DE1283532B - Process for the production of flame-retardant polyurethanes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN WTTWt PATENT OFFICE

EDITORIAL

Int. Cl .:

German class:

Number:
File number:
Registration date:
Display day:

C08g

C09j; D01f; E04h;
WKm C 09 g; C 09 f;

39b5-51 / 82; 22i-1;
2; 29b-3/60; 37f * © lt

39 b5 - 22/04

P 12 83 532.4-43 (M 67751)

December 22, 1965

November 21, 1968

The invention relates to a method for producing flame-retardant polyurethanes from high molecular weight Polyhydroxyl compounds, polyisocyanates, catalysts and ammonium phosphate as flame retardants and optionally blowing agents and surface-active substances. These contain polyurethanes a phosphorus and nitrogen containing flame retardant agent. In particular, the invention is based on directed the manufacture of flame retardant flexible and rigid polyurethane foam materials.

It is known that flame resistance can be imparted to polyurethane materials by incorporating non-reactive phosphorus- and nitrogen-containing compounds into a polyol-polyisocyanate reaction mixture. For example, ammonium orthophosphates such as. B. diammonium orthophosphate, has been used in polyurethane foams as a fire retardant, but these substances have, inter alia, the disadvantage that they are water-soluble and can therefore be leached out of the foam by water over time, that they have certain physical properties of the foam, such. B. the compressive strength and the content of closed cells, and that relatively large amounts of them, ie about 8 to 10 percent by weight or more, based on the total weight of the foam, are required to improve the fire resistance of the foam. Examples of other non-reactive phosphorus- and nitrogen-containing compounds that can be used as fire retardants in polyurethane foams are the water-insoluble compounds with N-P bonds, such as e.g. B. the reaction product obtained from melamine and P ₂ O _5. Such compounds which can be used in polyurethane foams are described in US Pat. No. 3,134,742. As described therein, these compounds do not improve the fire resistance of the foam when used as the sole fire retardant additive. They must therefore be used together with a liquid, phosphorus-containing polyol that has a certain degree of flame-retardant properties and that contains functional groups that are suitable for reacting with the isocyanate group so that the liquid, phosphorus-containing polyol can chemically bond with the foam components . A water-insoluble, phosphorus- and nitrogen-containing mass which, when incorporated in relatively small amounts into the polyurethane material, imparts flame resistance and does not noticeably change the physical properties of the material, would be a method for producing flame-retardant materials
Polyurethanes

Applicant:

Monsanto Company, St. Louis, Mo. (V. St. A.)

Representative:

Dr.-Ing. Hans Ruschke

and Dipl.-Ing. Heinz Agular, patent attorneys,

1000 Berlin and 8000 Munich

Named as inventor:

James C. Barnett, St. Louis, Miss. (V. St. A.)

Claimed priority:
V. St. v. America December 22, 1964
(420 453)

therefore represent an advance in this area.

The invention therefore relates to a process for the production of flame-resistant polyurethanes from high molecular weight polyhydroxyl compounds, polyisocyanates, catalysts and ammonium phosphate as Flame retardants and, if necessary, propellants and surface-active substances under shaping, which is characterized in that the flame retardant used is a practically water-insoluble one Ammonium polyphosphate of the general formula

in which «is an integer with an average value greater than 10 and m is an integer up to a maximum of η + 2 and min is between about 0.7 and 1.1, used in amounts of 5 to 15 percent by weight of the batch.

The production of rigid polyurethane foams with the in particular falls within the scope of the invention flame retardant properties.

The phosphorus- and nitrogen-containing compounds to be used according to the invention are are practically water-insoluble ammonium polyphosphates, d. H. to compounds called P-O-P bonds have and the general formula

correspond, where η is an integer with a

809 633/1548

In general, the ammonium polyphosphates can be used in any particle size that their mixing with the other components of the polyurethane material to form a uniform mixture 5 allowed. In particular, ammonium polyphosphates are preferred, the particle size of which is fine enough that they pass through a sieve with a mesh size of 0.177 mm. Particularly preferred be materials whose particle size is small enough

Average value is greater than 10 and m is an integer up to a maximum of η + 2 and m / n is between about 0.7 .. and about 1.1.

Polycondensation products are preferably used in which the average value of η is about
20 to about 400, determined by the end group titration method (van Waζer, Griffith and McCullough, Anal. Chem., 26,
P. 1755 [1954]), after the ammonium polyphosphates with the help of ion exchange resins are in the io that they have been converted through a sieve with a clear mesh acid shape (van Wazer width of 0.074 mm,
and Holst, Journ. Amer. Chem. Soc, 72, p. 639 According to the invention as flame retardants

[1950]). These polymeric compounds can be used, practically water-insoluble ammonium, either straight-chain structures or branched-chain polyphosphates according to various non-structures here. It should be noted that practically 15 claimed processes are produced, such as e.g. B. all of the nitrogen which is present in these compounds according to French Patent 1,411,254 or as ammoniacal nitrogen according to French Patent 1,461,027.
and that in the compounds practically no core The flame retardants can, as far as in the

nitrogen is present. Although the molar ratio of compounds contain reactive groups ammoniacal nitrogen to phosphorus in the 20, which are a conversion between the ammonium according to the invention compounds used about 1 polyphosphate, the polyhydroxyl compound and the

is, d. H.

m + 2

with m = n, lies in some cases

Allow polyisocyanate to be chemically bound in the mass. In any case, however, they show Ammonium polyphosphate a really surprising one

the molar ratio of ammoniacal nitrogen

to phosphorus below 1. Within the scope of the invention and completely unexpected effectiveness as a flame-retardant range, the use of the agent for polyurethane materials is accordingly,
of polymeric ammonium polyphosphates with a The ammonium polyphosphate is

Molar ratio of not less than about 0.7. If, in place of the polyurethane material, the ammonium polyphosphates used, which according to the invention are incorporated in amounts which are used for this purpose, continue to be practically water-rich, the finished product is characterized as being insoluble to the desired extent, this means giving it flame resistance. In general, when slurrying 10 g of one of the ammo, the ammonium polyphosphate is used in an amount of nium polyphosphate materials in 100 cm ^{3 of} water at which the finished polyurethane -25 ° C no more than about 5 g of the material dissolved material about 0, 1 to about 5 percent by weight of phosphorus, and that at least 5 g, based on the weight of the total mass, remain undissolved when the equilibrium state is reached. abide. Amounts that are sufficient to the poly-

The term "ammoniacal nitrogen" Working urethane material about 0.5 to 3 ° / ₀ phosphorus einzuzieht to those nitrogen laughed yew in the form of, are usually adequate. If an ammonium ion is present and polyurethane foam is produced by the Η-shape, a strong cation exchange resin, such as. B. the 40 from the polyhydroxyl compound, the Polyiso-H-form of a sulfonated polystyrene resin, removes cyanate, the catalyst or accelerator and the

can be. The term "non-ammoniacal nitrogen" or "nuclear nitrogen" refers to nitrogen, which cannot be removed like real ammonium nitrogen.

The ammonium polyphosphates can be produced in many different crystal forms, such as results from their X-ray diffraction diagrams. In general, according to the invention

Ammonium polyphosphate consisting of (E) a blowing agent and (F) a surface-active reaction mixture Means mixed.

The ammonium polyphosphates used according to the invention as fire retardants can be used for production of flame retardant polyurethane materials can be used by using any or several of the various components of the zur

Examples of crystalline forms of ammonium polyphosphates which can be used according to the invention are below others the following:

X-ray diffraction data (a)

all of these forms as well as the non-crystalline 50 production of the polyurethane material used nen or amorphous forms are used. Reaction mass are mixed. All components The ammonium polyphosphate included, can be mixed at once and become reactive Components are implemented, or the am-

Monium polyphosphate can with one or more of these ingredients, such as. B. with the polyhydroxyl compound, be mixed before the mixture obtained is mixed with the other ingredients will. The ammonium polyphosphate can also be mixed with the polyhydroxyl compound and / or the polyisocyanate or mixed with the catalyst in any suitable manner. The polyhydroxyl compound, the polyisocyanate, the catalyst and the ammonium polyphosphate can be metered in and through Pumps and / or in some other way are introduced into a common mixing vessel, after which the The resulting mixture can easily be transported to the point where the polyaddition reaction is to take place

shape 1 Form 2 there) Font i3 Form 4 there) Line ⁰ ) d {k) Line ¹¹ ) 5.70 Line") d {k) Line ⁶ ) 5.70 1 6.06 1 6.06 1 6.65 1 5.60 2 5.47 2 3.08 2 5.68 2 3.42 3 3.83 3 2.93 3 5.40 3 7.00 4th 3.50 4th 3.37 4th 3.52 4th 6.10 5 3.24 5 5 3.80 5

^a ) Cu-Ka radiation.

^b ) The five strongest lines in order of decreasing intensity.

5 6

It is used for the production of moldings, tabular adduct compounds, which are used in the addition of semi-finished products, etc. The am ethylene oxide, propylene oxide, 1,2- or 2,3-butylene oxide monium polyphosphate can also be mixed with the polyhydroxyl or other alkylene oxides to form an active hydrogen compound before it is combined with the polyisocyanate-containing compounds such as glycols or cyanate. It is also within 5 polyols, such as. B. ethylene glycol, propylene glycol, the scope of the invention to mix the ammonium polyphosphate glycerol, methyl glucoside, sucrose, sorbitol, hexane with the polyisocyanate before this triol, trimethylolpropane or pentaerythritol, or the mixture with the polyhydroxyl compound is combined with various alkylamines, alkylenediamines or. However, if a catalyst, such as. B. a polyalkylene polyamines have been obtained. In tertiary amine, and the ammonium polyphosphate depending on the intended use of the polyurethane material mixed and left at room temperature for a prolonged period of time, these alkylene oxides can be left in, a reaction can occur. It is therefore preferred that the polyhydroxyl compound or amine molecules have been attached to the most varied of amounts of the polyol mentioned. When the polyisocyanate and / or the catalyst and the z. B. If a flexible polyurethane end product is desired, ammonium polyphosphate is either used at the same time, should more alkylene oxide have been used to mix one another, or the poly- than for a rigid polyurethane product first.
hydroxyl compound and / or the polyisocyanate with In the technology of producing polydem to mix ammonium polyphosphate and urethanes, the use of so-called then this mixture with the catalyst for pre-addition product processes is also known. Combine here. For example, it is sometimes advantageous, ao it is a process in which first a polyhydroxyl compound-ammonium part of the reaction leading to the polyurethanes polyphosphate mixture is produced before all is carried out, with a pre-addition product components for the purpose of producing a rigid poly - Obtained of increased molecular weight, which can be combined as urethane foam; and in end groups, depending on the stoichiometric in this case, the ammonium polyphosphate is used before the proportion of the reactants used to prepare this addition product, preferably in amounts of about 5 to 15 percent by weight of the mixture. either hydroxyl groups or isocyanate groups

The ammonium used according to the invention contains. This pre-addition product then becomes

Polyphosphates can also be used together with others to produce the desired polyurethane end product

fire retardant ingredients, such as B. Another 3 ° used by it - depending on whether there is

Phosphorus-containing materials - either from the reaction with the end groups of the pre-addition product

tion type or of the inert additive type -, halogen to hydroxyl groups or isocyanate groups

gen-containing compounds containing atimony and boron - either with a polyisocyanate or

the compounds and inert inorganic compounds one of the desired polyhydroxy compounds

Strengthening materials. When the 35 is implemented. The ammonium polyphosphates can

Ammonium polyphosphates together with others according to the invention also in these systems in

fire-retardant ingredients are used, are used advantageously,

are usually amounts of about 10 to 90 weight- To produce the polyurethanes, the above-

percent of the total fire-retardant compound called polyhydroxyl compounds with organic

suitable. For example, the 4 ° polyisocyanates according to the invention can be implemented. The term »polyiso-

ammonium polyphosphates used in the pre- cyanate «here means all known polyiso-

standing mentioned amounts in an advantageous manner cyanates, which are used for the production of polyurethanes

have been applied or can be used together with those in US Pat. No. 3,076,010,

bis- (hydroxyalkyl) -aminoalkylphos- The term includes monomeric di- and polyisocyanates

phonic acid diesters or in particular with such 45 and pre-addition products of polyhydroxyl compounds

Materials used are diethyl-N, N-di- fertilizers and polyisocyanates that contain isocyanate groups

Ethanolaminomethylphosphonat, bis (j3-chloroethyl) - contained in excess, so that free isocyanate

N, N-diethanolammomethylphosphonate od. The like. Ent- are available with additional

keep. Polyhydroxyl compound can react if they

In the production of the polyurethane materials 50 with the polyisocyanate for the production of the fire can z. B. diols, polyols, polyethers, polyesters or permanent polyurethane polyadducts according to Polyester amides can be used, which are combined hydrogen of the invention. To the polyisoatoms have the cyanates to react with isocyanates, which are useful for the production of the polyurethanes are. In general, these bar materials include ethylene diisocyanate, ethylidene diiso molecular weights from about 62 to about 5000 and 55 containing cyanate, propylene-1,2-diisocyanate, butylene-1,3-diiso two to about eight or ten or more cyanate, hexylene-1,6-diisocyanate, cyclohexylene-1,2-di-hydroxyl groups per molecule or have an isocyanate or the arylene polyisocyanates with two to Hydroxyl group content of about 0.5 to about 25 Ge three isocyanate groups per molecule and one to three weight percentage on. Some even have a phenylene ring as the sole aromatic cyclic higher hydroxyl group content. In the general 60 ring system, such as B. m-phenylene diisocyanate, 2,4-tomeins Hydroxyl numbers from about 50 up to 500 or luylene diisocyanate, 1,6-tolylene diisocyanate, 3,3'-disogar 700. In the case of polyesters, the acid number should be methyl and a wide variety of other polyisos of 10 and usually the number 0 cyanate, such as. B. 4,4'-biphenylene diisocyanate, 3,3'-diso as closely as possible. This material methoxy-4,4'-biphenylene diisocyanate, 3,3'-diphenyllia For the sake of convenience, 65 4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate are hereinafter referred to as "Polyhydroxyl compounds" called. Among the nat, 3,3'-dichloro-4,4'-biphenylene diisocyanate, tributary, phenylmethane triisocyanate or 1,5-naphthylenediiso-polyhydroxyl compounds containing active hydrogen atoms belongs to the large cyanat family.

7 8

Useful catalysts that can be used as a "catalyst" - polysiloxane or alkylpolysiloxane polyoxyalkylene glycol constituent are under copolymers. For foaming polyurethane other tertiary amines, either individually or polyadducts, about 5 to 50 g in the form of mixtures, such as. B. the N-Alkylmor- parts by weight propellant and about 0.1 to 3 weight pholine or the Ν, Ν-dialkylcyclohexylamines, 5 parts of the foam stabilizer to 100 parts by weight of the methyl, ethyl, propyl reaction mixture used in the alkyl radicals are, or is butyl residues; furthermore triethylamine, the polyhydroxy 1 compound and the polyisocyanate tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperidine, dimethylhexahydroani- are usually in sufficient proportions that an NCO / OH ratio of about 1.05: 1 lin, diethylhexahydroaniline, the Reaction products io is given. Usually a small excess of Ν, Ν'-diethylaminoethanol and phenyl isocyanate, of the polyisocyanate is used to ensure a complete esterimide, l-methyl-4- (dimethylaminoethyl) piper reaction, but an accurate azine, N-ethylethyleneimine, Ν, Ν, Ν ', Ν'-Tetramethyl- adherence to this quantitative ratio not of 1,3-butanediamine, triethylamine, 2,4,6-tri- (dimethyl- essential importance. As an example is the aminomethyl) -phenol, Tetramethylguanidine, N-ethyl- 15 Manufacture of flexible foams, where the morpholine, 2-methylpyrazine, dimethylaniline or foams often using the nicotine; Metal compounds, such as B. bismuth, reaction of water with the polyisocyanate free lead, tin, titanium, iron, antimony, uranium, cad is caused by CO ₂ , a large excess of mium, cobalt, thorium, Aluminum, mercury, polyisocyanate used. The reaction mixture obtained in this way, zinc, nickel, cerium, molybdenum, vanadium, copper, ao, and manganese or zirconium compounds. Examples of this - during the induction period to the point where the for, among other things, bismuth nitrate, lead-2-ethyl polyaddition should take place, where it hexoate, lead benzoate, lead oleate, sodium trichloropheno- easily lost using conventional devices, sodium propionate, Lithium acetate, potassium oleate, can be poured, such as. B. in suitable forms. Tetrabutyltin, butyltin trichlorate, tin (IV) chloride, »5 The hardened foam pieces are replaced by the tributyltin-lo-phenylphenolate, tin (II) -octoate, incorporation of an ammonium polyphosphate in tin (II) -oIeate, dibutyltin-ethyl- (2-ät) , Di quantities of about 0.5 to about 20 percent by weight, (2-ethylhexyl) tin oxide, titanium tetrachloride, tetrabutyl based on the total weight, and preferably titanate, iron (III) chloride, antimony trichloride, cad from about 1 to 10%> in the reaction mixture made flammmium diethyldithiophosphate, thorium nitrate, triphenyl 30 inhibiting. The phosphorus content of erhalaluminium, nickel carbonyl. The polyurethane material contained in the catalyst impairs its good part - although it is not a single compound or physical properties, it cannot be a mixture - can be used in the usual amounts, which can usually be used in all areas used who-0.05 to about 4 parts of catalyst per 100 parts by weight of 35 den on which polyurethane materials are previously ver-reaction mixture. have been applied. Polyurethanes obtained according to the invention are used both in non-foamed and flexible phosphorus-containing polyurethane foams as well as in the so-called “foam” form for seat cushions or other upholstered goods. In general, polyurethane foam protective or shock pads, etc., will be used. The substances obtained when low-boiling liquids 40 rigid polyurethane foams are very useful or normally gaseous propellants from those used for building purposes, such as. B. as insulating panels and for polyurethane-forming reactants produces other uses in construction. Not foamed or incorporated into them. Often the polyurethane materials that are obtained according to the invention, heat of reaction, cause these low-boiling liquids to volatilize for the production of textile fibers or blowing agents, which causes the and as resin base materials to foam in the production of mass. Can be used in some curable coating compositions. In these cases, the boiling point of the propellant is chosen so that it is also used as impregnation adhesives during manufacture that it is well below room temperature. The laminates made from wood and other fibrous compounds can then be made to foam, such materials can be used before a substantial reaction between the poly- 50 The following examples serve to further elucidate the invention. Unless otherwise found or before heat is generated at all, parts are to be understood as parts by weight. Usable blowing agents that can be used in the manufacture and the percentages also relate to the position of foams, the weight, include water - either alone or in the 55

Mixture with other ingredients, such as. B. as B e i s ρ i e 1 1 aqueous solution of a serving as a catalyst

tertiary amine - or the chlorinated or fluorinated ones. This example illustrates the preparation of a rigid

Alkanes having 1 to about 2 carbon atoms, such as. B. polyurethane foam using

the chlorofluoromethanes or chloronuoroethanes. 60 ammonium polyphosphate as a flame retardant

When propellant is incorporated into the reaction mass, agent.

The various components can also be added to the mixture the most common foam stabilizers are incorporated into Potyol based on methyl, around the cell structure of the foamed glucoside 100.0 obtained

th polyurethane product. Used for 65 trichloromonofluoromethane 35.0

for this purpose the most diverse surface

active agents such as B. Various Siliconverbin- alkylsilane-silicone stabilizer 2.0

fertilize or silicone oil mixtures, such as. B. Dimethyl-tetramethylbutanediamine 1.5

Component parts

Ammonium polyphosphate (% 30.2% P) 10.00 Polymethylene polyphenylene polyisocyanate with a content of available NCO groups of about 32% ^and a viscosity of 200 ± 50 cP at 25 ° C 108.0

Phosphorus content of the finished foam about 1.18%.

All of the ingredients in the above formulation - with the exception of the polyisocyanate - became one homogeneous mixture mixed. The polyisocyanate was then added and the mixture thoroughly mixed. The foaming properties were shown in a "cream time" of about 32 seconds and one "Foam rise time" of about 170 seconds after placing the mixture in paper-lined boxes had been poured.

In the following Table I are the physical properties of the rigid polyurethane foam obtained specified.

Table I.

1. Density, g / cm ³ 0.032

2. Compressive strength, kg / cm ² , when the pressure limit is reached

parallel to the direction of foam rise 2.44

across the direction of foam rise .. 0.86 parallel to the direction of foam rise after 2 weeks at 70 ° C and 100% relative humidity 2.05

3. "K" factor 0.12

4. Approximate percentage of closed cells, corrected 96

5. dimensional stability,
% Change in volume

at 70 ⁰ C and 100 ° / ₀ relative humidity after 1 week 10

after 2 weeks 11

at 100 ⁰ C and the relative humidity of the environment

after 1 week 1

after 2 weeks 1

at - 40 ⁰ C and the relative humidity of the environment

after 1 week 1

after 2 weeks 1

Remarks:

The data in the table above was determined using the following standard test methods:

a) ASTM D-1622-59T density

b) Compressive Strength ASTM D-1621-59T

c) »K« factor (heating line source)

d) Cell count Microscopic count

e) Dimensional Stability ASTM D-2126-62T

In the following table II the flame resistance of the obtained according to the present example, Foam containing ammonium polyphosphate with the flame resistance of a rigid polyurethane foam compared that in the same way as above but using diammonium-5 orthophosphate as a fire retardant in an amount of about 14 percent by weight, making about the same phosphorus content in the foam, d. H. of about 1.26 weight percent had been.

Table II

Assessment of flammability

Average burn length, cm

Evaluation after 2 weeks

at 70 ° C and 100% rela-

s5 tive humidity

Average Benn length, cm

_ ₀ evaluation after 2 weeks
at 100 ⁰ C and the relative humidity of the environment

Average burn length, cm

Ammonium polyphosphate

self-extinguishing

0.76

self-extinguishing

3.8

self-extinguishing

5.1

Diämmo-

nium ortho-

phosphate

self-extinguishing

6.1

burns

10.2

burns

10.2

Standard Test Method ASTM D-1692-59T.

B e i s ρ i e 1 2

This example illustrates the manufacture of a rigid polyurethane foam using ammonium polyphosphate as a flame retardant.

Component parts

Sucrose based polyol 100.0

Trichloromonofluoromethane 35.0

Alkylsilane Silicone Stabilizer 2.0

J ₀ tetramethylbutanediamine 1.5

Ammonium polyphosphate (30.2% P) 10.0 polymethylene polyphenylene polyisocyanate with a content of available NCO groups of about 32% and a viscosity of 200 ± 50 cP

25 ° C 102.0

Phosphorus content of the finished foam about 1.20%.

All ingredients of the formulation, with the exception of the polyisocyanate, became homogeneous Mixture mixed. The polyisocyanate was then added and the mixture was again thoroughly mixed became. The foaming properties were shown in a "cream time" of about 35 seconds and one "Foam rise time" of about 160 seconds after placing the mixture in paper-lined boxes had been poured.

809 638/1548

In the following Table III are the physical Properties of the rigid polyurethane foam obtained according to the present example are compiled:

Table III

1. Density, g / cm ³ ... "0.0368

2. Compressive strength, kg / cm ² , at the pressure limit

parallel to the direction of foam rise 2.47 transversely to the foam rise direction .. 0.95

parallel to the foam rise direction after 2 weeks at 7O ⁰ C and 100% relative humidity 1.97

3. "K" factor ....> 0.12

4. Approximate percentage of closed cells, corrected 94

5. dimensional stability,
% Change in volume

70 ° C - 100% relative ^ humidity. ^!

after 1 week:. 6th

after 2 weeks. "" .. 5

100 ° C - relative humidity of the ambient,. - ... environment

after 1 week ... ...; ... 5

after 2 weeks .....'........ . ·. . '. 4 '

.-4O ⁰ C - relative humidity of the environment '! ^:

after 1 week,. <1

• after 2 weeks <1

Example 4

This example explains the use according to the invention of ammonium polyphosphate in polyurethane foam compositions at three different weight concentrations. In these three formulations, the ammonium polyphosphate is used in an amount corresponding to 0.6, 0.75 or 1.0 percent by weight of phosphorus, based on the total mass, is used.

Component in grams 0.6% P 0.75% P. 1.0% P Ammonium polyphosphate
Propoxylated methyl
glucoside
Alkylpolysiloxane polyoxy
alkylene copolymer ...
Haloalkane (trichloro
fluoromethane)
Tin (II) octoate
l-methyl-4- (dimethyl-
aminoethyl) piperazine ..
"Polyisocyanate A" 12.9
155.2
1.6
48.5
0.5.
1.6
190.4 16.1
152.4
1.6
48.5
1.6
189.2 21.5
144.7
1.6
48.5
0.5
1.6
188.5

Notes: ■ - ■ '■■ -; ■ "_.«:

The data in the table above were determined using the following standard test methods:

a) density "'

b) -compressive strength ~ .-. v

c) "K" factor ■ - ■■ - ■

d) number of cells'

e) Dimensional stability

ASTM D-1622-59T ASTM D-1621-59T (Heating line source) Microscopic count ASTM D-2126-62T

B eisρ Le I 3

This example illustrates the preparation of a flexible polyurethane foam using of ammonium polyphosphate as a flame retardant. ··· - ..

A mixture is prepared which contains about 120.0 g of a polyoxypropyl atriol having a hydroxyl number of 56.3 and a molecular weight of about 3000 (made from glycerine and propylene oxide), 12.0 g Ammonium polyphosphate,; 0.06 g: l * methyl-4- (dimethylaminoethyl) piperazine, 0.36 g of tin (II) octoate, 0.60 g of N-methylmorpholine, 1.20 g of a polysiloxane polyoxyalkylene copolymer as a surfactant and contains 3.48 g of distilled water. 53.7 g of tolylene diisocyanate are added to this mixture given, which is used in an amount sufficient to react with the polyol. The mixture is stirred until homogeneous and then placed on a container lined with aluminum foil poured where foaming progresses. The flexible polyurethane foam obtained is a High quality material with reduced flammability.

All components of the individual recipes, with the exception of "Polyisocyanate A", were closed mixed into a homogeneous mixture. Then became

the »Polyisocyanate Ä << added and with the Ingredients mixed. Then the resulting mixtures were poured into a prepared container and implement and let foam. All three recipes made high quality, fire retardant rigid foams.

"Polyisocyanate A" is an unpurified mixture of isomers of methylenebisphenyl isocyanates, where some molecules contain three aromatic rings and three isocyanate groups and being a total about 32% of NCO groups is present.

Example 5

This example illustrates the manufacture of fire-resistant. Polyurethane foams by the process according to the invention, the ammonium polyphosphate with the following polyols in a sufficient amount; is mixed that finished Polyurethanes can be obtained with a phosphorus content of about 0.75 to about 2.5 percent by weight.

Polyol

Methyl glucoside
+ Propylene oxide

Sorbitol. + Propylene oxide ...

of the polyol

13.2

14.7

Weight percent P incorporated by the ammonium polyphosphate

0,6,0,9,1,0,1,2 1,3,1,5,1,7,2,5

1.1, 1.7

Sucrose
+ Propylene oxide. '. 12.7 1,1,1,7

For the production of the above polyols, methyl glucoside, sorbitol or sucrose are sufficient Propylene oxide has been reacted in order to obtain the specified hydroxyl group content in%. With the obtained mixture of the ammonium polyphosphate and the polyol of about 170 g is a homo-

Claims (1)

13 14 Genes mixture of about 1.6 g of alkylpolysiloxane poly- All components, with the exception of the polyisooxyalkylene copolymer, about 48.5 g of trichlorofluorocyanate were mixed into a homogeneous mixture methane, about 0.5 g of tin (II) octoate, about 1.6 g of 1-Me- mixed. The polyisocyanate was then added, ethyl 4- (dimethylaminoethyl) piperazine and about 190 g and the mixture is thoroughly rerun "Polyisocyanate A" mixed. This mixture is mixed for 5. With a "cream time" of around 35 seconds poured into a prepared container and react the mixture has a foam rise time of and let it foam. All recipes left about 170 seconds on after the mixture was in high quality, fire retardant foams which have been cast in a suitable shape. From the keep. above recipe is a high quality, fire- "Polyisocyanate A" is an unpurified isomer-resistant rigid foam obtained,
mixture of methylenebisphenyl isocyanates, where
some molecules three aromatic rings and three Containing isocyanate groups and where the overall claims:
content of NCO groups is about 32%. B ice T he 1 6 ¹⁵ ^ "process for the manufacture of flame-retardant _ .. _,. ., ... .. ... Polyurethanes made from high molecular weight polyhydroxyl This example explains the production of a compounds, polyisocyanates, catalysts and rigid polyurethane foam using ammonium phosphate as a flame retardant and a bis (hydroxyalkyl) aminoalkylphosphonic acid, optionally blowing agents and surface-active esters, and an ammonium polyphosphate as fire- _{retardant substances with} shaping and thus inhibiting additive. ke η η ζ eich η et that the flame retardant components are a practically water-insoluble ammon poly-polyol based on methyl phosphate of the general formula
glucoside 100.0 Trichloromonofluoromethane 35.0 as a Ii ι · ι π · ι · n ^ ι_ · ι · * in "(n-mj + a (.-N" 4 / SrIlU ₃ ) I +! Alkylsilane Silicone Stabilizer 2.0 Tetramethylbutanediamine 1,5 ... ^ ,,. . ... ....., in which η is an integer with one above 10 Ammonium polyphosphate (30.2 ° / ₀ P) .. 5.0 is the average value and m is an integer up to Diethyl-N ^ -diäthanolaminomethyl- _{30 means} a maximum of η + 2 and m / n between about phosphonate 5.0 o, 7 and 1.1, in amounts of 5 to 15 weight Polymethylene polyphenylene polyisocyanate used as a percentage of the batch, with a content of available 2. Method according to claim 1, characterized in that NCO groups of about 32 ° / ₀ and records that in addition to the ammonium polyphosphate a viscosity of 200 ± 50 cP at 35 a bis- (hydroxyalkyl) -aminoalkylphosphon- 25 ° C 108.0 acid diester is also used. 809 638/15 «11. 68 ® Bundesdruckerei Berlin