mol of 2-chloro-1,3,2-dioxaphospholane in 2 liters of methylene chloride was added 5 mol dibromoneopentyl to the extent that the reaction temperature did not exceed 2O ⁰ C. Chlorine gas was then passed into the resulting reaction solution until the appearance of a yellow-green colored solution indicated the end of the reaction. The excess chlorine and the hydrogen chloride formed were expelled by passing in nitrogen. ", '

57o g "of the intermediate product dissolved in methylene chloride (corresponding to 1.3 mol) were then reacted with 165 g of ethylene glycol (2.6 mol) at room temperature while simultaneously introducing nitrogen, the hydrogen chloride formed being expelled. The solvent was then distilled off 1 g of Na ₂ HPO ^ was added to the residue and epoxidized with ethylene oxide at about 90 ° C. 12. g of ethylene oxide were taken up

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509820/0957

Ethylene oxide uptake corresponded to about 1.5 moles of ethylene oxide per Mole of substance.

Analysis result:

found theoretically

P 8.0 % 8.8 % Cl 9.2% 1o, 1 %

Example 4

The procedure was as in Example 3, with 228 g of ρ, ρ ¹ pylidenediphenol (1 mol) dissolved in methylene chloride and 253 g of 2-chloro-1,3,2-dioxaphospholane (2 mol) being added dropwise to the solution. With the progress of reaction, the solution became clear, the reaction temperature was 25 ~ 35 ° C was then introduced into the solution at -5 ⁰ C to +5 ⁰ C, chlorine gas until a yellow coloration of the solution.

0.8 mol of the intermediate product dissolved in methylene chloride were reacted at room temperature with 1.6 mol of ethylene glycol while passing in nitrogen. The solvent was then distilled off and 1 g of Na ₂ HPO was added. epoxidized at 100 ° C with ethylene oxide. The ethylene oxide uptake corresponded to 1.5 moles of ethylene oxide per mole of substance.

The acid number was less than 1 mg KOH / g substance.

Analysis result:

found theoretically

P 8.9 % 9.3 % Cl 11.8 % 1o, 3 % OH 7.6 % 5.1 %

509820/0957

Example 5

To test the flame-retardant effect of the according to Example 1-4 manufactured products, these were incorporated into flexible polyurethane foams and then these foams were subjected to the burn test Subject to ASTM D 1692-59T. In corresponding comparative tests, known flame retardants such as tris (dichloropropyl) phosphate, Tris (dibromopropyl) phosphate, tetra (dipropylene glycol) -2,3-dibromobutene-1,4-diphosphonate as well as ethylene bis (2-chloroethyl) phosphonate tested. The flexible polyurethane foams were produced as follows:

It was mixed;

100 g of a partially branched polyether polyol based on propylene oxide with a hydroxyl number of 46 mg KOH / g, a molecular weight of 35oo, a viscosity at 25 ° C of 575 cP and a ratio of primary to secondary OH groups such as 22 to (Desmophen 38οο ^ , Bayer, Leverkusen) 10 g flame retardant
4.2 g of water
o, 12 g of triethylenediamine
0.2g tin (II) octoate

1, above-mentioned polyethylene-polydimethylsiloxane block copolymer with a viscosity at 25 ⁰ C of 12oo cst and a specific weight of 1, o3 (L 54o ^ H Union Carbide)

53.2 g of toluene diisocyanate (8o: 2o mixture of the 2,4- and 2,6-isomers) were added to this mixture with rapid stirring. After about 20 seconds the mixture began to foam and was poured into a container. After a certain rise time, the foam began to harden. After 15 minutes storage of actor Longines at Sun ⁰ C. The curing process was complete. The foams produced in this way were tested for their flammability in accordance with the ASTM D 1692-59T standard, both in their freshly produced state and after artificial aging by storage for 7 days at 80 ° C. and 100 % relative humidity. The results obtained are summarized in the table below:

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Flame I. SE 34 mm II sec protective agent SE 3o mm sec A. 9o SE 41 mm , 29 sec B. 92 SE 38 mm , 18 sec C. 84 SE 64 min , 23 sec D. 95 SE 46 mm , 29 sec E. 85 SE 42 mm , 44 sec F. 9o SE 3o mm , 37 sec G 11o , 28 H 7o , 16

- 14 -

TABEL

III

SE 26 mm, 9 sec

■ SE 25 mm, 11 sec

SE 40 mm, 19 sec

SE 32 mm, 9 sec B 114 mm / min

SE 62 mm, 41 sec

SE 69 mm, 43 sec

SE 45 mm, 23 sec

Product according to example 2 of the application

Product according to example 3 of the application

Product according to example 4 of the application

Tris (dichloropropyl) phosphate

Tris (dibromopropyl) pho sphat

Tetra- (dipropylene glycol) ~ 2,3-dibromobutene-1,4-diphos-

In the table:

Flame retardant:

A: Product according to example 1 of the application

phonate (corresponds to example 4 of the USA patent 3 22o 961) H: ethylene bis (2-chloroethyl) phosphite (corresponds to

Example 2 of the USA patent 3 147 299)

Column I: Rise time of the foam in seconds

Column II: Burning test according to ASTM D 1692-59T, with the Test immediately after completing the

Foam made »
Column III i Burning test according to ASTM D 1692-59T, the test being carried out after the foam had been stored for 7 days at 80 ° C. and 100 % relative humidity.

509820/0957

SE: self-extinguishing after .... mm and .... seconds B: combustible with a burning rate of .... mm per minute.

As can be seen from the results shown in the table, those with flame retardants according to the invention equipped foams · consistently have a shorter burning time until the foam self-extinguishes than the known flame retardants and are therefore technically superior to the latter.

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509820/0957

Claims (9)

Patent claims: Process for the production of polyurethane molding compounds with reduced flammability by condensation of an organic polyol and a flame retardant containing alcoholic hydroxyl groups with equivalent amounts of an organic isocyanate compound, optionally in the presence of activators, blowing agents and / or cell regulators, characterized in that the flame retardant - agent is a compound of the general formula (I), Cl-CH ₂ -CH ₂ H- (O-CH-CH) _x - (O-CH ₂ -CH ₂ ) _n -0 R ₂ R ₁ -0-POROPO-CH ₂ -CH ₂ -Cl 0- (CH ₂ -CH ₂ -O) _n - (CH-CH-O) ₇ -H in which R is an optionally halogen-substituted alkylene radical with 2-6 carbon atoms, a -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ radical, a phenylene or ein.alkyl- or haloalkyl-substituted diphenylenemethane radical, R ₁ or R _{2 is} a Η atom, an alkyl radical or a halogen-substituted alkyl radical with 1-4 C atoms χ + y equal to 0.1 to 3 and η denote the number 1 or 2. 2. The method according to claim 1, characterized in that R is an ethylene or hexamethylene radical, a radical of the formula CH ₂ Br -CH ₂ - or a radical of the formula is. - 17 - 509820/0 957 3. The method according to claim 1 or 2, characterized in that the flame retardant containing alcoholic hydroxyl groups is one of the following compounds a) - k): Cl-CH ₂ -CH ₂ O-P-O- CH ₂ - Cl-CH ₂ -CH ₂ H- (OCH ₂ -CH ₂ ) _{0 4} - ( -C-P-O-1, -0 CH ₂ - Il Cl-CH ₂ -CH ₂ OP-OCH ₂ H- (O-CH-CH ₂ ) ₀ j, CH Cl-CH ^ -CH ^ O-P-OCH ^ - H- (OCH-CH ₂ ) ₀ 509 8 2 0/0957 c— ■ ι -0-E-OCH ₂ -CH ₂ Cl CH ₂ -CH ₂ O- (CH ₂ -CH ₂ O) ₀ O-PO-CH ₂ -CH ₂ Cl ) CH ₂ -CH ₂ 0- (CH ₂ -CH ₂ O) ₀ ^ - ^D -O-CH ₂ -CH ₂ C1
) -CH ₂ -CH ₂ -0- (CH ₂ -CH ₂ O) ₀ , 4. The method according to claim 1-3 _y, characterized in that the proportion of the flame retardant in the polyurethane molding compound is about 3 "to 4o weight ^, in particular 5 to 15% by weight, based on the amounts of the organic polyol. 5. The method according to claim 1-4, characterized in that the organic polyol is a halogen- and phosphorus-free polyether polyol or polyester polyol. 6. The method according to claim 5, characterized in that the organic polyol is a partially branched polyether polyol based on propylene oxide with a hydroxyl number of 46 mg KOH / g, a molecular weight of 35oo and a viscosity at 25 ⁰ C of 575 cP. 5 09820/0957 7. The method according to claim 1-6, characterized in that the isocyanate component is 2,4- and / or 2,6-tolylene diisocyanate or diphenylmethane-4,4-diisocyanate, 8. The method according to claim 1-7, characterized in that the activators are tertiary amines and / or organotin compounds. 9. The method according to claim 1-8, characterized in that the blowing agents are chlorofluoroalkanes and / or water. .1o. Process according to Claims 1-9, characterized in that the cell regulators are polysiloxanes, in particular polyethylene-polydimethylsiloxane block copolymers. 509820/0957