Nitrogen

Chapter 17

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Comparison of the Impact of Phosphorus and Phosphorus/Nitrogen on the Flammability of Styrenic Oligomers Bob A. Howell* and Adina Dumitrascu Department of Chemistry, Center for Applications in Polymer Science, Central Michigan University, Mt. Pleasant, Michigan 48859-0001 *E-mail: [email protected]

Phosphorus compounds have long been utilized as flameretarding additives for polymeric materials. The development of new, highly effective, nontoxic phosphorus flame retardants is an area of great current interest because of the increasing regulatory restrictions on the use of organohalogen compounds for flammability control. It has been broadly suggested that the flame retardant activity of phosphorus compounds may be enhanced by the presence of nitrogen. To provide a direct assessment of the merits of this suggestion, the flammability behavior of oligomers derived from styrene monomers containing phosphorus moieties has been compared to that of similar structures containing both phosphorus and nitrogen.

Introduction Organophosphorus compounds have been widely used as flame retardants for polymeric materials (1–4). Many of these have been utilized as polymer additives while others have been incorporated into the polymer either as components of the mainchain or as pendant groups (5–29). The development of new, more effective organophosphorus agents has been stimulated by the increasing regulatory restrictions on the use of organohalogen flame retardants (30). Organohalogen compounds, particularly the brominated aryl ethers, are © 2012 American Chemical Society In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


persistent in the environment, tend to bioaccumulate and may pose potential to human health risks (31–34). A significant advance has been the utilization of derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to replace tetrabromobisphenol A as flame-retarding entities in epoxy resins and poly(carbonate) (35–41). These materials are effective at low levels of incorporation and do not significantly degrade the physical properties of the polymer into which they are placed. It has often been suggested that the effectiveness of organophosphorus flame retardants may be enhanced by the presence of nitrogen (42–49). To assess the impact of nitrogen on the effectiveness of phosphorus flame retardants two sets of styrene oligomers, one containing only phosphorus and the other containing both phosphorus and nitrogen, have been synthesized, characterized by thermal and spectroscopic methods, and subjected to pyrolysis combustion flow calorimetry.

Experimental General In general, reactions were carried out in a dry three-necked, round-bottomed flask fitted with a Liebeg condenser bearing a gas-inlet tube, a magnetic stirring bar, and a pressure-equalizing dropping funnel. All glassware was flame-dried and allowed to cool under a stream of dry nitrogen prior to use. Chromatography was accomplished using ultrapure synthetic silica gel SilaFlash P60 (230-400 mesh silica) in a column of appropriate size, and combinations of hexane and ethyl acetate as eluents. Silica-coated (fluorescence UV254) Whatman plates (Whatman Ltd.) were used for thin layer chromatography (TLC).

Materials Diethylphosphite (98%), diphenylphosphite (~85%), 4-tert-butylcatechol (TBC) and sodium hydride (NaH) as a 60% suspension in mineral oil were purchased from the Aldrich Chemical Company and dimethylphosphite (98%) from Alfa-Aesar, and used as received. 4-(Chloromethyl)styrene (min. 90%), 4-aminostyrene and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) were supplied by TCI America and used as received. Styrene (≥ 99%, Sigma Aldrich) was passed through a column of basic alumina prior to use, in order to remove polymerization inhibitors. 2,2′-Azobis(isobutyronitrile) (AIBN) (Sigma Aldrich), which was used as a radical initiator, was recrystallized from methanol. All solvents and other common reagents were obtained from usual laboratory suppliers and were purified prior to use by standard methods.

236 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


Analytical Techniques Nuclear magnetic resonance (NMR) spectra were obtained using 10% to 25% solutions in deuterochloroform and a Varian Mercury 300 MHz spectrometer. Proton and carbon chemical shifts (δ) were reported in parts-per-million (ppm) with respect to tetramethylsilane (TMS) as internal reference (δ = 0.00 ppm). 31P-NMR spectra were referenced relative to the signal for triphenylphosphate at δ : –18.0. Infrared (IR) spectra were obtained using thin films between sodium chloride plates or solid solutions (1%) in anhydrous potassium bromide (as discs) and a Nicolet MAGNA-IR 560 spectrometer. Absorptions were recorded in wavenumbers (cm-1), and absorption intensities were classified in the usual fashion as very weak (vw), weak (w), medium (m), strong (s), and very strong (vs) relative to the strongest band in the spectrum. Mass spectra were obtained using a Hewlett-Packard 5890A gas chromatograph/mass spectrometer (GC-MS) with an ionizing potential of 70 electron volts and temperature programmed elution into the spectrometer inlet (90-200°C). Melting points were determined by differential scanning calorimetry (DSC) using a PYRIS Diamond DSC (Perkin Elmer). All samples were analyzed in a constant nitrogen purge of 50 ml/min at a heating rate of 5°C/min. Thermogravimetric analysis (TGA) was performed using a TA Instruments 2950 Hi-Res TGA instrument interfaced with the Thermal Analyst 2100 control unit. Most generally, a heating rate of 10°C/min was used. Samples (5-10 mg) were contained in a standard platinum pan. The sample compartment was purged with dry nitrogen at 50 ml/min during analysis. TA Universal Analysis software was used for data analysis. Glass transition temperatures (Tg) were determined using a DSC Q 2000 (TA Instruments). The samples were contained in standard aluminum DSC pans. Samples were heated from –20 to 200 °C in a nitrogen atmosphere at a rate of 10 °C/min. The Tgs were obtained from the second heating cycle, using TA Universal Analysis software. Gel permeation chromatography (GPC) was used to determine molecular weights and molecular weight distributions of polymer samples using a Waters 1525 GPC system equipped with a differential refractive index detector and Wyatt Technologies Dawn Helios II multi-angle light scattering detector. Tetrahydrofuran was used as eluent at a flow rate of 1.0 mL/min. Sample concentration of 20 mg/mL and injection volumes of 20 μL were used. Pyrolysis combustion flow calorimetry (PCFC) was performed using a Govmark microscale combustion calorimeter. Small polymer samples (1-10 mg) were dried for at least 8 hours at 75°C in a convection oven and held in a dessicant chamber until testing. The samples were heatead at a constant rate (1°C/sec) from 150 to 700 °C. The volatile pyrolysis products generated during the temperature ramp were swept from the pyrolyzer into the combustion chamber (900 °C) by nitrogen gas flowing at 80 cm3/min to which was added 20 cm3/min of pure oxygen. Deconvolution of the oxygen consumption signal was performed during the test, and the heat release rate was calculated in watts per gram of sample. 237 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.

Monomer Synthesis


The styrene monomers required for this study are shown below. A detailed description for the synthesis of two of these is presented below. All others were prepared in an analogous manner (5, 42).

Dimethyl (4-Vinylbenzyl)phosphonate Sodium hydride (0.55 g, 0.024 mmol) as a 60% suspension in mineral oil was added to 20 mL of dry THF and the suspension was stirred at room temperature, under nitrogen for 0.5 hours. A solution of dimethyl phosphite (2.6 g, 0.024 mol) and 10 mL of THF was added slowly and the mixture was allowed to cool at 0-5°C and stirred for 0.5 hours. 4-(Chloromethyl)styrene (3 g, 0.02 mol) and TBC (100 mg, 0.6 mmol) in 25 mL of THF were added dropwise. The reaction mixture was stirred at ambient temperature for 2 hours and then at the solvent reflux for 12 hours. The salt which formed during the reaction was removed by filtration. The solvent was removed from the filtrate by rotary evaporation at reduced pressure. The residual material was dissolved in 100 mL of methylene chloride. The solution was washed, successively, with two 100-mL portions of distilled water and 100 mL of saturated aqueous sodium chloride solution. The solution was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation at reduced pressure. The residue was purified by flash chromatography (eluant: ethyl acetate/hexane 50/50, v/v). The pure product was obtained as a pale yellow oil (4.02 g, yield 90.13 %): IR (thin film, cm-1) 3003 (w, Ar-H), 2909 (m, CH2), 1630 (m, vinyl), 1515 (C=Caromatic), 1410 (m, P-C), 1250, vs (P=O), 1030 (vs, P-O-C); 1H-NMR (300 MHz, CDCl3, δ) 2.75 (d, 2H, JPH=21.7 Hz, CH2-P); 3.1 (d, 6H, JPH=10.89 Hz, CH3–O); 5.09 (d, 1H, JHH=10.8 Hz, CH=CH2); 5.42(d, 1H, JHH=17.6 Hz, CH=CH2); 6.61-6.71 (dd, 1H, cis JHH=10.8 Hz, trans J=17.6 Hz, CH=CH2); 6.95-7.33 (m, 4Haromatic); 13C-NMR 238 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.

(75.46 MHz, CDCl3, δ) 33.5 (d, JPC=127.8 Hz, CH2-P), 53.3 (d, JPC=6.8 Hz, CH3-O); 113.6 (1C, CH=CH2), 130.04, 131.10 (d, J=9.8 Hz, CH=CH2), 126.15, 126.25 (d, JPC=3.45 Hz, 1Caromatic), 130.5, 136.3 (2C aromatic); 31P-NMR (121.48 MHz, CDCl3, δ) + 34.5; GC-MS: calcd. for C11H15O3P: 226, found: 226.


Phosphoramidic Acid, N-(4-Vinylphenyl)dimethylester A stirred mixture of dimethyl phosphite (3.3g, 0.03 mol) and 30 mL of carbon tetrachloride was allowed to cool to 0°C, in a nitrogen atmosphere. 4-Aminostyrene (3.0 g, 0.025 mol) and TBC (100 mg, 0.6 mmol) dissolved in 25 mL of THF were then added and the mixture was stirred for one hour. Triethylamine (TEA) (3 g, 0.03 mol) in 10 mL of carbon tetrachloride was added dropwise and the resulting solution was stirred overnight. After approximately 20 hours, TLC (eluant: ethyl acetate) indicated that 4-aminostyrene had been completely consumed. The triethylammonium chloride formed in the reaction was removed by filtration and washed with 30 mL of carbon tetrachloride. The organic solution was washed successively with two 100-mL portions of distilled water and 100 mL of saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation at reduced pressure. The residue was purified by column chromatography using a mixture of ethyl acetate:hexane (50:50, v/v) as eluant to provide 5.1 g of phosphoramidic acid, N-(4-vinyl-phenyl)dimethylester (89.5% yield) as a colorless liquid: IR (thin film, cm-1) 3200 (N-H), 1610 (s, vinyl group); 1025, 1400 (s, m P–O–alkyl); 1520 (υC=C in the phenyl ring); 1167 (P=O stretching); 1230, 840 (m, vs, υC-N and υP-N); 1H-NMR (300 MHz, CDCl3, δ) 3.7 (d, JPH=11.4 Hz, OCH3); 5.12 (d, 1H, JHH=10.8 Hz, CH=CH2); 5.61 (d, 1H, JHH=17.6 Hz, CH=CH2); 6.59-6.68 (dd, 1H, cis JHH=10.8 Hz, trans J=17.6 Hz, CH=CH2); 6.75 (d, JPH= 9, NH); 6.96-6.99 (dd, 2Haromatic); 7.28-7.31 (dd, 2Haromatic); 13C-NMR (75.46 MHz, CDCl3) 53.10-53.15 (d, JPC=5.2 Hz, CH3 from phosphoramidate P(O)CH3); 112.0 (CH=CH2); 117.25-117.34 (d, JPC=6.79 Hz, Caromatic–P); 127.2, 131.4, 136.1, 139.2 (s, 4Caromatic); 31P-NMR (121.48 MHz, CDCl3, δ) +6.6; GC-MS: calcd. for C10H14NO3P: 227, found: 227.

Polymer Synthesis In a typical preparation a solution in N,N-dimethylacetamide (DMAC) of monomer (40% wt) and initiator (0.5% mol AIBN/mol monomer) was placed in a Pyrex polymerization tube, sealed under nitrogen, and heated in an oil bath for a period of 3 hours at 70°C. Subsequently, the tube was transferred to an oven and kept at 110°C for 16 hours, to provide a viscous solution of polymer. The polymer was separated by precipitation in water. The crude polymer was dried and re-dissolved in DMAC and then precipitated by the addition of hexane. The polymer was washed repeatedly with hexane then dried at 15 torr and 50°C for 24 h. The purity of the polymers was assesed by 1H-NMR spectroscopy which showed no traces of monomer. 31P-NMR (121.48 MHz, δ) of the polymers: HMP1 (CDCl3):+30.2; HPM2 (CDCl3): +5.9; HPM3 (CDCl3): +21.1; HPM4 239 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


(CDCl3): +34.4; HPM5 (DMSO-d6): +7.9; HPM6 (DMSO-d6) +3.9; HPM7 (DMSO-d6): -5.2; HPM8 (DMSO-d6): +9.4. The structures of the polymers generated are shown below.

Results and Discussion Phosphorus compounds are commonly used as flame retardants for polymeric materials. It has widely been suggested that the effectiveness of these flame retardants is enhanced in the presence of a nitrogen-containing compound. To directly assess the impact of the presence of nitrogen on the effectiveness of phosphorus compounds as flame retardants in styrene polymers, two series, one containing only a phosphorus moiety and the second containing both phosphorus and nitrogen, have been prepared, characterized, and evaluated for potential flame retarding effect.

Scheme 1. Synthesis of styrene monomers containing flame-retarding moieties 240 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


Monomers were prepared from 4-chloromethylstyrene or 4-aminostyrene as illustrated in Scheme 1.

Scheme 2. Polymerization of styrene monomers containing flame-retarding moieties

Figure 1. Infrared spectra of styrenic polymers containing phosphonate or phosphoramide flame-retarding moieties. 241 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


These monomers were purified by chromatography and characterized spectroscopically (5, 42). The monomers were converted to the corresponding polymers using standard radical techniques as illustrated in the Scheme 2. The polymers were purified by repeated precipitation, dried at reduced pressure and characterized using chromatographic and spectroscopic techniques. A sample of poly(styrene) was prepared under the same conditions to be used as refernce. Molecular weights [SEC; THF; refractive index] were 70,000-82,000 with dispersities of 1.4-1.6.

Figure 2. Proton NMR spectra of styrenic polymers containing phosphonate or phosphoramide flame-retarding moieties. 242 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.

The infrared spectra of phosphorus-containing polymers contains specific absorptions not present in the poly(styrene) spectrum at 1200-1275 cm-1 (very strong, -P=O), 1116 and 967 cm-1 (-P-O-Ph) and 1030 cm-1 (-P-O-C), reflecting the presence of the phosphonate groups pendant to the polymer chain and peaks at 1000-1250, 870 due to υC-N, υP-N absorptions. In the phosphoramidate series, the presence of a broad absorbtion at about 3200 cm-1 due to the N-H stretch may be noted. These features are illustrated in Figure 1.


Table I. Glass transition temperatures for styrenic polymers containing phosphonate or phosphoramide flame-retarding moieties Polymer

Tg [°C]

Polymer

Tg [°C]

HPM1

122.4

HPM5

131.5

HPM2

130.2

HPM6

132.4

HPM3

-

HPM7

136.1

HPM4

153.4

HPM8

126.2

PS

102

PS

102

Figure 3. Thermal degradation of styrene polymers bearing phosphorus-containing pendant groups.



The 1H-NMR spectra of these polymers are illustrated in Figure 2 and contain the following characteristic peaks: δ ≈ 1.4 (Ph- CH- CH2); δ ≈ 1.8, (Ph- CH- CH2), aromatic protons from former vinyl segments, at δ ≈ 6.5 and δ ≈ 7.05; methyl protons (P-CH2-CH3) from diethylphosphonate groups at δ ≈ 1.2-1.25; methylene protons (P-CH2-CH3) from phosphonate groups at 4-4.25 ppm; benzylic Ph-CH2-P signals at δ ≈ 3 - 3.4, aromatic protons from diphenylphosponate residues at 7.2-7.3 ppm and signals at δ ≈ 4 due to NH protons from phosphoramidate pendants. The glass transitions temperatures (Tg) for these polymers are generally higher than that for poly(styrene) as shown in Table I. This may be reflective of strong intermolecular interactions between the polar groups pendant to the polymer mainchain. Thermal decomposition of the polymers bearing only phosphorus-containing pendants is depicted in Figure 3. As can be seen, the onset temperature for degradation is higher for the polymers with phosphorus–containing pendant groups than for unsubstituted poly(styrene).

Figure 4. Thermal degradation of styrene polymers bearing pendant groups containing both phosphorus and nitrogen. Further, the residue from degradation of the phosphorus–containing polymer is significantly greater (16-27 % of the initial sample mass) than for the degradation of unsubstituted poly(styrene) (0%). The degradation of the polymers bearing pendants groups containing both phosphorus and nitrogen is depicted in Figure 4. Again, the onset temperature for degradation of the polymers with phosphorus/ nitrogen containing pendant groups is generally higher than that for unsubstituted poly(styrene). Degradation of these polymers also leads to significant levels of 244 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.

residual material (25-40% of the initial sample mass). Not only is the level of residue much higher than that for unsubstituted poly(styrene) but is significantly greater than that for degradation of polymers with pendant groups containing only phosphorus. Based on these simple observations, it would seem that the beneficial impact of phosphorus on the thermal stability of poly(styrene) is strongly enhanced by the presence of nitrogen. Data for the degradation of both sets of polymers are displayed in Table II.


Table II. Thermal degradation data for the polymers from phosphorus- and phosphorus- and nitrogen- containing monomers Sample

Tonset [°C]

Mass loss [%]

Residue at 600 °C [%]

Sample

Tonset [°C]

Mass loss [%]

Residue at 600 °C [%]

PM1

414

64.2

32.5

PM5

239; 366

63.6

36.4

PM2

425

69.9

26.5

PM6

340

59.2

40.8

PM3

412

84.4

15.6

PM7

391

68.7

31.3

PM4

416

83.6

16.3

PM8

426

72.8

26.2

PS

384

100

0

PS

384

100

0

Figure 5. Heat release rate for the combustion of styrene polymers bearing phosphorus-containing pendant groups. 245 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


A reflection of the impact of the presence of the pendant groups on the combustion of the polymers is provided by the data from pyrolysis combustion flow calorimetry. Plots of heat release rates versus time for the polymers are displayed in Figures 5 and 6.

Figure 6. Heat release rate for the combustion of styrene polymers bearing phosphorus/nitrogen-containing pendant groups.

Table III. Heat release (HR) values for the combustion of the homopolymers from phosphorus- and phosphorus- and nitrogen- containing monomers Homopolymer

HR [kJ/g]

Homopolymer

HR [kJ/g]

P1

25.8

PM5

14.02

PM2

27.9

PM6

22.6

PM3

28.3

PM7

22.9

PM4

26.6

PM8

25.23

PS

42.4

PS

42.4

First, it is apparent that the presence of phosphorus in the polymer dramatically alters heat release rate for combustion of the polymer. As may be seen from the plots in Figure 6, this impact is enhanced by the presence of nitrogen in the phosphorus/nitrogen-containing pendant groups. 246 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.

Heat release values for the polymers are collected in Table III. The heat release values for the combustion of polymers containing both phosphorus and nitrogen are only marginally smaller than those for the polymers containing only phosphorus.


Conclusions Two sets of styrene monomers, one containing a phosphorus moiety as a substituent and the other containing a substituent with both phosphorus and nitrogen components, have been prepared, characterized, and used to generate a set of polymers containing, in the first instance, only phosphorus and, in the second, both phosphorus and nitrogen. Both the thermal degradation and the combustion characteristics of the polymers have been examined. Thermogravimetry suggests that the presence of nitrogen enhances the impact of phosphorus on the stability of the polymers (higher onset temperature for degradation and significantly higher levels of residue after decomposition). Polymers containing both phosphorus and nitrogen display slightly depressed combustion heat release rates compared to those containing only phosphorus.

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