阅读说明：本技术 具有无卤素的阻燃剂的软质泡沫 (Flexible foams with halogen-free flame retardants ) 是由 R.W.阿尔巴赫 P.文纳 于 2018-07-11 设计创作，主要内容包括：本发明涉及具有磷腈的阻燃的聚氨酯软质泡沫以及通过组分A与组分B的反应制备PUR-软质泡沫的方法：组分A包含：A1,异氰酸酯-反应性组分,A2,发泡剂,包含水,A3,任选的助剂和添加剂,和A4,阻燃剂,B,异氰酸酯组分,其特征在于,阻燃剂A4包含式(I)的磷腈：[P<Sub>m</Sub>N<Sub>m</Sub>X<Sub>k</Sub>](I),其中,X彼此独立地代表O-芳基或NR-芳基并且至少一个芳基基团是被取代的,其中X可以代表桥,R选自H、C<Sub>1</Sub>-C<Sub>4</Sub>烷基和芳基,和m代表数字1-5,特别优选3或4,k取决于m并且代表数字0-2m,和磷腈不带有异氰酸酯反应性的基团。(The invention relates to flame-retardant polyurethane flexible foams having phosphazenes and to a method for producing PUR flexible foams by reacting a component A with a component B: component A bagComprises the following components: a1, an isocyanate-reactive component, a2, a blowing agent comprising water, A3, optional auxiliaries and additives, and a4, a flame retardant, B, an isocyanate component, characterized in that the flame retardant a4 comprises a phosphazene of formula (I): [ P ] m N m X k ](I) Wherein X independently of one another represents O-aryl or NR-aryl and at least one aryl group is substituted, wherein X may represent a bridge, R is selected from H, C 1 ‑C 4 Alkyl and aryl radicals, and m represents a number from 1 to 5, particularly preferably 3 or 4, k depending on m and representing a number from 0 to 2m, and the phosphazenes not carrying isocyanate-reactive groups.)

1. A process for preparing open-celled PUR flexible foams by reacting component A with component B,

component A comprises

A1 an isocyanate-reactive component,

a2, a blowing agent, comprising water,

a3 optional auxiliaries and additives,

a4 flame retardant

B an isocyanate component selected from the group consisting of,

characterized in that the flame retardant A4 comprises a phosphazene of formula (I)

[P_mN_mX_k](I)，

Wherein

X independently of one another represent O-aryl or NR-aryl and on average at least 10% of the aryl groups in all phosphazenes are substituted, where X may represent a bridge,

r is selected from H, C₁-C₄Alkyl and aryl radicals and

m represents a number from 1 to 5, particularly preferably 3 or 4,

k depends on m and represents the number 0-2m

And the phosphazene is free of isocyanate reactive groups.

2. A process according to claim 1, characterized in that a polyether polyol having a hydroxyl number of from 25 mg KOH/g to 2000 mg KOH/g is contained in the isocyanate-reactive component a 1.

3. The process according to any of claims 1 or 2, characterized in that the isocyanate-reactive component a1 comprises a PHD-polyol.

4. Process according to any of claims 1 to 3, characterized in that blowing agent A2 comprises at least one compound selected from halogen-free chemical blowing agents, halogen-free physical blowing agents and (hydro) fluorinated olefins.

5. A process according to any of claims 1 to 4, characterized in that the flame retardant A4 does not contain a component having isocyanate-reactive groups.

6. The process as claimed in any of claims 1 to 5, characterized in that the flame retardant A4 comprises from 50% to 100% by weight of phosphazene of the formula (I), based on the total mass of the flame retardant A4.

7. A process as claimed in any one of claims 1 to 6, characterized in that the phosphazene of formula (I) is present in an amount of from 0.5% by weight to 40.0% by weight, based on reaction mixture A1 to A4 without B.

8. A process according to any of claims 1 to 7, characterized in that the flame retardant A4 comprises at least one compound selected from halogen-free phosphoric acid esters and halogen-free phosphonic acid esters.

9. The process according to any one of claims 1 to 8, characterized in that at least one substituent of the at least one substituted aryl group of the O-aryl or NR-aryl group of the substituent X is selected from CN-, C₁-C₄Alkyl-, nitro-, sulfonate-, carboxylate-or phosphonic acidEster group, wherein N (aryl) is preferably substituted by at least one C₁-C₄Alkyl-substituted and O-aryl is preferably substituted by at least one CN, COOR or C₁-C₄Alkyl substitution.

10. Method according to any one of claims 1 to 9, characterized in that the phosphazene is a cyclic phosphazene and preferably has a structure of the general formulae (III) to (VI)

Wherein

X independently of one another represent O-aryl or NR-aryl,

aryl independently represents a substituted aryl group and

r is selected from H, C₁-C₄Alkyl groups and aryl groups.

11. The process according to any one of claims 1 to 10, characterized in that component A comprises

A139.50 to 99.28 wt.% (based on components A1 to A4) of a polyether polyol or a mixture of polyether polyols, preferably based on propylene oxide and ethylene oxide, having an average equivalent weight of 0.8 to 2.2 kg/mol and an average functionality of 1.8 to 6.2,

a20.2 to 20.0% by weight, based on components A1 to A4, of water,

a30.02 to 3.02% by weight, based on components A1 to A4, of an aliphatic amine, preferably those containing OH or NH groups, as catalyst, and up to 30% by weight, based on components A1 to A4, of a filler which is stably dispersed in A1 and is not isocyanate-reactive,

a40.5 to 8.0% by weight, based on components A1 to A4, of flame retardants.

12. Process according to any one of claims 1 to 11, characterized in that component B comprises at least one compound chosen from: 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate and polyisocyanates derived from 2, 4-and/or 2, 6-tolylene diisocyanate or derived from 4,4 '-and/or 2,2' -diphenylmethane diisocyanate having a carbodiimide group, a urethane group, an allophanate group, an isocyanurate group, a urea group or a biuret group.

13. The process according to any of claims 1 to 12, characterized in that the content of difunctional isocyanate in component B is 60 to 100% by weight, preferably 75 to 90% by weight, based on component B.

PUR-flexible foam obtainable by the process according to any of claims 1 to 13, wherein the PUR-flexible foam has a coarse density, in particular

• 10 kg/m³-20 kg/ m³Or is or

• 35 kg/ m³-80 kg/ m³And an isocyanate characteristic number of 60 to 110, or

• 200 kg/ m³-300 kg/ m³And an isocyanate characteristic number of 75 to 120.

15. Use of the PUR-flexible foams according to claim 13 or 14 for the preparation of furniture cushions, textile underlays, mattresses, car seats, head rests, armrests, sponges and components and seat-and dashboard facings.

Examples

The invention is further illustrated by the following examples, but is not limited thereto.

A1-1 glycerol-initiated polyoxyalkylene having a molecular weight of 4800g/mol was used as suspension with A3-1

A2-125 wt.% urea/water

Reaction product of A3-1 Toluene Diisocyanate (TDI) and hydrazine hydrate used as suspension with A1-1

A3-2 Jeffcat^®Mixture of ZF-10 (Huntsman) and Dabco NE1070 (Air Products) in a weight ratio of 1:20

A3-3 Tegostab^®B8738 LF2 polyether Dimethicone (Evonik)

A4-1 Rabitle^®FP 200, cyclic phosphazenes (halogen-free) with phenoxy-and methoxy-substituents

A4-2 Rabitle^®FP 300-B, Cyclic phosphazene with Cyanophenoxy substituent (halogen free)

A4-3 Rabitle^®FP 366 Cyclic phosphazenes with propoxy substituent (Fushimi Pharmaceuticals, halogen-free)

A4-4 Rabitle^®FP 390, cyclic phosphazenes with tolyloxy-and phenoxy substituents (halogen-free)

A4-5 trichloropropyl phosphate, halogenated flame retardants

A4-6 Melamine, a halogen-free solid flame retardant, insoluble in all other components

A4-7 at 10 bar on Pd/C as catalyst consisted of 60g of A4-2 and 8dm³Hydrogen of 0.42dm³The NCO-reactive reaction product of THF (1). 884g/mol CH was obtained from 66.45 mg KOH/g amine number₂-NH₂Equivalent weight of (c).³¹P-NMR (400 MHz, CDCl₃) 8.01 and 7.94 ppm vs. H₃PO₄(comparison A4-2: 7.49, 7.54 ppm).¹H-NMR(400MHz，CDCl₃) The complete disappearance of the double peaks at 7.50ppm and 7.40ppm in A4-2 means complete hydrogenation of the nitrile groups in A4-2. In that¹In H-NMR, CH₂-NH₂The signal of the radical is located at 3.70ppm vs. TMSTo (3). ASAP-MS M/z694 (10%, M + H)⁺, C₃₆H₃₀N₃O₆P₃, CAS 1184-10-7), m/z 708 (10%, M+H⁺, C₃₇H₃₂N₃O₆P₃),m/z 723 (60%, M+H⁺, C₃₇H₃₃N₄O₆P₃, CAS 81525-08-8), m/z 737 (100%, M+H⁺,C₃₇H₃₅N₅O₆P₃), m/z 752 (40%, M+H⁺, C₃₈H₃₆N₅O₆P₃)。C₃₇H₃₃N₄O₆P₃CAS 81525-08-8, contains one aminomethyl group. C₃₈H₃₆N₅O₆P₃Comprising two aminomethyl groups. Both are therefore suitable for reacting with isocyanates

B-1 Desmodur^®44V20L, isocyanate having 31.5% by weight of NCO groups and a viscosity of 0.2Pa s at 298K (Covestro)

B-2 Desmodur^®T80, isocyanate having 48% by weight of NCO groups, a mixture of 80% by weight of 2,4-TDI and 20% by weight of 2,6-TDI (Covestro)

Preparation and testing of PUR Flexible foams

The burn test was based on british standard BS 5852: 1990-part 2, with ignition source 4("Crib"), but without a textile overlay.

The measurement of the crude density was carried out according to DIN EN ISO 845 (10 months 2009).

The press hardness and the damping of the PUR flexible foams were measured in accordance with DIN EN ISO 3386-1 (9 months 2010).

To prepare the PUR flexible foams, the required amount of component A was pre-filled into a cardboard beaker (volume: about 850ml) with a metal sheet bottom and loaded with air at 4200 revolutions/min for 45 seconds with a stirring apparatus (Pendraulik) with a standard stirring disk (d =64 mm). Component B was then added to component a and the mixture was mixed thoroughly with a stirring device for 5 seconds. The precise composition of each component is shown in table 1. To determine the characteristic reaction time, the mixing is startedA stopwatch is started. Approximately 93g of the reaction mixture were then poured into a 23 ℃ warm Teflon-lined film aluminum box mold having 1.6dm³The volume of (a). The mold was closed and locked for 6 minutes. Mechanical studies and flame retardancy test measurements were performed on the molded foams and reaction kinetics measurements were performed on the free-foaming reaction mixture in a beaker.

When the mixture is observed to swell (the reaction of isocyanate and water begins), the starting time t is reached_c. Setting time t_GThe time for pulling out the yarn from the surface of the PUR-flexible foam being lifted by twisting the yarn with a wooden bar (Holzsiedestäbchen) was determined, and when the expansion of the PUR-flexible foam was finally stopped, the lifting time t was reached_s. It should be noted here that some systems tend to sag a section and then rise again.

As can be seen from table 1, the "kinetic and mechanical properties" section, examples 2-5 with phosphazene as flame retardant have a similar core coarse density (RD) as examples 1 and 6 without flame retardant or with TCPP as flame retardant. The PUR flexible foam from example 7 with melamine as flame retardant has an increased coarse density compared with the remaining PUR flexible foam. However, the plasticizing effect is not as pronounced as TCPP. It can also be seen that the flame retardants from examples 2 to 6 have an effect as plasticizers, and accordingly they are particularly well suited for PUR flexible foams. Example 1 and especially example 7 show a marked hardening of the PUR flexible foam. The damping of the PUR-flexible foams of examples 3 to 5 is good compared with the PUR-flexible foams with TCPP and with melamine without flame retardant.

The properties of the PUR-flexible foams in the burning test are shown in the "burning test Performance data" section of Table 1. The efficiency of the flame retardant was evaluated from the molar ratio of the flame retardant a4 used in examples 2-7: the larger the difference, the faster the flame extinguishes and the more efficient the flame retardant.

It can be seen that examples 2 and 4, which use phosphazenes which do not have the general formula (I) according to the invention as flame retardants, do not lead to self-extinguishing PUR flexible foams. It can also be seen that example 7, which was prepared with a non-low melting or liquid flame retardant, produced the same fire performance as example 1. In particular example 3 shows a particularly marked reduction in the time to self-extinguishment per mmol of flame retardant A4 used. The flame retardant of example 5 worked as well or slightly more effectively than the flame retardant of example 6, where example 6 contained a halogenated flame retardant and accordingly had disadvantages such as corrosive hydrochloric acid in the smoke.