DE2359700C3 - Flameproofing of polyurethanes - Google Patents

Description

, as a flame retardant for polyurethanes Jcsten ^ A ^ ^ make-up component preferred

ntStn ^ nium _P oly _P hospha _S ^ J ^^ S ^ SX

600 m ^ S i t ll

tn ^ nium _P oly _P hosp _S ^ J ^^ S ^ integer between about 600 i ₅ m ^ Sastet. In this way .st e. ,, fully-

ohates that by heating about the equimole mixture ι _{hatsalzes in} the mixing container

molecular-weight quantities of ammonium orthophosphate sinking de ι _sediment em corresponds result,

„Nd sosphorus pentoxide to temperatures between under B.Wung _ierte p _{asten> die} be. the after-

S "° d 350 ⁰ C in the presence of gaseous ^ S stand en ungie«, _{the IsO} cyanate component

ZnZtJu ^ steady simultaneous _; Mi- ^ «^ *? Different flame retardants

STSSSSv & ÄÄÄ

^ denotes that "^ f _ol y _phosph ate can be avoided if Pha contains comprising about aqu by heating, ^" a Ammoniumpolyphos- 30 "^ Soniu'mpo.yphosphatmU high condensate

tf ^ VÄ ^ l ^ ar'SSien Sonsg ^ - ^ SS S ₁ ^ _n

tf ^ VÄ ^ l ^ arSSien Sonsg ^ - ^ SS S ₁ ^ _n

I see 17o 'u5d 35O "C in the presence of gas- less soluble ^. JJ 8 _{suspension for} cel formation.

Smigem ammonia under constant and equal- 35 P ^ f ^ J thus relates to the use of

Mixing, kneading and crushing the _A ^ _om ^r ^ _poly ^g _pho s _P hat _e n, as well as given f. _S

Da1 «S corresponds to ammonium polyphosphate

the general formula

PO

It is known that H ₀₁ -WNH ₄ WP ₁₁ O *, m.

_{Polyurethanes phosphorus nitrogen compounds} , such as a number average

ζ B diammonium orthophosphate, to be used 45 '"^ ₄₀₀ ^ ^ _{1 (χχ) means and the V} e, -

which are added to the polyurethane approach. - _{t is} .

Di'm non'umorthophosphat has, however, due ^ha ^ ^IS ^ _{w 'else is} according to the invention an ammonia

Sn "serlöslichleit the disadvantage of the arts ^V ° ^ _with a _{calcium phosphate Product} Kondensat.onsgra".

fabric to be washed out when exposed to moisture, mump J. » _{800> in} particular 600 to 800

thus giving the plastic its original non- 50 ^ n et ^. ^ ^., Phosphate e ^ a 0.5

^ dSSTin the German inscription ^ Ä ^^ SÄ / Ä j

83 53 ™ Ammoniumpoly- the use emäß used by largely water ^BEZ _D ^O _{a s} ^{g s a} _{he findungsg}

foe Poipb " _S pha, c of the general formula ™ Partial flame retardant substance, ₅ t proof.

e, _"s pree" e "in" * "er" an ₈ on "Za ,,, t, it s," e ", MJJ""---","." _{CESM, g} EWIC _h t, before, ie ₅ e »

"Ä? ISÄS" »Her _s , e de. P — n.

about 0.7 and 1.1. The well-known Ammon.um i ht unm

S '5, "Ä? ISÄS" θ "» Her _s , e de. P — n. ^, J- ^

about 0.7 and 1.1. The well-known ammonium urethane _foam r _cs is not directly counter-

End group titration method (van

a, he.

O 3 4

pflächen-iktiven substances and other processed materials, such as are for example for building insulation loading ° beitungshilfsmitteln ^{nutrition 'TCN.} Highly branched polyols with ^a [. . jj _e production of a large number of hydroxyl groups used according to the invention, ammonium polyphosphates are already described in the ammonium coaches used according to the invention patent application P 23 30 174.8 for example in polyurethane _{molding compounds compared to conventional * u nl} oleolecular amounts of ammonium orthophosphate ammonium polyphosphates due to a lower ^a ? _{t un (j} phosphorpenioxid intermediate to temperatures solubility in water, so that the risk, we washed the P. 170 "and 350 ^r C in the presence of gaseous plastic with moisture to form ^S \ monia with continuous and simultaneous micro io will not be given . Insofar the Flammhen kneading and crushing remains of the reaction mixture festiekeit of "plastic for a long time maintained ^sc j |. _{itz 't"} Because of the gel-forming properties of ammonium ^ AIs polyhydroxy compounds for niumpolyphosphate is a constant uniform lyurethanhersteliung diols, polyols, Polyethers, distribution in the polyurethane batch, especially p ° lvester or polyester amides in question. Generally 15 in the polyol premix, guaranteed and these substances exclude a molecular weight from sedimentation of the phosphate. Inf-a 60 to 5000 and contain at least two if possible the polyp ¹ -'-— '■ ·''"the supply OH groups per molecule. Their hydroxyl salts l is keeping of "phosphate-containing polyol premix ingen. Usually between about 40 and 700 mg KOH / g. Since the Gefanr sedimentation does not exist over a long period of time, the phosphate component required as a further starting component does not exist, the polyisocyanate can be an aromatic or ali- The subject of the invention is to be explained in more detail by the post-static isocyanate with at least two NCO- the following examples The solubility of an inventive or polymeric polyisocyanate or ammonium polyphosphate used with polyols to give so-called "prepolymers" 25 degree of condensation η of about 700 was set, a ratio polyisocyanate can act. of m to η equal to 1 and a P., O ₅ content of To accelerate the reaction be bought 72 weight ^0; determined in water and the result • öhnlich 'catalysts or their "mixtures" in solubilities in comparison to the subsequent "rineen amounts" added. As such, commercially available ammonium polyphosphates, in the case of welfertiary amines or organometallic compounds, the degree of condensation η between 20 and 400, such as divalent tin or lead compounds, are suitable. lies, set.

Usually one proceeds so that a small

stoichiometric excess of NCO-Gruppcn overall _{χ) A Proc} j _u kt with a phosphorus content (P ₂ O ₅₎

cen over the hydroxyl groups of the polyol compound _{from 71 to 72} ·> / _and an N content of 14

is present in the polyurethane approach. It may, however, also 35 _b is I5 ^l \ ', with a specific gravity of

with a deficiency of NCO groups worked ₁ 8 c / cm ³ and Zersetzunastemperatur at 33O ~ C

will. The limits for the NCO group content ^ £ 1 _{in a} slurry of 1 g of the pro-

eecene over the hydroxyl groups has a pH of around 100 g of water

90 "to 130". ',, in particular 102 to HO ⁰ ,,, based on 45 ^ j _s g

^the je ^t after ° d ^{n r} em Gew'ünsch ^{I te?} * 2) Another product is characterized by the following physical polyurethane approach approx. 0.5 to 20 ^{weight- 0} ; ,, kaiische data:

in particular from 1 to 10 weight ^0;, Ammoniumpoly- phosphorus content 32 _"0

phosphate, based on the total weight of the initial _{weight 19}

sentence, added. The ammonium polyphosphate is 45 z _ersetzunBSt enneratur 375-400

usually before the polyol is mixed with the replacement temperature.

the polyisocyanate compound incorporated into the polyol pH value of a dispersion of

brings. It can also be used with other liquid flame 10 g / 100 g H ₂ O ⁰ ^

Protective agents mixed and this mixture the refractive index 1.48 to 1.49

^P r ^e S; ⁿ S ^ s £ Ser "use her- * 3) Another product contains 30 to 32 °, P and

Polyurethanes can be made both in more compact ^ * Properties of this product are:

as well as in foamed form. Wtitere ti ^ enscruiiei

For the production of polyurethane foams specifically Weight 0.4 to U, 8

Customary blowing agents, such as low-boiling chlorine decomposition temperature 330 to 450 ° C.

ized, fluorinated alkanes and / or water are used. Refractive index 1.486

The amount of propellant depends on the

desired density of the polyurethane foam _solubility, 5 g of the am-

Sfhlieniich serve as processing aids for 60 monium polvphosnhates in 100 ml of water for 1 hour the pol urethane foam production still foam at 40 ° C then stirs the stabilizers to regulate the cell structure, whereby the temperature is cooled and in the course of

nisses

at the choice of the polyol and the proportions 65 decanted and for cleavage

of the individual batch components can be dissolved ammonium polyphosphate

until rigid polyurethane foam sticks are produced. For the production of rigid foam

on eventuclll each-

Tem ammonium polyphosph briefly boiled In aliquots of the individual solutions, the

Conductivity, density and the dissolved fraction of the

Share of

Phosphates determined. The results obtained are shown in table 1.

Table 1

product I. 11th 111 1) 1665 1.003 20.9 2) 1644 1.003 19.5 3) 2018 1.004 31.8 Product according to the invention 605 1.001 9.3 used

Entered 150 g of methylcndiphenyl 4,4'-diisocyanate and poured the resulting reaction mixtures into two 5 liter cardboard boxes. After a rise of 30 seconds and a rise time of 120 seconds, two rigid polyurethane plastic blocks were formed which cured within 10 minutes. The foam blocks owned the
Properties shown in Table 1.

Table II

properties

Foam
1 Il

In table 1:

Column I: electrical conductivity of the solution

([JS = - micro Siemens)
Column II: Density of the solution at 20C (g / ml)

Column III: Dissolved phosphate content at 40 ^c C (% by weight)

As can be seen from Table 1, the product used according to the invention has a significantly lower product Solubility in water than the comparison products.

Volume weight (g / l) 36 35

Compressive strength according to DIN 53 421 2.71 2.63
(kp / cm ² )

Flexural strength according to DIN 53 423 2.20 2.27

(kp / cm ² )
Shear strength DIN 53 422 1.50 1.54

(kp / cm ² )

Dimensional stability (volume- -6.3-3.7
change at 70 ^; C / 95% relative
Humidity after 2 weeks (° / ₀ )

example 1

There were two polyethane foams. produced the following composition, where batch I had an ammonium polyphosphate with a degree of condensation η of about 700 as the flame retardant, while batch II contained no flame retardant. The following substances were initially intimately mixed at room temperature:

approach

1 Il

Polyether polyol (propoxylated
Glycerine / cane sugar mixture with
the OH number 520 mg KOH / g,
Molecular weight approx. 350, viscosity 6000 cP

100 g 100 g

water ig σο - Triehlorfluoromethane 24 g 24 g Triethylamine 3g 3g Dimethylpolysiloxane polyoxy ί g ig alkylene ether copolymer Ammonium polyphosphate 10 g

In each of the mixtures prepared from the above substances, while stirring vigorously

Table III

Proved in a burn test according to ASTM-D1692 Foam I appears to be "self-extinguishing" after a burn-off distance of 26 mm, while Foam II "Completely" burned down.

Example 2

8 samples of a homogenized mixture were prepared from the components designated in Example 1 with batch II, with the exception of trichlorofluoromethane, and samples 1 to 4 10 g of an ammonium polyphosphate with a degree of condensation η of ~ 800 or samples 5 to 8 10 g of ammonium polyphosphate product 2 with a degree of condensation of> -300 are mixed in. The samples were stored η in beakers for 4 weeks. After each week, the sedimentation volume of the ammonium polyphosphate was determined as a percentage of the total volume of a sample from samples 1 to 4 or 5 to 8, then the sample was homogenized again by stirring with a paddle stirrer at 150 revolutions per minute and the homogenization was achieved up to visible homogeneity: time required. The sample was then foamed to form a polyurethane foam by adding 24 g of trichlorofluoromethane and 150 g of methylenediphenyl-4,4'-diisocyanate.

The sedimentation volumes and homogenization times determined in the test series are can be seen from Table III.

sample 1 2 3 4th 5 6th 7th 8th 4th Number of weeks 1 2 3 4th 1 2 3 > 180 Homogenization time (see) 10 10 15th 20th 25th 40 60 10 Sedimentation volume ° / ' 0 0 I. 6th 6th 14th 12th

Sample 8 was below 65 after standing for 4 weeks. In general, samples 1 to 4 required

No more homogenization under the specified conditions - a shorter homogenization time than the samples 5

sable, since the sedimented ammonium poly- to 8 and were in contrast to the after 2 weeks

nhosn has turned into a strongly solidified sediment - comparative samples still completely homogeneous.

Example 3

The following components were intimately mixed at room temperature:

100 g polyester polyol (adipic acid diethylene glycol polyester) with an OH number of 60 mgKOH / g, Molecular weight approx. 2000, viscosity approx. 20,000 ocP

4.7 g water

1.0 g of polyoxyalkylene polydimethylsiloxane copolymer

1.0 g dichlorotetrafluoroethylene 0.4 g dimethylbenzylamine
0.15 g of tin (II) octoate

7 g ammonium polyphosphate with a degree of condensation η of 700

51 g of a mixture of the 2,4- and 2,6-isomers of tolylene diisocyanate were rapidly added to the mixture obtained (Mixing ratio of the isomers 80:20) is stirred in. After 33 seconds of cream time and A flame-retardant, elastic polyurethane foam was created in a cardboard box with a rise time of 116 seconds.

In a comparative experiment, a corresponding foam was produced in an analogous manner, the contained no flame retardant. The foams produced were those listed in Table IV Properties.

Table IV

Properties of the foam A. B. Volume weight, (g / 1) 24 23 Compression set according to DIN
53 572 (22 h / 70 ° C / 50% compression 6.3 5.2 Tensile strength according to DIN 53 571
(kp / cm ² ) 0.95 1.05 Dimensional stability (volume
change at 70 ⁰ C and 95%
relative humidity after 2 weeks -2.4 + 0.4

A - · with flame retardant additive
B - without the addition of flame retardants

In the burning test according to ASTM D 1692, foam A proved to be self-extinguishing after one Burning distance of 22 mm, while foam B burned down completely.

The experiment shows that by adding the flame retardant to the foam, its properties can only be changed insignificantly.

Example 4

There were 10 samples of a mixture homogenized at room temperature, consisting of the following Components manufactured

100 g polyester polyol (adipic acid diethylene glycol polyester) with an OH number of 60 mgKOH / g, Molecular weight approx. 2000, viscosity approx. 20,000 cP "

4.7 g water

1.0 g of polyoxyalkylene polydimethylsiloxane copolymer

0.4 g dimethylbenzylamine
0.15 g of tin (II) octoate

Samples 1 to 5 were mixed with 7 g of ammonium polyphosphate product 3 with a degree of condensation η of -200 and samples 6 to 10 were mixed with 7 g of an ammonium polyphosphate with a degree of condensation of ~ 600. The samples were stored in beakers for 5 weeks. After each week, the volume of the clear liquid layer formed over the suspension by sedimentation of the ammonium polyphosphate was determined for one of the samples 1 to 5 or 6 to 10 and related as a percentage to the total volume of the sample. The sample was then renewed by stirring with a paddle stirrer at 150 revolutions per minute

4.5 homogenized and at the same time the homogenization up to the visible required time measured. The respective; The measurement results obtained are shown in Table V.

Table V

Sample no.

Number of weeks 1 ^{2 3}

Homogenization time (see) 30 55 90

Volume of the clear 9. 14 21 liquid layer " _u

4th 5 6th 7th 8th 9 10 4th 5 1 2 3 4th 5 150 210 10 35 45 60 75 Ti 30th 0 1 4th 10 12th

WieT-ibclleV zeiet require the samples 6 to 10 65 as follows from the following ¹ IaWIcVI, no

fine shorter homogenization time than the comparison - more obvious if m;, n samples 1 to 10 /

samples 1 to 5 and also have a lower one with 1 g of water added.

Tendency to sedimentation. These F.ffckie be, / oniiM '/,

Table VI

ίο

Sample no.

10

Number of weeks 1

Homogenization time (see) 20

Volume of the clear 11
Liquid layer%

3 4th 5 1 -> 3 4th 5 50 80 140 195 0 20th 30th 50 65 IS 27 32 36 0 1 2 4th 7th

Sample no.

Samples 1 and 6 according to Table V were each mixed with 1 g of dichlorotetrafluoroethylene and the Mixture with 51 g of a mixture of the 2,4- and 2,6-isomers of toluene diisocyanate (mixing ratio of isomer 80:20) implemented. The properties of the foams obtained differed differ only insignificantly from the properties of the flame retardant produced according to Example 4 Foam.

Example 5

There were 6 samples of a mixture homogenized at room temperature, consisting of the following Components, manufactured.

100 g polyether (propoxylated trimethylolpropane

with the hydroxyl number 375 mg KOH / g, molecular weight approx. 400, viscosity 650 cP)

35 g trichlorofluoromethane

1.5 g dimethylpolysiloxane polyoxyalkylene ether

copolymer

0.5 g triethylenediamine
2.0 g of triethylamine

15th

236

104

In the samples 2 to 6 different amounts were an ammonium polyphosphate having a condensation degree π of ~ 700 blended and then reacted all samples with 100 g of polymethylene polyphenylene polyisocyanate having a content of reactive NCO groups of about 32% and a viscosity at 20 ⁰ C of 25OcP . The samples placed in cardboard boxes formed rigid polyurethane foam blocks of good quality. In the burning test according to ASTM D 1692, the individual polyurethane samples showed the burning behavior shown in Table VIl.

40

45

Amount of flame retardant (g)

class

Burn-off

speed

(mm / min) Burning distance - - 55 19 11 10
(mm)

b = combustible

s = self-extinguishing

Example 6

A paste was made from 40% by weight ammonium polyphosphate with a condensation Degree /; from -1000 and 60% by weight Tris (2-chlor ethyl) phosphate. 10 g of this paste were mixed with the following substances:

100 g polyether polyol (propoxylated Äthylendiarrui with an OH number of 480 mg KOH / g, molecular weight 400, viscosity (25 ⁰ C) for about 300OcP

2 g of hexamethyltriethylenetetramine
20 g trichlorofluoromethane
2 g of water

1 g of dimethylpolysiloxane polyoxyalkylene ether copolymer

150 g methylenediphenyl-4,4'-diisocyanate

The mixture was poured into a cardboard box and gave after 30 seconds: cream time and 112 seconds rise time a rigid foam with a density of 32 g / l of good quality. In the burn test after According to ASTM D 1692, the foam was found to be self-extinguishing after a burn distance of 21 mm.

Claims (1)

¹ rriffiter and Mc C u 1 1 ough, Anal. Chem. V / Π 9511 S 1755), after the Ammon.umpoly patent claims: phosphate with the help of ion exchange resin m the 1 Use of ammonium polyphosis- ^ f ν ^ Γ ^^ phaten of the general formula "* ^ _a degree of condensation" of e wa ^ ₀₀ ΛΛΟ ,,, Ice 400 at ^^^ Γ ^ Π ^ ffss; ¹ - ™ s