LOW TOXICITY ORGANIC TERTIARY AND QUATERNARY AMINES AND USES THEREOF
Tertiary amine and quaternary ammonium compounds of Formula I and/or Formula II are provided. The present technology also provides compositions that include one or more of the compounds that may be useful for electronics processing (e.g., semiconductor processing composition), cleaning, stripping, degreasing, or a combination of two or more thereof. The compounds of Formula I and/or Formula II may be useful as a low toxicity substitute for tetramethylammonium hydroxide.
1 . A composition comprising a compound of Formula I, a compound of Formula II, or a combination thereof:
wherein:
R 1 and R 5 are individually H, hydroxyl, or CH 3 ;
R 2 and R 6 are individually H, hydroxyl, CH 3 , N(CH 3 ) 2 , or + N(CH 3 ) 3 ;
Y is OR 3 or N(R 8 ) i , Z is OR 7 or N(R 10 ) j ,
wherein:
R 3 and R 7 are individually H or C 1 -C 6 alkyl; and
R 8 at each occurrence is individually C 1 -C 6 alkyl optionally substituted with one or more hydroxyl groups;
R 10 at each occurrence is individually H or a C 1 -C 6 alkyl optionally substituted with one or more hydroxyl groups;
R 4 is H or a C 1 -C 6 alkyl group optionally substituted with one or more hydroxyl, amine, or ammonium groups;
a, b, d, e, f, and h are individually 0 or 1;
c and g are individually 0, 1, or 2;
i and j are individually 2 or 3; and
X − is an anion and present in the amount equal to the cations present in Formula I or Formula II.
2 . The composition of claim 1 , wherein the compound of Formula I is a compound of Formula IA and/or the compound of Formula II is a compound of Formula IIA:
wherein:
R 1 , R 2 , R 5 , and R 6 are individually H, hydroxyl, or CH 3 ;
R 3 and R 7 are individually H or C 1 -C 6 alkyl;
R 4 is H or a C 1 -C 6 alkyl group optionally substituted with one or more hydroxyl groups;
a, b, d, e, f, and h are individually 0 or 1;
c and g are individually 0, 1, or 2; and
X − is the anion.
3 . The composition of claim 1 , wherein the compound of Formula I is a compound of Formula IB and/or the compound of Formula II is a compound of Formula IIB:
wherein:
R 1 and R 5 are individually H, hydroxyl, or CH 3 ;
R 2 and R 6 are individually H, CH 3 , N(CH 3 ) 2 , or + N(CH 3 ) 3 ;
wherein:
R 8 at each occurrence is individually C 1 -C 6 alkyl optionally substituted with one or more hydroxyl groups; and
R 10 at each occurrence is individually H or a C 1 -C 6 alkyl optionally substituted with one or more hydroxyl groups;
R 4 is C 1 -C 6 alkyl optionally substituted with one or more hydroxyl, N(CH 3 ) 2 , or + N(CH 3 ) 3 groups;
a, b, d, e, f, and h are individually 0 or 1;
c and g are individually 0, 1, or 2; and
X − is the anion.
4 . The composition of any one of claims 1 - 3 , wherein a+b+c+d≥1 and e+f+g+h≥1.
5 . The composition of any one of claims 1 - 4 , wherein a+b+c+d≥2 and e+f+g+h≥2.
6 . The composition of any one of claims 1 - 5 , wherein R 1 and R 5 are individually hydroxyl or CH 3 .
7 . The composition of any one of claims 1 - 5 , wherein R 1 and R 5 are H or CH 3 .
8 . The composition of any one of claims 1 - 7 , wherein R 3 and R 7 are H.
9 . The composition of any one of claims 1 - 7 , wherein R 3 and R 7 are individually C 1 -C 6 alkyl.
10 . The composition of claim 9 , wherein R 3 and R 7 are CH 3 .
11 . The composition of any one of claims 1 - 10 , wherein R 4 is C 1 -C 4 alkyl optionally substituted with one or more hydroxyl groups.
12 . The composition of claim 11 , wherein R 4 is a methyl group optionally substituted with one or more hydroxyl groups.
13 . The composition of claim 11 or claim 12 , wherein R 4 is terminally substituted with the one or more hydroxyl groups.
14 . The composition of any one of claims 1 - 13 , wherein R 4 is substituted with two or more hydroxyl groups.
15 . The composition of any one of claims 1 - 13 , wherein R 4 is CH 2 CH(CH 3 )OH.
16 . The composition of any one of claims 1 - 10 , wherein R 4 is C 1 -C 4 alkyl optionally substituted with one or more amine or ammonium groups.
17 . The composition of claim 16 , wherein R 4 is a methyl group optionally substituted with one or more amine or ammonium groups.
18 . The composition of claim 16 or claim 17 , wherein R 4 is terminally substituted with one or more + N(CH 3 ) 3 groups.
19 . The composition of any one of claims 1 - 10 or 16 , wherein R 4 is a CH 2 C(CH 3 ) 2 —N(CH 3 ) 3 + .
20 . The composition of any one of claims 1 - 19 , wherein R 2 and R 6 are H.
21 . The composition of any one of claims 1 - 19 , wherein R 2 and R 6 are hydroxyl.
22 . The composition of any one of claims 1 - 19 , wherein R 2 and R 6 are CH 3 .
23 . The composition of any one of claims 1 - 19 , wherein R 2 and R 6 are N(CH 3 ) 2 or + N(CH 3 ) 3 .
24 . The composition of any one of claims 1 - 23 , wherein R 8 and R 10 at each occurrence are individually C 1 -C 6 alkyl optionally substituted with one or more hydroxyl groups.
25 . The composition of any one of claims 1 - 24 , wherein R 8 and R 10 at each occurrence are CH 3 .
26 . The composition of any one of claims 1 - 24 , wherein R 8 and R 10 are selected from the group consisting of CH 3 and C(CH 3 ) 2 CH 2 OH.
27 . The composition of any one of claims 1 - 26 , wherein X − is a halide, sulfate, methosulfate, carbonate, carboxylate, phosphate, or hydroxide.
28 . The composition of any one of claims 1 - 27 , wherein X − is a hydroxide.
29 . The composition of any one of claims 1 - 28 , wherein the compound of Formula I is a compound of Formula IA selected from the group consisting of
and combinations of two or more thereof.
30 . The composition of claim 29 , wherein the compound of Formula I is a compound of Formula IA selected from the group consisting of DMAMPD, iso-DMAMPD, and combinations thereof.
31 . The composition of any one of claims 1 - 30 , wherein the compound of Formula II is a compound of Formula IIA selected from the group consisting of
and combinations of two or more thereof.
32 . The composition of claim 31 , wherein the compound of Formula II is a compound of Formula IIA that is DMAMPD-AH.
33 . The composition of any one of claims 1 - 32 , wherein the compound of Formula I is a compound of Formula I selected from the group consisting of
and combinations of two or more thereof.
34 . The composition of any one of claims 1 - 33 , wherein the compound of Formula II is a compound of Formula IIB selected from the group consisting of
and combinations of two or more thereof.
35 . The composition of any one of claims 1 - 34 , wherein the composition has about 0.1 wt % to about 80 wt % of the compound of Formula I, the compound of Formula II, or a combination thereof, based on the total composition.
36 . The composition of any one of claims 1 - 35 , wherein the composition has about 1 wt % to about 50 wt % of the compound of Formula I, the compound of Formula II, or a combination thereof, based on the total composition.
37 . The composition of any one of claims 1 - 36 , wherein the composition is an electronics processing composition (e.g., semiconductor processing composition), cleaning composition, stripping composition, a degreasing composition, a catalyst, a phase transfer agent, or a combination of two or more thereof.
38 . The composition of 37, wherein the electronics processing composition is a wafer cleaning composition, anisotropic etching composition, photolithography composition, photoresist developing composition, post chemical mechanical planarization cleaning composition, printed circuit board cleaning composition, or a combination of two or more thereof.
39 . The composition of any one of claims 1 - 38 further comprising a stabilizer (e.g., an antioxidant, oxygen scavenger, or reducing agent such dithionite salts, amines, hydroxylamines, sulfites, hydroquinones, hydrides, carboxylic acids, piperazines, formaldehyde, thiourea, borates, butylated hydroxytoluenes, butylated hydroxyanisoles, ascorbic acid, and the like and combinations of two or more thereof).
40 . The composition of any one of claims 1 - 39 further comprising a corrosion inhibitor.
41 . The composition of any one of claims 1 - 40 further comprising alcohol, pyrocatechol, glycerin and/or glycerin derivative.
42 . The composition of any one of claims 1 - 41 , wherein the compound of Formula I and/or the compound of Formula II is an etching agent.
43 . The composition of any one of claims 1 - 42 further comprising a hydroxylamine (e.g., hydroxylamine, hydroxylamine sulfate, hydroxylamine chloride, hydroxylamine oxalate, N,N-diethyl hydroxylamine, isopropyl hydroxylamine, dimethyl hydroxylamine hydrochloride and/or hydroxylamine phosphate).
44 . The composition of any one of claims 1 - 43 further comprising an inorganic alkali compound.
45 . The composition of any one of claims 1 - 44 further comprising water.
46 . The composition of any one of claims 1 - 45 further comprising a hydrotropic component.
47 . The composition of any one of claims 1 - 46 further comprising a pH adjusting agent, buffering agent, or a combination thereof.
48 . The composition of any one of claims 1 - 47 further comprising at least one organic solvent or surfactant (e.g., DMSO, an alcohol, ethoxylated alcohol, betaine, alkylsulfonic acid, arylsulfonic acid, or combinations of two or more thereof).
49 . The composition of any one of claims 1 - 48 further comprising a rheology modifier (e.g., polymeric rheology modifier such as polyacrylic acid).
50 . The composition of any one of claims 1 - 49 further comprising a chelating agent (e.g., ethylenediamine tetraacetic acid (“EDTA”)).
51 . The composition of any one of claims 1 - 50 , wherein the composition comprises at most about 1000 ppb of a metal selected from the group consisting of Na, Mg, Al, K, Ca, Mn, Fe, Ni, Cu, Zn, Ag, Pd, and Cr.
52 . The composition of any one of claims 1 - 51 , wherein the composition has a reduced toxicity compared to a composition comprising the same wt % of tetramethylammonium hydroxide (TMAH), based on rat dermal toxicity.
53 . The composition of any one of claims 1 - 52 , wherein the composition is essentially free of TMAH.
54 . A compound of Formula I or a compound of Formula II as recited in any one of claims 1 - 34 .
55 . A process for making the compound of Formula II as recited in claim 54 , the process comprising:
providing a solution comprising a compound of Formula I as recited in any of claims 1 - 34 and an organic solvent;
optionally heating the solution to between about 25° C. and about 45° C.;
adding a methylating agent to the solution to produce a mixture, wherein the methylating agent is optionally added over a period of about 1 hour;
mixing the mixture;
optionally cooling the mixture to less than about 20° C.;
optionally filtering the mixture.