Organic Materials as Fire and Flame Retardant Synergists

Abstract

Use of oligomeric or polymeric compounds according to the general formula I

##STR00001##

as organic synergists of fire and flame retardants in self-extinguishing polymeric compositions.

Claims

1. A polymer composition containing fire and flame retardants and compounds of Formula I ##STR00012## wherein X is a halogen or ##STR00013##  or a heterocyclic radical containing in the ring at least one nitrogen atom which radical is linked to the triazine ring through one of such nitrogen atoms, R.sub.2 is alkyl or cycloalkyl, R.sub.1 is a divalent radical of piperazine of the formula ##STR00014## or a divalent radical of the type ##STR00015## n is an integer from 2 to 30, extremes included having a value of 2-30, m is an integer from 2 to 6, extremes included having a value of 2-6, p is an integer from 2 to 12, extremes included having a value of 2-12, X.sub.1=OH, NH.sub.2 or X whereby X and X.sub.1 may be the same or different, X.sub.2=hydrogen or a C.sub.1-C.sub.4 alkyl group: a polymer selected from the group consisting of ethyl vinyl acetate, a polyolefinic polymer or copolymer, a polyamide or a polyester; and, at least one further flame retardant selected from the group consisting of metal hydroxides, metal phosphinates, halogenated fire retardants, and N-alkoxy hindered amine radical generating compounds.

2. (canceled)

3. (canceled)

4. (canceled)

5. (canceled)

6. (canceled)

7. (canceled)

8. An electronic or electrical apparatus comprising a polymer composition according to claim 1.

9. A cable comprising a polymer composition according to claim 1.

10. An outdoor article or construction article comprising a polymer composition of claim 1.

11. A polymer composition according to claim 1 comprising ethyl vinyl acetate as the polymer.

12. A polymer composition according to claim 1 comprising a polyolefinic polymer or copolymer as the polymer.

13. A polymer composition according to claim 1 comprising polyamides or polyesters as the polymer.

14. A polymer composition according to claim 1 comprising 0.1 to 10% by weight of the compound of Formula I.

15. A polymer composition according to claim 14 comprising 0.5 to 7.5% by weight of the compound of Formula I.

16. A polymer composition according to claim 1 wherein the fire and flame retardants and compounds of Formula I and the at least one further flame retardant form a synergistic blend.

Description

[0036] FIG. 1 illustrates flame retarding properties of certain compositions according to the invention.

[0037] FIG. 2 illustrates flame retarding properties of certain compositions according to the invention.

[0038] FIG. 3 illustrates flame retarding properties of certain compositions according to the invention.

[0039] FIG. 4 illustrates flame retarding properties of certain compositions according to the invention.

[0040] FIG. 5 illustrates flame retarding properties of certain compositions according to the invention.

[0041] An aspect of the invention, is therefore, polymer compositions containing fire and flame retardants and compounds of Formula I

##STR00006##

wherein [0042] X is a halogen or

##STR00007##  or a heterocyclic radical containing in the ring at least one nitrogen atom which radical is linked to the triazine ring through one of such nitrogen atoms, [0043] R.sub.2 is alkyl or cycloalkyl, [0044] R.sub.1 is a divalent radical of piperazine of the formula

##STR00008## [0045] or a divalent radical of the type

##STR00009## [0046] n is an integer from 2 to 30, extremes included, [0047] m is an integer from 2 to 6, extremes included, [0048] p is an integer from 2 to 12, extremes included, and [0049] X.sub.1=OH, NH.sub.2 or X whereby X and X.sub.1 may be the same or different, [0050] X.sub.2=hydrogen or a C.sub.1-C.sub.4 alkyl group.

[0051] Such compound is present in the composition in amounts from 0.1 to 10% by weight of the composition, preferably in amounts from 0.5 to 5% by weight.

[0052] As fire and flame retardants, phosphorus based flame retardants or inorganic flame retardants or nitrogen based flame retardants or halogen based flame retardants or N-alkoxy hindered amine radical generating fire and flame retardants can be used.

[0053] It has been found that the compounds of formula “I” surprisingly exhibit exceptional properties as fire retardant synergists by so-called “self-immolation” principle of fire retardancy, without the use of phosphates. In the event of a fire, compounds of formula “I” undergo a self-burning and charring process, thereby forming fire shields and nipping the fire in the bud. Table 1 below underlines such excessive char formation in the event of fire. Thus, there is a 15-20% more fire protecting char formation in case of samples containing compound of Formula II than in case of the samples not containing this compound.

[0054] The resulting polymer composites, such as EVA, containing such fire retardants according to this invention also release very low heat upon burning. Importantly, the smoke toxicity and corrosivity are also low because of low or no halogens in the fire retardants according to this invention. Table 2 and FIGS. 1, 2 and 3 further underline the effectiveness of the compounds of formula I as fire and flame retardant synergists. Thus, in spite of replacing 50 parts of aluminium trihydroxide (ATH) with just 2.5-5 parts of the compound of Formula II in a typical cable polymer composition, all critical parameters of fire and flame retardancy such as flame out time, heat release rate (HRR), peak heat release rate (pkHRR), total heat release (THR) remain the same, in spite of almost 15% more incinerable organic material present (Table 2). Moreover, the resulting polymer compositions when used for cable applications show the following advantages: [0055] e) For the same amount (100%) of base polymer/resin required to be used for insulation jacketing of the same length of cable, almost 18% less requirement (in weight) of the corresponding polymer composition (Example: 100 parts of base polymer=250 parts of compound A (polymer+ATH)=205 parts of compound AP (polymer+ATH+PPMT) i.e. 82% of compound A) [0056] f) For the same thickness of the insulation ca. 10% less of the corresponding polymer composition is needed (Table 2) [0057] g) Ease of processing, more productivity, less energy demand [0058] h) Non-ionic, for better E&E (IEV) conformity of insulating materials [0059] i) Less abrasion of the processing equipment [0060] j) Lighter-weight, better-quality, and eco (disposal) cable (LW-0LH-HQ-E=Light weight-zero/low halogen-high-quality eco cable)

[0061] Nano-clays and composites are also used as synergists for flame retardants. They are inorganic materials with the following advantages for the compounds of formula I: [0062] Light-weight purely organic materials of high efficacy [0063] In the event of fire own expanded char formation as fire-wall, due to high C & N content [0064] Non-ionic! Perhaps better E&E (IEV) conformity of insulating materials [0065] Better heat stability versus organo-clays [0066] Light stabilizing effect due to chemical relationship with light stabilizers [0067] Universal applications

[0068] Similarly, other inorganic compounds such as antimony oxides, and borate salts are also used as synergists for certain applications. However, their efficacy is low, as is to be expected of inorganic materials, alone due to their high density.

[0069] Organic synergists of high efficacy, as is to be expected due to their low density and better chemical relationship to the organic polymers, are few and far between.

[0070] Thus it has now been found that the compounds of Formula I are also suitable as synergists of halogen containing flame retardants in place of antimony oxides. Antimony oxides are no more desired as flame retardant synergists because of their potential toxicity.

[0071] For engineering polymers such as polyamides and polyesters, dialkyl phosphinates such as aluminium diethylphosphinate, with synergists, are commonly used as fire retardants. This chemistry increases corrosion in processing equipment and lowers mechanical properties (compounding world, December 2012). It has now been found that the compounds for Formula I combined with such dialkyl phosphinates do not cause such corrosion and degradation of the mechanical properties of the resulting polymer formulations.

[0072] It has also been found that compounds of I are also suitable as synergists for N-alkoxy hindered amine radical generating fire retardants such as Flamestab NOR of BASF, besides alleviating their deficiencies such as low heat stability.

[0073] Description of the Cone Test

[0074] The tests are done with the samples and have the purpose to give an assessment about the combustion behaviour under cone calorimeter conditions.

[0075] The ISO 5660 norm defines cone calorimeter parameters driving. During the cone calorimeter test, the materials are subjected to a heat flux of 50 kW/m.sup.2.

[0076] The samples are ignited by a spark created by an electrical device. Combustion products are aspirated in a duct, where they are analyzed.

[0077] Heat Release Rate (HRR [kW/m.sup.2) curve is obtained from measuring the oxygen percentage that is consumed during the combustion. HRR is one of the most used parameters to evaluate the burning behavior.

[0078] Other important factors are:

[0079] Total Heat Evolved (THR [MJ/m.sup.2])

[0080] Flame Out (FO [s])

[0081] Peak of Heat Release Rate (pkHRR [kW/m.sup.2])

[0082] All tests are performed three times to check repeatability. All parameters are reported with their experimental deviation, calculated as (maximum value−minimum value)/2.

[0083] Surface temperature measurements were performed during cone calorimeter tests, using K-type 0.5 mm stainless steel sheathed thermocouple. Thermocouple was carefully placed and supported to keep contact with the upper surface of the sample throughout the experiment.

[0084] The temperature of the sample bottom layer was measured inserting a K-type 1 mm stainless steel sheathed thermocouple parallel to the specimen's surface between the polymer specimen and the aluminium foil.

[0085] The following examples illustrate certain embodiments of the invention.

EXAMPLES

Example 1

[0086] The following materials were used [0087] PPMT/T1 and/T2: two samples of Poly(piperazinyl,morpholinyl,triazine); compound of formula II

##STR00010##

[0088] Formula II (Example 3 compound Ma of the U.S. Pat. No. 8,202,924) [0089] EVA(ethyl vinyl acetate): ELVAX® 470 DuPont (19% VA) [0090] ATH (aluminium trihydroxide): Nabaltec Apyral® 40CD

[0091] The materials were dry-blended in the required proportions and extruded using a twin screw co-rotating extruder Leistriz 18-40D.

[0092] The resulting granulates were pressed to samples of 100 mm×100 mm×6 mm size and subjected to the cone calorimeter test as described above

Cone Test Results

[0093]

TABLE-US-00001 TABLE 1 Residue mass (char) at the end of cone calorimeter test at 50 kW/m.sup.2 Residue Residue Residue Materials Specimen mass mass % mass % (parts) number (g) of materials of ATH EVA = 100 1 32.01 38 100 ATH = 150 2 32.31 38 100 PPMT = 0 3 31.54 38 100 EVA = 100 1 22.43 30 120 ATH = 100 2 22.33 30 120 PPMT/T1 = 2.5 3 22.04 29 115 EVA = 100 1 22.28 30 115 ATH = 100 2 22.14 29 120 PPMT/T2 = 2.5 3 22.16 29 120 EVA = 100 1 23.20 30 120 ATH = 100 2 23.05 30 120 PPMT/T1 = 5 3 23.00 30 120 EVA = 100 1 22.68 30 120 ATH = 100 2 22.46 30 120 PPMT/T2 = 5 3 22.47 30 120 EVA(ethyl vinyl acetate): ELVAX ® 470 DuPont (19% VA) ATH (aluminium trihydroxide): Nabaltec Apyral ® 40CD PPMT/T1 and/T2: two samples of Poly(piperazinyl, morpholinyl, triazine); compound of formula II

TABLE-US-00002 TABLE 2 Average data of the cone calorimeter test at 50 kW/ m.sup.2 Weight For Sample same Flame Materials weight Incinerableorganic volume Out HRR pkHRR THR (parts) (g) material (%) (%) (s) (kW/m.sup.2) (kW/m.sup.2) (MJ/m.sup.2) EVA = 100 83.3 ± 0.1 100 100 859 ± 36   173 ± 21.8 .sup. 356 ± 22.1  155.4 ± 13.0 ATH = 150 (EVA 100) PPMT = 0 EVA = 100 75.4 ± 0.1 113 89 766 ± 11 202.9 ± 7.0 443.8 ± 25.6 164.5 ± 3.6 ATH = 100 (EVA 110) PPMT/T1 = 2.5 EVA = 100 75.3 ± 0.1 113 89.3 780 ± 24 201.3 ± 6.6 393.1 ± 14.4 169.2 ± 7.1 ATH = 100 (EVA 110) PPMT/T2 = 2.5 EVA = 100 76.3 ± 0.1   115.8 90.5 835 ± 7  178.5 ± 1.1 357.1 ± 14.1 157.0 ± 0.8 ATH = 100 (EVA 110) PPMT/T1 = 5 EVA = 100 75.9 ± 0.1   115.3 90 860 ± 21 174.7 ± 4.7 364.3 ± 13.8 .sup. 160 ± 2.3 ATH = 100 (EVA 100) PPMT/T2 = 5 EVA(ethyl vinyl acetate): ELVAX ® 470 DuPont (19% VA) ATH (aluminium trihydroxide): Nabaltec Apyral ® 40CD PPMT/T1 & PPMT/T2: Poly(piperazinyl, morpholinyl, triazine); compound of formula II HRR: Heat Release Rate PkHRR: Peak Heat Release Rate THR: Total Heat Release

[0094] FIG. 1 illustrates the Heat Release Rate versus time of the samples, FIG. 2 illustrates the temperature profiles of the surface of the samples versus time, and FIG. 3 illustrates the temperature profiles of the of the bottom of the sample versus time.

Example 2

[0095] Study on combustion behaviour and fire performance of polypropylene (PP) based composites

[0096] The following materials were used [0097] PPMT/T1 and/T2: two samples of Poly(piperazinyl,morpholinyl,triazine); compound of formula II [0098] PP: Polypropylene, Moplen HP 500N (LyondellBasell) [0099] MDH: Magnesium hydroxide, APYMAG 60S (Nabaltec) [0100] CaCO3: Calcium carbonate, Omyacarb 1T-AV (Omya) [0101] PTFE: Polytetrafluoreethylene, Lubeflon K100 (Polis srl)

[0102] The materials were dry-blended in the required proportions and extruded using a twin screw co-rotating extruder Leistriz 18-40D.

[0103] The resulting granulates were pressed to samples of 100 mm×100 mm×6 mm size and subjected to the cone calorimeter test as described above

TABLE-US-00003 TABLE 3 Composition of the studied formulations Product Formulation parts: 0 1 2 3 4 5 6 7 8 9 10 PP 100 100 100 100 100 100 100 100 100 100 100 MDH 0 200 150 150 150 150 150 0 0 0 0 CaCO3 0 0 0 0 0 0 0 150 150 150 150 PPMT T1 0 0 2.5 0 0 2.5 0 0 5 0 0 PPMT T2 0 0 0 2.5 2.5 0 5 0 0 5 5 PTFE 0 0 0 0 0.1 0.1 0 0 0 0 0.1

TABLE-US-00004 TABLE 4 CONE TEST RESULTS cone data normalized with non-combustible content % residue MDH CaCO3 Residue (%) based on content Content after the cone inorganic PHR PHR test Content PP HP 500N 0 0 Formulation 1 200 51 100 Formulation 2 150 45 117.6 Formulation 3 150 40 104.5 Formulation 4 150 47 122.9 Formulation 5 150 44 115 Formulation 6 150 46 120 Formulation 7 150 57 100 Formulation 8 150 66 116 Formulation 9 150 69 121 Formulation 10 150 62 108.8

TABLE-US-00005 TABLE 5 cone data normalized with non-combustible content HRR pkHRR [kW/m2] [kW/m2] Reduction Reduction normal- normal- PP ized with ized with content HRR PP content PkHRR PP content (%) [kW/m2] (%) [kW/m2] (%) PP HP 500N 100 846.1 — 1560.1 — Formulation 1 33.3 64.5 77.1 135.7 73.9 Formulation 2 39.6 62.8 81.2 140.9 77.2 Formulation 3 39.6 67 80 149.4 75.8 Formulation 4 39.6 62.2 81.4 134.1 78.3 Formulation 5 39.6 66.1 80.3 138.6 77.6 Formulation 6 39.2 62.7 81.1 136.8 77.6 Formulation 7 40 88.3 73.9 165.3 73.5 Formulation 8 39.2 76.3 77.0 169.3 72.3 Formulation 9 39.2 85.4 74.2 159.7 73.9 Formulation 10 39.2 83.4 74.8 203.0 66.8 • 13-

[0104] Summary of the test: With the calculation of reduction of heat release rate normalized by the content of polypropylene (PP), it can be clearly seen that compound of formula II could help to reduce the heat release rate of polypropylene (PP). The Heat Release Rate (HRR) and the peak Heat Release Rate (PkHRR) are reduced by 66.1 to 81.1%, a measure of the intensity of heat generated in the event of fire (Table 5).

[0105] Samples containing MDH performed better compared to CaCO3 containing composites. Moreover, the increased weights of the residues formed at the end of the cone test normalized by the content of non-combustible inorganic materials clearly indicate much slower or in-complete burning in the presence of the compound of Formula II (Table 4), and hence the better fire retardancy.

[0106] The foregoing results are illustrated on FIGS. 4 and 5. FIG. 4 illustrates the Heat Release Rate versus time of the samples, FIG. 5 illustrates the temperature profiles of the surface of the samples versus time. Each of the figures includes an inset which is a detail of a portion of the larger x-y graph illustrated in the figure.

Example 3

[0107] Combination with Phosphinates

TABLE-US-00006 Formulation 1 Formulation 2 Formulation 3 (%) (%) (%) Polyamide 6 1) 55 55 55 Glass fibres 25 25 25 Aluminium 20 15 0 diethylphosphinate 2) Compound of Formula 0 5 0 II 3) Melamine 0 0 20 polyphosphate 4) Total burning time(s)* >250 s 30 s >250 s UL 94 V(1.6 mm)* None V-0 None 1) Ultramid B3S, BASF, 2) Exolite OP 1230, Clariant, 3) MCA PPM Triazine HF 4) Melapur 200, BASF *The total burning time and the UL 94 test of the Underwriters Laboratory are most widely used and recognized test methods (besides more elaborate cone test described and employed above in example 1 and 2) for fire retardancy. The rating is based on the ability to self-extinguish after ignition by a naked flame. The shorter the time, the better the performance. J. Troitzch: International Plastics Flammability Handbook; Hanse Publishers; Munich-Vienna-New York 1990

Example 4

[0108] Combination with Halogenated Flame Retardants

TABLE-US-00007 Formulation 1 Formulation 2 Formulation 3 (%) (%) (%) PP HP 500N 1) 75 75 75 Decabromodiphenyl 10 10 0 ethane 2) Compound of 0 3.75 0 Formula II 3) ammonium 15 11.25 25 polyphosphate 4) Antimony trioxide 0 0 0 Total burning time(s) >250 s 12 s >250 s UL 94V(1.6 mm) None V-2 None 1) Moplen HP 500N (LyondellBasell) 2) ICL 3) MCA PPM Triazine HF, MCA Technologies GmbH 4) Exolite AP 422, Clariant

Example 5

[0109] Combination with NOR (N-Alkoxy Hindered Amines) Technology

TABLE-US-00008 Formulation 1 Formulation 2 Formulation 3 (%) (%) (%) PP HP 500N 1) 84 84 84 Flamestab NOR 2) 1 1 1 Compound of 0 3.75 0 Formula II 3) ammonium 14 11.25 15 polyphosphate 4) Total burning time(s) >250 s 40 s >250 s UL 94V(1.6 mm) None V-2 None 1) Moplen HP 500N (LyondellBasell) 2) BASF 3) MCA PPM Triazine HF, MCA Technologies GmbH 4) Exolite AP 422, Clariant

Example 6

[0110] Polyester Fibres in Combination with Compound of Formula III

##STR00011##

[0111] The compound (CAS 63562-33-4) was obtained from Hongwei New Materials Technology Co. Ltd, PR China.

[0112] The process of making flame retarded polyester with compound II and Compound of formula III is briefly described as follows:

[0113] 7.2 kgs of ethylene glycol and 10 kgs of dimethyl terephthalate are subjected to a transesterification process at temperatures between 170° C. and 220° C. in the presence of 2.3 g of Mn(OCOCH.sub.3).H.sub.2O to give the terephthalic acid-glycol ester pre-condensate.

[0114] 500 g of the compound of Formula III and 3.5 g of Sb.sub.2O.sub.3 are then added at 220° C. The reaction vessel is now evacuated to a pressure of 1 mm Hg and heated to 250° C. (reaction mixture temperature) followed by polycondensation at 0.2 mm Hg and 275° C. until a relative viscosity of 1.85 is obtained. To the resulting polymer melt are now added 150 g of the compound of Formula II and stirred for 15 minutes.

[0115] Thereafter, the polymer is spun into the filaments following the usual process of making polyester fibre filaments.

[0116] The burning characteristics of flame retarded polyester are assessed by the common methods like Self Ignition Temperature (DIN 51794), Ignition Temperature (DIN 51794), Limiting Oxygen Index (LOI), Small Burner Test (DIN 53906).

[0117] The resisting fire-retarded polyester shows the following characteristics [0118] Self-ignition temperature: 530-550° C. [0119] Ignition temperature; 380-400° C. [0120] LOI: 27