Flame retardant composition

Abstract

A liquid flame retardant composition which comprises one or more flame retarding agents, which are the epoxides obtainable by reacting tetrabromobisphenol A with epichlorohydrin and their end-capped derivatives represented by Formula (1) is provided. The liquid composition is especially useful in the preparation of rigid polyurethane foams.

Claims

1. A liquid composition comprising: A) One or more solid flame retarding agents represented by Formula 1b: ##STR00014## wherein n, the degree of polymerization, is an integer in the range from 0 to 5; B) one or more liquids selected from the group consisting of polyols and esters of a pentavalent phosphorus acid; and C) tribromoneopentyl alcohol; said polyols comprising a polyol with a number of hydroxyl groups of not less than 3 and a hydroxyl number in a range of 150 to 850 mg KOH/g; wherein the liquid composition is a solution in which the one or more solid flame retardants of Formula 1 b and the tribromoneopentyl alcohol are dissolved in the one or more liquids, with the bromine content of the liquid composition being not less than 25% w/w.

2. A liquid composition according to claim 1, wherein the one or more solid flame retarding agents are in the form of a mixture comprising the individual tribromophenol-terminated compounds represented by Formula 1b wherein n is 0, 1 and 2.

3. A liquid composition according to claim 2, wherein the weight concentrations of the tribromophenol-terminated compounds represented by Formula 1b wherein n is 0 and 1 are in the ranges of 55-70% and 20-35%, respectively, relative to the total weight of all tribromophenol-terminated compounds represented by Formula 1b in the liquid composition.

4. A liquid composition according to claim 1, wherein the weight concentration of the one or more solid flame retarding agents represented by Formula 1b is between 10 and 60%.

5. A liquid composition according to claim 1, comprising a polyether-polyol.

6. A liquid composition according to claim 5, wherein the polyether-polyol is non-halogenated.

7. A liquid composition according to claim 1, wherein said one or more liquids comprise an ester of a pentavalent phosphorus add.

8. A liquid composition according to claim 4, which is a solution comprising 20-40 by wt % the one or more solid flame retarding agents of Formula 1b and 20-40 by wt % tribromoneopentyl alcohol.

9. A process for preparing the liquid composition of claim 1, comprising heating one or more flame retarding agents represented by Formula 1b and tribromoneopentyl alcohol together with one or more liquids selected from the group consisting of polyols and esters of a pentavalent phosphorus acid until a clear solution is obtained, following which the liquid composition is cooled and stored until use.

10. A process, which comprises: providing a liquid composition as defined in claim 1, mixing said liquid composition with one or more polyols, and optionally with at least one blowing agent, at least one catalyst and at least one surfactant thereby affording a polyol component suitable for the preparation polyurethane or polyisacyanate foams.

11. A process according to claim 10, which further comprises reacting the polyol component with a diisocyanate component in the presence of at least one blowing agent, at least one catalyst, at least one surfactant and at least one phosphate ester to obtain a polyurethane or polyisocyanate foam.

12. A process according to claim 11, which is carried out on-site at the environmental temperature at the working site.

13. A process according to claim 11, wherein the process produces a rigid polyurethane foam.

14. A rigid polyurethane foam, obtainable by the process of claim 13, which foam comprises a structural unit prepared by reacting the diisocyanate compound with one or more of the compounds represented by Formula 1b: ##STR00015## wherein n is an integer in the range from 0 to 5.

Description

EXAMPLES

Preparation 1

Preparing a Flame Retarding Agent of Formula 1(b)

(1) To a 1-liter glass kettle equipped with stirrer, electric heating mantle, a thermometer and a reflux condenser were added 100 grams of brominated epoxy resin (commercially available as F-2001) having the following characteristics: EEW of 398 grams per mole and bromine content of 49% (w/w), 300 grams methyl isobutyl ketone and 155 grams of tribromophenol. The mixture was stirred until all solids dissolve and then 0.75 grams of tributyl amine was added. The reaction mixture was heated slowly to reflux and the reaction continued for 6 hours.

(2) After cooling to room temperature, the reaction mixture was washed 3 times with distilled water followed by phase separation of the aqueous phase. Finally the methyl isobutyl ketone was distilled off at 160 under vacuum.

(3) 250 grams of the resin according to Formula (1b) were obtained having the following properties:

(4) Softening point: 101 C.

(5) Average molecular weight (as determined by GPC): 1460

(6) Bromine content: 59 wt %.

(7) The procedure described above may be modified in order to obtain different resins of Formula (1b), namely, mixtures comprising the monomer (1b-I), the dimer of Formula (1b-II), the trimer of Formula (1b-III) and higher oligomers in different proportions, by changing the weight ratio of the reactants (e.g., reacting 574 g of YDB 400 or F-2001, 294.6 g of tribromophenol and 127 g of tetrabromobisphenol A).

Examples 1-6

Liquid Flame-Retardant Compositions which Contain the Epoxy Resins of Formula (1a)

(8) Table 1 summarizes the compositions of several liquid flame-retardant formulations of the present invention and stability tests carried in respect thereto, which compositions are based on a flame retarding agent of Formula (1a), or a combination thereof with tribromoneopentyl alcohol. The general preparative procedure was as follows:

(9) A 0.5 liter reactor, equipped with a mechanical stirrer, a thermometer and a reflux condenser, was charged with the liquid component (a non-halogenated polyether polyol, which is Alcupol C-5710; or halogen-substituted organic phosphate, which is tris(2-chloropropyl)phosphate (TCPP), or a mixture thereof) and was heated to 60 C. The flame retarding agent (F-2001 or F-2001 and subsequently FR-513, or vice versa) was then added to the reactor, after which the temperature was increased to 70-100 C. The resulting mixture was heated for about two hours at 70-100 C., until a clear solution was obtained. After cooling to room temperature, a stable solution was obtained.

(10) TABLE-US-00001 TABLE 1 Compositions based on F-2001 C5710 OH F-2001, FR-513, TCPP, (polyol), num- Br, Stability, Ex. wt % wt % wt % wt % ber wt % Days* 1 60 40 ~0 ~30 ~180 2 20 30 50 52 ~32 ~180 3 30 30 40 52 ~36 ~180 4 20 30 50 337 ~32 ~180 5 60 20 20 114 ~30 ~180 6 20 30 30 20 166 ~32 ~180 The values given for the stability represent the length of time during which the compositions have been stored under ambient temperature conditions without the formation of a precipitate. The tests are continuing and thus the values given are not the limits of the stability.

(11) The liquid compositions of the present invention were used as flame retardants in standard formulations for rigid polyurethane foams. The foams were prepared either by continuous or discontinuous processes (Examples 7-11 and Examples 12-16 below, respectively).

(12) In addition to the flame retardant liquid compositions of the present invention, the following materials were used in the preparation of the polyurethane foams:

(13) Polyols Used for Continuous Production:

(14) 1. Terol 516-Polyester polyol having a hydroxyl value of 305 mg KOH/g.

(15) 2. Fox-O-Pol M530-polyol having a hydroxyl value of 530 mg KOH/g.

(16) 3. Glycerol.

(17) Polyols Used for Discontinuous Production:

(18) 1. Alcupol R-2510-Glycerol initiated polyether polyol having a hydroxyl value of 250 mg KOH/g.

(19) 2. Alcupol C-5710-Glycerol initiated polyether polyol having a hydroxyl value of 570 mg KOH/g.

(20) 3. Alcupol R-4720-Sorbitol initiated polyether polyol having a hydroxyl value of 475 mg KOH/g.

(21) Ancillary Chemicals

(22) DMCHA dimethylcyclohexylamine

(23) AM 58 trimerisation catalyst

(24) DC 193 silicone surfactant

(25) TCPP tris(chloropropyl)phosphate

(26) TEP triethylenephosphate

(27) Pentane blowing agent

(28) Isocyanate

(29) MDI: polymeric diphenylmethane diisocyanate

Examples 7-11

Continuous System for Preparing Rigid Polyurethane Foams Using F-2001 Based Liquid Flame Retardant Compositions

(30) The procedure for the foam preparation was as follows: The polyols, water, surfactant, the F-2001 based flame retardant compositions of Examples 2 to 6 (abbreviated FR of Example x in table 2 below)phosphate esters and catalysts were weighed and placed in a mixing beaker and mixed to form a homogeneous solution. To this solution was added pentane, and after additional mixing, the polymeric isocyanate. The mixture was stirred at 3000 rpm for 6 sec and poured into another beaker. The foam that formed was kept at least 24 hr at room temperature and then removed from the beaker and cut into test specimens with a saw. The samples were then tested for flammability according to the DIN 4102 B2 test procedure (a flame height of 15.0 cm or less means that the foam has passed the test). Table 2 summarizes the ingredients and parameters for the foam preparation and the results of the testing of the foams.

(31) TABLE-US-00002 TABLE 2 Pentane-blown B2 continuous system using compositions based on F-2001 (mixed at 20 C.) Example Example Composition (g) Example 7 Example 8 Example 9 10 11 M530 30 30 30 30 30 Terol 516 30 30 30 30 30 Glycerol 7 7 5 5 5 FR of Example 2 37.2 F-2001/FR-513/TCPP 20:30:50 FR of Example 3 37.2 F-2001/FR-513/TCPP 30:30:40 FR of Example 4 37.2 F-2001/FR-513/C5710 20:30:50 FR of Example 5 37.2 F-2001/TCPP/C5710 60:20:20 FR of Example 6 37.2 F-2001/FR-513/TCPP/C5710, 20:30:30:20 TCPP 20 20 20 20 20 TEP 2.8 2.8 2.8 2.8 2.8 DMCHA 2 2 2 2 2 AM58 1 1 1 1 1 DC193 1.5 1.5 1.5 1.5 1.5 Water 2.49 2.49 2.49 2.49 2.49 Pentane 13.2 13.2 13.2 13.2 13.2 Total 147.19 147.19 145.19 145.19 145.19 Isocyanate, g 154.57 154.57 173.72 150.84 156.17 (Urestyl-10) Mix time, sec 6 6 6 6 6 Cream time, sec 12 12 13 12 12 Gel time, sec 33 32 39 32 34 Tack free time, sec 38 39 45 36 40 Cure time, sec 118 125 115 94 121 Br content in polyol 8.9 10.2 9.0 8.5 9.0 mixture, wt % Br content in foam 4.2 4.8 3.9 4.0 4.2 wt % Flame height, cm 8.9 7.6 9.1 8.8 8.5 (DIN 4102)

(32) In table 2 (and also in the tables 3 and 5 below) the parameters related to the foam preparation are defined as follows:

(33) Cream time: The time between the discharge of the foam ingredients from the mixing beaker and the beginning of the rise of the foam.

(34) Gel time: The time between the discharge of the foam ingredients from the mixing beaker and the time that the foam will stick to an introduced probe, and strings out from it when withdrawn.

(35) Tack-free time: The time between the discharge of the foam ingredients from the mixing beaker and the time that the outer skin of the foam mass loses its stickiness or adhesive quality.

(36) Cure time: The time required for sufficient reaction completion to develop the desired polymer properties such as strength, dimensional stability, elongation, etc.

Examples 12-16

Discontinuous System for Preparing Rigid Polyurethane Foams Using F-2001 Based Liquid Flame Retardant Compositions

(37) The procedure for the foam preparation was as follows:

(38) The polyols, water, surfactant, F-2001 based flame retardant compositions of Examples 2 to 6 (abbreviated FR of Example x in table 3 below)phosphate esters and catalysts were weighed and placed in a mixing beaker, and mixed to form a homogeneous solution. To this solution was added the polymeric isocyanate, then the mixture was stirred at 3000 rpm for 15 sec and poured into another beaker. The foam that formed was kept at least 24 hr at room temperature and then removed from the beaker and cut into test specimens with a saw. The samples were then tested for flammability according to the DIN 4102 B2 test procedure (a flame height of 15.0 cm or less means that the foam has passed the test). Table 3 summarizes the ingredients and parameters for the foam preparation and the results of the testing of the foams.

(39) TABLE-US-00003 TABLE 3 Water-blown B2 discontinuous system using compositions based on F-2001 (mixed at 20 C.) Example Example Example Example Example Composition (g) 12 13 14 15 16 R4720 35 35 35 35 35 R2510 20 20 23 23 23 C5710 21 21 18 18 18 FR of Example 2 20 F-2001/FR-513/TCPP 20:30:50 FR of Example 3 20 F-2001/FR-513/TCPP 30:30:40 FR of Example 4 20 F-2001/FR-513/C5710 20:30:50 FR of Example 5 20 F-2001/TCPP/C5710 60:20:20 FR of Example 6 20 F-2001/FR-513/TCPP/C5710, 20:30:30:20 TCPP 25 25 25 25 25 DMCHA 0.9 0.9 0.9 0.9 0.9 DC 193 1.5 1.5 1.5 1.5 1.5 Water 4.6 4.6 4.6 4.6 4.6 Total 128 128 128 128 128 Isocyanate, g 167.00 167.00 179.50 167.73 170.48 Mix time, sec 15 15 15 15 15 Cream time, sec 25 25 25 25 25 Gel time, sec 102 107 121 120 107 Tack free, time 231 209 220 239 216 Br content in polyol 5.0 5.8 5.0 4.7 5.0 mixture, wt % Br content in foam, 2.2 2.5 2.1 2.0 2.1 wt % Flame height, cm 9.4 11.8 11.4 13.0 11.6 (DIN 4102)

Examples 17-27

Liquid Flame-Retardant Compositions which Contain the Tribromophenol-Terminated Resins of Formula (1b)

(40) Table 4 summarizes the compositions of several liquid flame-retardant compositions of the present invention and stability tests carried out in respect thereto, which compositions are based on a flame retarding agent of Formula (1b), or a combination thereof with tribromoneopentyl alcohol. The general preparative procedure was as follows:

(41) A 0.5 liter reactor, equipped with a mechanical stirrer, a thermometer and a reflux condenser, was charged with the liquid component (a non-halogenated polyether polyol, which is Alcupol C-5710; or halogen-substituted organic phosphate, which is tris(2-chloropropyl)phosphate (TCPP); or a mixture thereof) and was heated to 50-60 C. The flame retarding agent (F-3014, or F-3014 and subsequently FR-513, or vice versa) was then added to the reactor, after which the temperature was increased to 65-100 C. The resulting mixture was heated for about two hours at 65-100 C., until a clear solution was obtained. After cooling to room temperature, a stable solution was obtained.

(42) TABLE-US-00004 TABLE 4 Compositions based on F-3014 C5710 OH Exam- F-3014, FR-513, TCPP, (polyol) num- Br, Stability, ple wt % wt % wt % wt % ber wt % Days* 17 60 40 48 36 ~180 18 20 30 50 68 34 ~180 19 30 30 40 76 37 ~180 20 20 30 50 353 34 ~180 21 20 25 55 373 30 ~180 22 20 20 60 393 27 ~180 23 20 30 10 40 296 34 ~180 24 20 30 20 30 239 34 ~180 25 20 40 40 313 41 ~180 26 20 40 25 15 173 41 ~180 27 15 30 55 379 31 ~180 The values given for the stability represent the length of time during which the compositions have been stored under ambient temperature conditions without the formation of a precipitate. The tests are continuing and thus the values given are not the limits of the stability.

Examples 28-38

Continuous System for Preparing Rigid Polyurethane Foams Using F-3014 Based Liquid Flame Retardant Compositions

(43) The compositions of Examples 17-27 were used for the preparation of rigid polyurethane foams according to the following procedure:

(44) The polyols, water, surfactant, the F-3014 based flame retardant compositions of Examples 17-27 (abbreviated FR of Example x in Table 5 below)phosphate esters and catalysts were weighed and placed in a mixing beaker and mixed to form a homogeneous solution. To this solution was added pentane, and after additional mixing, the polymeric isocyanate. The mixture was stirred at 3000 rpm for 6 sec and poured into another beaker. The foam that formed was kept at least 24 hr at room temperature and then removed from the beaker and cut into test specimens with a saw. The samples were then tested for flammability according to the DIN 4102 B2 test procedure (a flame height of 15.0 cm or less means that the foam has passed the test). Table 5 summarizes the ingredients and parameters for the foam preparation and the results of the testing of the foams.

(45) TABLE-US-00005 TABLE 5 Pentane-blown B2 continuous system using compositions based on F-3014 (mixed at 20 C.) Composition, g Example 28 Example 29 Example 30 Example 31 Example 32 M530 30 30 30 30 30 Terol 516 30 30 30 30 30 Glycerol 7 7 7 5 5 FR of Example 17 37.2 F-3014/TCPP 60:40 FR of Example 18 37.2 F-3014/FR-513/TCPP 20:30:50 FR of Example 19 37.2 F-3014/FR-513/TCPP 30:30:40 FR of Example 20 37.2 F-3014/FR-513/C5710 20:30:50 FR of Example 21 37.2 F-3014/FR-513/C5710 20:25:55 TCPP 20 20 20 20 20 TEP 2.8 2.8 2.8 2.8 2.8 DMCHA 2 2 2 2 2 AM58 1 1 1 1 1 DC193 1.5 1.5 1.5 1.5 1.5 Water 2.49 2.49 2.49 2.49 2.49 Pentane 13.2 13.2 13.2 13.2 13.2 Total 147.19 147.19 147.19 145.19 145.19 Isocyanate, g 154.36 156.21 157.03 174.54 176.59 (Urestyl-10) Mix time, sec 6 6 6 6 6 Cream time, sec 11.5 11.5 11.5 12.5 12 Gel time, sec 32 32 32 37 38 Tack free time, sec 36 35 37 43 42 Cure time, sec 93 99 108 112 106 Br content in 10.0 9.5 11.2 9.6 8.6 polyol mixture, wt % Br content in foam, wt % 4.7 4.4 5.2 4.2 3.7 Flame height, cm 9.3 11.3 9.3 11.4 11.8 (DIN 4102) Composition, g Example 33 Example 34 Example 35 Example 36 Example 37 Example 38 M530 30 30 30 30 30 30 Terol 516 30 30 30 30 30 30 Glycerol 5 5 5 5 7 5 FR of Example 22 37.2 F-3014/FR-513/C5710 20:20:60 FR of Example 23 37.2 F-3014/FR-513/TCPP/C5710; 20:30:10:40 FR of Example 24 37.2 F-3014/FR-513/TCPP/C5710; 20:30:20:30 FR of Example 25 37.2 F-3014/FR-513/C5710 20:40:40 FR of Example 26 37.2 F-3014/FR-513/TCPP/C5710; 20:40:25:15 FR of Example 27 37.2 F-3014/FR-513/C5710 15:30:55 TCPP 20 20 20 20 20 20 TEP 2.8 2.8 2.8 2.8 2.8 2.8 DMCHA 2 2 2 2 2 2 AM58 1 1 1 1 1 1 DC193 1.5 1.5 1.5 1.5 1.5 1.5 Water 2.49 2.49 2.49 2.49 2.49 2.49 Pentane 13.2 13.2 13.2 13.2 13.2 13.2 Total 145.19 145.19 145.19 145.19 147.19 145.19 Isocyanate, g 178.64 169.51 163.66 171.26 166.98 178.03 (Urestyl-10) Mix time, sec 6 6 6 6 6 6 Cream time, sec 12 12 12 12 12 12 Gel time, sec 38 35 34 34 34 37 Tack free time, sec 44 42 37 40 36 43 Cure time, sec 100 95 94 106 109 99 Br content in 7.5 9.6 9.6 11.7 11.5 8.8 polyol mixture, wt % Br content in foam, wt % 3.2 4.2 4.3 5.1 5.2 3.8 Flame height, cm 12.4 9.9 10.1 10.3 9.1 11.5 (DIN 4102)

Examples 39-42

Liquid Flame-Retardant Compositions which Contain the Tribromophenol-Terminated Resins of Formula (1b)

(46) Table 6 presents the ingredients of several liquid flame-retardant compositions of the present invention and stability tests carried out in respect thereto, which compositions are based on a flame retarding agent of Formula (1b), or a combination thereof with tribromoneopentyl alcohol. The compositions were obtained by mixing the ingredients at 70-90 C. and subsequent cooling.

(47) TABLE-US-00006 TABLE 6 Compositions based on F-3014 and/or F-3020 F-3014 F-3020 FR-513 C5710 Terol 516 R-4720 OH Br Stability Ex. wt % wt % wt % wt % wt % wt % number wt % months 39 20 30 50 222 34 6 40 20 30 50 307 34 6 41 20 30 50 345 33 2 42 10 10 30 50 345 34 2 *The values given for the stability represent the length of time during which the compositions have been stored under ambient temperature conditions without the formation of a precipitate. The tests are continuing and thus the values given are not the limits of the stability.

Examples 43-46

Continuous System for Preparing Rigid Polyurethane Foams Using F-3014 and/or F-3020 Based Liquid Flame Retardant Compositions

(48) The compositions of Examples 39-42 were used for the preparation of rigid polyurethane foams according to the previously described procedures. Table 7 summarizes the ingredients and parameters for the foam preparation and the results of the testing of the foams.

(49) TABLE-US-00007 TABLE 7 Pentane-blown B2 continuous system using compositions based on F-3014 and/or F-3020 (mixed at 20 C.) Example Example Example Example Composition, g 43 44 45 46 M530 30 30 30 30 Terol 516 30 30 30 30 Glycerol 5 5 5 5 FR of Example 39 37.2 F-3014/FR-513/Terol 516 20:30:50 FR of Example 40 37.5 F-3014/FR-513/R-4720 20:30:50 FR of Example 41 37.2 F-3020/FR-513/ C5710 20:30:50 FR of Example 42 37.2 F-3014/F-3020/ FR-513/C5710 10:10:30:50 TCPP 20 20 20 20 TEP 2.8 2.8 2.8 2.8 DMCHA 2 2 2 2 AM58 1 1 1 1 DC193 1.5 1.5 1.5 1.5 Water 2.49 2.49 2.49 2.49 Pentane 13.2 13.2 13.2 13.2 Total 145.19 145.19 145.19 145.19 Isocyanate, g (Urestyl- 161.92 170.64 174.54 174.54 10) Mix time, sec 6 6 6 6 Cream time, sec 12 14 14 13 Gel time, sec 31 36 36 37 Tack free time, sec 41 49 49 52 Cure time, sec 136 102 98 97 Br content in polyol 9.6 9.6 9.3 9.6 mixture Br content in foam 4.3 4.2 4.0 4.2 Flame height, cm DIN 11.6 11.7 11.7 11.9 4102

Example 47 (Comparative)

Comparison of the Solubility of Various Flame Retardants

(50) A structural analogue of tetrabromobisphenol A, which is tetrabromobisphenol S (wherein a sulfur bridge connects the two aromatic rings) was reacted with epichlorohydrin in isopropanol, in order to obtain the analogues of the flame retardant of Formula 1a. The resulting reaction product, whose structure was confirmed by means of .sup.1H NMR, has very poor solubility both in methyl isobutyl ketone and in mixtures of polyols and phosphate esters, and as a result it cannot be transformed into its end-capped derivatives (the analogues of Formula 1b) nor can it be easily delivered into the polyurethane foaming system.

Examples 48-49 (Comparative)

(51) The composition according to Example 20, which is a solution of 20% F-3014 and 30% FR-513 in polyol C5710 (with a bromine content of 34%), was compared with a 50% solution of FR-513 in polyol C5710 (37% bromine) in respect to their flame retarding efficacy in rigid polyurethane foams. To this end, the two compositions were incorporated in pentane-blown continuous foaming systems to give the foams as described in Table 8 below.

(52) TABLE-US-00008 TABLE 8 Pentane-blown B2 continuous system using compositions based on F-3014 (mixed at 20 C.) Composition, g Example 48 Example 49 M530 30 30 Terol 516 30 30 Glycerol 5 5 FR of Example 20 37.2 F-3014/FR-513/C5710 20:30:50 FR-513/C5710 50:50 37.2 TCPP 20 20 TEP 2.8 2.8 DMCHA 2 2 AM58 1 1 DC193 1.5 1.5 Water 2.49 2.49 Pentane 13.2 13.2 Total 145.19 145.19 Isocyanate, g (Urestyl-10) 174.54 177.26 Mix time, sec 6 6 Cream time, sec 14 15 Gel time, sec 37 36 Tack free time, sec 51 51 Cure time, sec 88 90 Br content in polyol mixture 9.6 10.4 Br content in foam 4.2 4.5 Flame height, cm (DIN 4102) 11.4 11.8

(53) As can be seen from the data in Table 8, the composition of the invention shows better flame retardancy (flame height 11.4 cm) than the FR composition based on FR-513 only (flame height 11.8 cm) despite the fact that the bromine content in the second composition is higher.