Production of trimethylaluminum (Me₃Al) with counterfeit refrigerant chloromethane (R-40), reactivity of Me₃Al with refrigerant oils and methods to deactivate Me₃Al

Figures & data

Table 1. A summary of chloromethane reactions with Al containing materials in Parr bomb

Entry	Reagents	Condition	Duration (day)	Outcome
1	0.3 g Al dust + CH3Cl	100°C, 250 Psi	4	No reaction
2	0.5 g Al chunk + CH3Cl	100°C, 400 Psi	5	No reaction
3	0.5 g Al beads + 5 mL 2012 Supercool PAG 46 + CH3Cl	100°C, 120 Psi	4	No reaction
4	0.5 g Al chunk + 5 mL 2012 Supercool PAG 46 + CH3Cl	100°C, 120 Psi	5	No reaction
5	0.4 g Al dust + 5 mL 2012 Supercool PAG 100 + CH3Cl	100°C, 260 Psi	4	No reaction
6	0.3 g Al foil + 5 mL 2012 Supercool PAG 100 + CH3Cl	100°C, 330 Psi	4	No reaction
7	0.3 g Al dust + CH3Cl + trace water	100°C, 350 Psi	4	No reaction
8	0.5 g Al beads + 0.25 g Mg dust + CH3Cl	100°C, 320 Psi	5	Reaction detected

Table 2. Chloromethane reactions with Al-containing materials in flask

Entry	Reagents	Condition	Duration (day)	Outcome
1	0.3 g Al dust + 0.15 g Mg dust + CH3Cl	Room temp, mercury bubbler pressure	10	No reaction
2	0.3 g Al dust + 0.15 g Mg dust + CH3Cl	100°C, mercury bubbler pressure	6	No reaction
3	0.1 g Al dust + 0.1 g Al foil + 0.1 g Mg dust + CH3Cl	100°C, mercury bubbler pressure	7	No reaction
4	0.2 g Al dust + 0.1 g Al foil + 0.2 g MgCl2 + CH3Cl	Room temp, mercury bubbler pressure	6	No reaction
5	0.2 g Al dust + 0.1 g Al foil + 0.2 g MgCl2 + CH3Cl	100°C, mercury bubbler pressure	6	No reaction
6	0.3 g Al dust + 0.15 g AlCl3 + CH3Cl	Room temp, mercury bubbler pressure	20	No reaction
7	0.3 g Al dust + 0.15 g AlCl3 + CH3Cl	100°C, mercury bubbler pressure	5	Reaction detected
8	0.2 g Al dust + 0.21 g Al foil + 0.2 g AlCl3 + CH3Cl	100°C, mercury bubbler pressure	5	Reaction detected
9	0.2 g Al dust + 0.21 g Al foil + 0.2 g AlCl3 + CH3Cl + 5 mL 2012 Supercool PAG 46	100°C, mercury bubbler pressure	5	Very weak reaction

Figure 1. GC spectrum of gas collected from Al-Mg-CH₃Cl reaction.

Figure 2. Corroded Parr bomb in Al-Mg-CH₃Cl reaction.

Figure 3. A liquid product formed in Al-AlCl₃-CH₃Cl reaction.

Figure 4. GC spectrum of gas collected from Al-AlCl₃-CH₃Cl reaction.

Figure 5. Fresh Al foil (left), corroded Al foil (middle) in Al-AlCl₃-CH₃Cl reaction and foil in Al-AlCl₃-CH₃Cl-PAG 46 reaction (right).

Figure 6. SEM image of corroded Al foil Al-AlCl₃-CH₃Cl reaction.

Figure 7. SEM image of Al foil in Al-AlCl₃-CH₃Cl-PAG 46 reaction.

Figure 8. GC spectrum of gas collected from Al-AlCl₃-CH₃Cl-PAG 46 reaction.

Table 3. Gas measurements for refrigerant oil-Me₃Al-sec-butanol reactions

	Temperature	After Me3Al injection (mL)	After sec-butanol injection (mL)	Total (mL)
Calibration 1	Room temperature	0	128.0 ± 2.8	128.0 ± 2.8
	80°C	0	143.8 ± 2.0	143.8 ± 2.0
3GS Suniso	Room temperature	4.4 ± 0.5	124.7 ± 2.9	129.1 ± 2.9
	80°C	24.3 ± 2.5	118.5 ± 7.2	142.8 ± 4.8
2012 Supercool PAG 46	Room temperature	48.1 ± 3.0	80.9 ± 2.4	128.9 ± 0.6
	80°C	66.8 ± 4.1	79.3 ± 5.3	146.1 ± 1.2
Calibration 2	Room temperature	0	132.8 ± 1.0	132.8 ± 1.0
	80°C	0	143.8 ± 2.0	143.8 ± 2.0
2012 Supercool PAG 100	Room temperature	83.7 ± 5.0	48.2 ± 4.4	131.9 ± 1.7
	80°C	93.5 ± 4.6	55.7 ± 4.3	149.2 ± 1.0
2014 Supercool PAG 46	Room temperature	124.5 ± 2.5	5.9 ± 1.9	131.2 ± 0.8
	80°C	143.7 ± 0.3	2.9 ± 0.1	146.6 ± 0.4
Napa PAG 46	Room temperature	122.2 ± 2.7	10.2 ± 0.7	132.4 ± 2.0
	80°C	145.2 ± 0.3	1.0 ± 0.5	146.2 ± 0.7
Four seasons ester 100	Room temperature	5.4 ± 0.5	124.5 ± 0.7	130.0 ± 0.3
	80°C	28.2 ± 2.8	80.9 ± 6.8	109.2 ± 5.7
Behr Hella PAO oil 68	Room temperature	9.9 ± 2.9	125.2 ± 0.5	135.1 ± 2.9
	80°C	22.9 ± 2.0	117.5 ± 2.6	140.4 ± 0.8

Table 4. Gas measurements for deactivating reagent-Me₃Al-sec-butanol reactions

	Structure	Temperature	After Me3Al injection (mL)	After sec-butanol injection (mL)	Total (mL)	Ratio (%)
Calibration		Room temperature	0	132.8	132.8	100
		80°C	0	143.8	143.8	100
Benzaldehyde		Room temperature	78.1	12.1	90.2	67.9
		80°C	100.6	11.7	112.3	78.1
Phthalaldehyde		Room temperature	26.9	44.8	71.7	54.0
		80°C	19.5	49.8	69.3	48.2
Benzophenone		Room temperature	11.0	81.8	92.8	69.9
		80°C	13.8	94.4	108.2	75.2
Cyclohexanone		Room temperature	77.7	30.9	108.6	81.8
		80°C	124.8	0	124.8	86.8
Ethyl acetate		Room temperature	25.8	103.4	129.2	97.3
		80°C	26.0	65.1	91.1	63.4

Scheme 1. Schematic representation of seven oils. 1. 3GS Suniso oil. 2. Behr Hella PAO oil 68, R = hydrocarbons (HC). 3. 2012 Supercool PAG 46 or PAG 100 (R₁ and R₂ represent –C(O)R or –H). 4. 2014 Supercool PAG 46 or Napa PAG 46. 5. Four seasons ester 100, R₁-R₄ = HC.