JPS6198722A - Fire retardant based on freely flowable powdery ammonium polyphosphate, its production and fire resistant polyurethane or polyurethane foam containing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The subject of the present invention relates to a hydrolytically stable finely filled flame retardant based on free-flowing powdered ammonium polyphosphate and a process for its preparation.

The prior art - the use of ammonium triphosphate as a 1111 fuel for socystinox is generally known13, for example in West German Patent Application No. 1 283 532 - has been used to prepare polymeric trihydroxyl compounds, 1 lyne/anate and catalysts. A method is described for producing fire-retardant polyurethane from, in this case the general formula.

H(n-m)+2(NH4)mPnO3n++ [n in the formula
is an integer having an average value above 10, m is an integer up to n+2, and m/n is about 07 to 11] has been proposed as a flame retardant additive. .

When used in polyurethane, ammonium polyphosphate of the general formula above imparts good flame resistance to polyurethane, but
This has the disadvantage that it is not sufficiently water-insoluble and is therefore washed out of the silastic over time due to weather effects. Seidoin Patent Application Publication No. 12835
As is clear from column 3 of No. 32 &+ll; Ammonium phosphate 1 (
ammonium polyphosphate at 25°C.
．． ! Up to 9 are dissolved.

That is, up to 50% of the amount of ammonium polyphosphate used is a soluble component.

West German Patent Application No. 2949537 and No. 30
No. 05252 describes a method for producing hydrolytically stable ammonium polyphosphate powders by encapsulation with melamine/formaldehyde resins as well as phenol/formaldehy 1 resins. In both cases, by this measure their water solubility is clearly reduced compared to uncoated ammonium polyphosphate.

However, the drawback when used as a flame retardant is that the coating releases only small amounts of formaldehyde.

Finally, German Patent Application No. 3,217,816 describes the preparation of TFa water-lysis stable powdered ammonium i4' phosphate by surrounding it with a hardened epoxy/resin. The apparent effect of reducing sexual components is less than with melamine/formaldehyde resins.

Problems to be Solved by the Invention Accordingly, it is desirable to prevent as fully as possible the risk of leakage of am/monium BoII tzate due to the influence of weather when used as a flame retardant in silastic, wooden or paper products. I
Thus, the problem arose of providing means and methods for reducing the solubility of formal ammonium phosphate in water.

It must be ensured that the material does not release harmful substances Tf1.

while! Solution to the 11α point: According to the present invention, it has been shown that great advantages are obtained by replacing maleic and phenolic resins with polyurea, and that this does not require preloading in any way. In other words, the present invention provides a free-flowing powdered polyphosphoric acid having the general formula %, where n represents an integer with an average value of about 20 to 800, and the ratio of m to n is about 1. Regarding ammonium-based flame retardants, the flame retardant comprises: a) about 75 to 99,5 parts by weight of ammonium polyphosphate; ;surrounding ammonium phosphate particles)
It is characterized by comprising about 0.5-25% by weight. According to the present invention, it is possible to obtain a low-temperature fuel with low hydrolytic stability.

The agent according to the invention generally has a mean particle size of between about 0.001 and 0.1, and the degree of condensation n of the ammonium polyphosphate is preferably an integer with an average value of between 450 and 800.
Van Wazer), Glyph Iter (Gr 1f
fiter ) and macro (McCul tough
) Author r 7f-Luke o・J (Ana l
, Chem, ), Vol. 26, p. 1755 (1954)
- Determined by titration method].

According to another advantageous embodiment of the shaver according to the invention, the polyurea component is from 2 to about 15% by weight.

Polyurea is a reaction product formed by the addition of polyamide/anate with polyino-7-ite, which is formed by the reaction of polyino/anate with water and with separation of carbon dioxide.

The term polyino/anate includes all commercially available aromatic or aliphatic and polyino/anate as well as prepolymers based on polyurethane-1 or polyhydric diimides or haphorino/annulate-modified polyino/anates, which prepared from commercially available aromatic or aliphatic no- and poly-ino/anoates by partial reaction with polyhydroquino compounds, or by partial carbodiimidization, or by partial trimerization; This can be for example polyurethane, polyino/americate or polycal 1.
Used to produce 1+' Neumidor form.

The method of the present invention for producing this hydrolytically stable, finely loaded flame retardant is based on the diluent and the general formula A suspension of free-flowing powdered ammonium polyphosphate, polyino/anate and water is kept under stirring at a temperature of 30-200°C for 05-5 hours and subsequently cooled. characterized by filtering and drying the ammonium polyphosphate, which at this point is micro-filled with polyurea.

In particular, the method optionally comprises the following aspects: a) preparing a suspension consisting of a diluent and ammonium polyphosphate, and subsequently adding a polyiso/anate solution in the diluent to this suspension; Gradually add water in a diluent; b) In the general formula of ammonium polyphosphate, n is an average value of 45
is an integer from 0 to 800; C) as diluent a proto/inert water-miscible solvent such as, for example, aliphatic, aromatic and mixed aliphatic/aromatic ketones, preferably acetate; or Using solvent mixtures; d) Aromatic or aliphatic no and polyino/anoates commercially available as polyino7i- and polyurethane/-
or using a prepolymer based on a polyruzenimide or a polyinoanurate-modified polyino/anate, in which the prepolymer from a commercially available aromatic or aliphatic compound and polyiso/anate is partially or by partial Cal, P neumidization, or by partial trimerization.

e) Partial carbodiimidation as poly(1+1)/anate (obtained by two-layer synthesis; f) as a reaction component for polyino/anate;
4-ilj Ills7. g) ammonium polyphosphate in the suspension, diluent sariino/anate, water ratio of 115-25:0.05-0.
25 20,005~0.1, advantageously]: 2:
0.1: Maintained at 0.02 1), h) Reaction time 50~
at a temperature of 100° C. for 1 to 2 hours; i) drying is carried out at a temperature of 80° to 150° C. in an inert gas atmosphere, preferably within 90° C.; J) as a flame retardant The average particle size of ammonium polyphosphate is 0.0
k) The polyurea component in the flame retardant is from 2 to about 15% by weight.

Finally, the invention relates to the use of said agent for the fire protection adjustment of polyurethane or polyurethane foam, in which case the content of shavings in the polyurethane foam is 71! 'About 5-25% by weight based on the amount of lyol component.

Addition of the polyurea to the ammonium polyphosphate particles is accomplished by adding polyurea to the polyphosphoric acid in a proton-inert, water-miscible solvent or solvent mixture, such as an aliphatic, cyaromatic or ρ-aromatic ketone. This can be carried out by adding a suspension of ammonium/bolyne/anate/water, the polyaddition reaction being carried out under heating.

By coating the ammonium polyphosphate particles with polyurea according to the invention, the solubility of the ammonium polyphosphate in water is significantly reduced, which is why ammonium polyphosphate pretreated in this way is used, for example, as a flame retardant in polyurethane foams. If you do, it will work to your advantage.

Polyurea is still used as a coating material for ammonium polyphosphates due to its reduced water solubility compared to the known coating materials phenol/formaldehyde resins and epoxy/resins. This is superior in that it does not liberate form)'aldehyde.

EXAMPLES The flame retardant according to the invention, its preparation and advantages are detailed in the following examples. Commercially available ammonium polyphosphate as well as various similarly commercially available polyisocyanates were used to carry out the experiments described in the Examples. 1. In detail, the following products are: 1. Exolit 422■ (manufactured by Hoechst Akchengesellschaft, Frankfurt am Main): Finely divided ammonyl polyphosphate A that is sparingly soluble in water: ( NH4POρ.

and its degree of condensation n is ~700.

2. Body? (Caradate) 30■(
47F - Nissier Chemie GmbH, Frankfurt am Main) Mixtures of two different aromatic non- and tri-isocyanates and 4°4'-diphenylmethane diisocyanate (as main component).

The product is a deep brown to black liquid. The isocyanate content is 30.2% NGO. Density (23
℃) is 1.22-1.24 y/mt, viscosity (25
℃) is 160-240 mP, aste.

3 Suzorasec (5uprasec) 1042■
(1 Manufactured by Isocie ICC GmbH,
Frankfurt am Main): Density (at 25°C)
1.24y/- and viscosity (at 25°C) 235 mPa
5 black solvent-free liquid. Incyanate content is NGO
It is 28.8 to 30.2%.

4, Tesmonoyu = /l/ (Desmodur)
T8σ10 (manufactured by Bayer Akchengesellschaft, C.Z.-Kusen): isomer mixture of aromatic diisocyanates having 80% by weight of 2,4-diisocyanate doluol and 20% by weight of 2,6-diisocyanate doluol. The product is a colorless liquid with an isocyanate content of approximately 48% NGO. The density (at 25°C) is approximately 1.2 f/-.

5 Inophorone diisocyanate (3-incyanate methyl-3,5,5-trimethyl 7 chlorohexyl isocyanate) (Hemitsusier).

Manufactured by Värke Fuyürs Akchengesernjaft,
(Marl): Insya Foil Content NGO37,5-37
．． 8% liquid colorless product. Density (at 20℃) is 1.05
8-1.0649/mt, viscosity (at 20℃) is 15mP
It is a5.

Example 1 Acetone (moisture content: <0.3%) in a glass stirrer
) Suspend Exolit 422 x 2502 in 1000-, then suspend Caladate 30''1 in acetone 100-
5. A solution of Or was added dropwise. The suspension was then heated slightly to the boil and a solution of 52 mm of water in 5 mm of acetone was added dropwise. After stirring for 2 hours, it was cooled to room temperature and filtered. The resulting filter cake was dried at 110° C. in a nitrogen stream.

A coated ammonium polyphosphate 2531 was obtained.

The polyurea content was 4.5% by weight.

To measure the water-soluble components, the produced product 102 was mixed with water 1
00-, and the five suspensions were stirred at 25°C and 60°C for 20 minutes. The water-insoluble constituents of the product were subsequently pipetted into aluminum dishes, which had been centrifuged for no more than 40 minutes, and evaporated at 120° C. in a drying cabinet. Water-soluble components were calculated from the amount of evaporation residue. The results are shown in Table 1.

Example 2 The procedure was as in Example 1. However, a solute of Karaguete 3σ"30r in acetone 100 was used.

A coated ammonium polyphosphate 2672 having a polyurea content of 97% by weight was obtained. Average values for water-soluble components are shown in Table 1.

Example 3 Processed as in Example 1. However, a solution of Szolasec 1042 and 1502 in acetone 100 was added. A coated ammonium saryphosphate 2492 was obtained having a polyurea content of 51% by weight. Average values for water-soluble components are shown in Table 1.

Example: Treated in the same manner as in Example 1. However, a solution of Sprasec 1042.3Of in 100% acetone was added. A coated ammonium polyphosphate 2641 having a urea content of 10.2% by weight was obtained. Average values for water-soluble components are shown in Table 1.

Example 5 Suspend 422 @ 250 t of Echinolite in 400 d of acetone in a glass stirrer, then add 10 d of acetone.
A solution of Desmo, Joule T80, 152 in 100 ml and a solution of 52 water in acetone 50, were added. The suspension was then heated slightly to boiling. After stirring for 2 hours, it was cooled to room temperature and filtered. The resulting oak slag was dried at 100° C. in a nitrogen stream. A coated ammonium polyphosphate 257f having a polyurea content of 4.3% by weight was obtained. Average values for water-soluble components are shown in Table 2.

Example 6 Each case was treated in the same manner. However, acetone 100Wd
! A solution of 30ml of Desmonil T80 was used. A modified +r' ammonium phosphate 2727 with an isourea component of 75% by weight was obtained. The average values for the water-soluble components are given in Table 2.

Example 7 Processed as in Example 5. However, a solution of inophorone noisocyanate 152 in acetone 100 was used. 252 t of coated ammonium polyphosphate having a polyurea content of 52% by weight were obtained. Average values for water-soluble components are shown in Table 2.

Example 8 1 treated in the same manner as Example 5, Shikashi Acetone 10Q
A solution of 30 g of inholonoiso7a in methane was added. Coated with a polyurea component of 89% by weight. Ammonium polyphosphate 2661? r) l') I fell asleep. The average values for water-soluble components are shown in Table 2.Example 9 The treatment was carried out in the same manner as in Example 5. However, carragete 30" modified with polycarbo diimide in acetone 100"
(This is a carbodiimilation catalyst (
For example, 1-methyl-1-oxo-phosphor: Hoechst Akchengesellschaft, Frankfurt.
Am Main) 15 ppm and 30 g of a solution prepared by heating at 110° C. until the isocyanate content was 27.5% was added. Polyurea component 8
．． coated ammonium polyphosphate with 7% by weight 2
72v was obtained. Average values for water-soluble components are shown in Table 3.

Example 1゜Processed in the same manner as in Example 9. However, a polycarbodiimide modified Carragete 30 with an isocyanate content of 25.4% was used. A coated ammonium polyphosphate 266f having a polyurea content of 83% by weight was obtained. Average values for water-soluble components are shown in Table 3.

Example 11 Processed as in Example 9. However, Caladate 30, modified with polycarbo and Neumibi, having an isocyanate content of 227% was used. 269 v of coated ammonium polyphosphate with a polyurea content of 88% by weight were obtained. Average values for water-soluble components are shown in Table 3.

Example] 2 Processed in the same manner as in Example 9. However, polycarbodiimide-modified Caladate 30 (l?) with an incyanate content of 198% was used. Polyurea component 91% by weight
A coated ammonium polyphosphate 279f having the following properties was obtained. Average values for water-soluble components are shown in Table 3.

From the values shown in Tables 1 to 3 it can be seen that by using the regulator according to the invention the content of water-soluble components can be significantly reduced (up to 90% at 25°C, 9% at 6.0'C).
up to 7%).

Continuation from page 1

Claims (1)

[Claims] 1. General formula: H_(_n_-_m)_+_2(NH_4)_mP_n
O_3_n_+_1 [where n represents an integer with an average value of about 20 to 800 and the ratio of m to n is about 1] in a flame retardant based on free-flowing powdered ammonium polyphosphate; a) about 75-99.5% by weight of ammonium polyphosphate b) about 0.5-25% by weight of the reaction product from polyisocyanate and water (the resulting polyurea surrounds the individual ammonium polyphosphate particles) Flame retardant based on free-flowing powdered ammonium polyphosphate, characterized in that it consists of: 2. The flame retardant according to claim 1, which has an average particle size of about 0.01 to 01 mm. 3. The flame retardant according to claim 1 or 2, wherein n is an integer with an average value of 450 to 800. 4. A flame retardant according to any one of claims 1 to 3, wherein the polyurea component is from 2 to about 15% by weight. 5. The flame retardant according to any one of claims 1 to 4, wherein the polyurea is a reaction product produced by polyaddition of a polyisocyanate and water. 6. Diluent and general formula: H_(_n_-_m_)_+_2(NH_4)_mP_
nO_3n_+_1 [wherein n represents an integer with an average value of about 20 to 800, and the ratio of m to n is about 1], a suspension consisting of free-flowing powdered ammonium polyphosphate, polyisocyanate, and water. The suspension is maintained at a temperature of 30 to 200 °C under stirring for 0.5 to 5 hours, subsequently cooled and filtered, at which point the ammonium polyphosphate microfilled with polyurea is dried. , a process for the preparation of a flame retardant based on free-flowing powdered ammonium polyphosphate. 7. A claim consisting of preparing a suspension consisting of a diluent and ammonium polyphosphate, and gradually adding a polyisocyanate solution in the diluent and then water in the diluent to this suspension. The method described in Section 6. 8. In the general formula of ammonium polyphosphate, n is an average value of 45
8. The method according to claim 6 or 7, wherein the number is an integer from 0 to 800. 9. The claimed invention consists of using as diluent a proton-inert, water-miscible solvent or solvent mixture, such as for example aliphatic, aromatic and mixed aliphatic/aromatic ketones, preferably acetone. The method according to any one of the ranges 6 to 8. 10. Aromatic or aliphatic di- and polyisocyanates commercially available as polyisocyanates, and polyurethanes
10. The process as claimed in claim 6, comprising using a prepolymer based on a polycarbodiimide- or polyisocyanurate-modified polyisocyanate. 11. The method according to claim 10, which comprises using as polyisocyanate a polycarbodiimide-modified polyisocyanate obtained by partial carbodiimidation, such as polycarbodiimide-modified 4,4'-diphenylmethane diisocyanate. 12. Claims 6 to 1, which consist of using water as a reaction component for polyisocyanate.
The method described in any one of items 1 to 1. 13. The ratio of ammonium polyphosphate: diluent: polyisocyanate: water in the suspension is 1:1.5 to 2.5:0.0.
5-0.25: 0.005-0.1, advantageously 1:2:
13. A method according to any one of claims 6 to 12, comprising maintaining the ratio 0.1:0.02. 14. The method according to any one of claims 6 to 13, wherein the reaction time is 1 to 2 hours at a temperature of 50 to 100°C. 15. Drying is carried out at a temperature of 80 to 150° C. in an inert gas atmosphere, preferably in a stream of nitrogen.
The method according to any one of paragraphs 1 to 14. 16. The average particle size of the ammonium polyphosphate finely filled as a flame retardant is 0.01 to 0.1 mm, preferably 0.03 mm.
~0.06 mm, claims 6 to 1
The method described in any one of items 5 to 5. 17. The method of any one of claims 6 through 16, wherein the polyurea component in the flame retardant is from 2 to about 15% by weight. 18, General formula: H_(_n_-_m)_+_2(NH_4)_mP_n
O_3_n_+_1 (wherein n represents an integer with an average value of about 20 to 800 and the ratio of m to n is about 1) is based on free-flowing powdered ammonium polyphosphate, and a) about ammonium polyphosphate; 75-99.5% by weight and b) about 0.5-25% by weight of the reaction product from polyisocyanate and water (the resulting polyurea surrounding the individual ammonium polyphosphate particles). A fire-retardant polyurethane or polyurethane foam containing a flame retardant consisting of from about 5 to 25% by weight, based on the amount of the polyol component of the polyurethane.