Polymeric sorbents for aldehydes
Polymeric sorbents for aldehydes including formaldehyde are provided. More particularly, the polymeric sorbents are a reaction product of a divinylbenzene/maleic anhydride precursor polymeric material with a nitrogen-containing compound. The nitrogen-containing compound is covalently attached to the resulting polymeric sorbent. Additionally, methods of sorbing aldehydes (i.e., aldehydes that are volatile under use conditions) on the polymeric sorbents and compositions resulting from the sorption of aldehydes on the polymeric sorbents are provided. The polymeric sorbents typically are porous with the pores often being in the size range of mesopores and/or micropores.
1. A polymeric sorbent comprising a reaction product of
(a) a precursor polymeric material having maleic anhydride monomeric units and comprising a polymerized product of a polymerizable composition comprising
(1) 8 to 65 weight percent maleic anhydride based on the total weight of monomers in the polymerizable composition;
(2) 30 to 85 weight percent divinylbenzene based on the total weight of monomers in the polymerizable composition; and
(3) 0 to 20 weight percent of a styrene-type monomer based on the total weight of monomers in the polymerizable composition, wherein the styrene-type monomer is styrene, an alkyl-substituted styrene, or a combination thereof; and
(b) a nitrogen-containing compound that is selected from ammonia, a compound having a single primary amino group (—NH 2 ), or a compound having at least two amino groups of formula —NHR where R is hydrogen or alkyl, wherein at least 50 mole percent of the nitrogen-containing compound is added based on total moles of maleic anhydride monomeric units in the precursor polymeric material and wherein the polymeric sorbent has a covalently attached nitrogen-containing group.
2. The polymeric sorbent of claim 1 , wherein the polymerizable composition comprises 15 to 65 weight percent maleic anhydride, 30 to 85 weight percent divinylbenzene, and 0 to 20 weight percent of a styrene-type monomer.
3. The polymeric sorbent of claim 1 , wherein the polymerizable composition comprises 25 to 65 weight percent maleic anhydride, 30 to 75 weight percent divinylbenzene, and 1 to 20 weight percent styrene-type monomer.
4. The polymeric sorbent of claim 1 , wherein the polymerizable composition comprises 30 to 65 weight percent maleic anhydride, 30 to 70 weight percent divinylbenzene, and 1 to 20 weight percent styrene-type monomer.
5. The polymeric sorbent of claim 1 , wherein the nitrogen-containing compound is of Formula (V)
R 4 NHR 1 (V)
wherein
R 1 is hydrogen or an alkyl;
R 4 is hydrogen, alkyl, a group of formula —R 5 —NHR 6 , or —(C═NH)—NH 2 ;
R 5 is a covalent bond, an alkylene, an arylene, an aralkylene, a heteroalkylene having one or more oxy (—O—) groups, or a heteroalkylene having one or more —NH— groups; and
R 6 is hydrogen, alkyl, or —(C═NH)—NH 2 .
6. The polymeric sorbent of claim 5 , wherein the nitrogen-containing compound of Formula (V) has a molecular weight no greater than 2000 Daltons.
7. The polymeric sorbent of claim 4 , wherein the nitrogen-containing compound is of Formula (VI)
R 7 —(NHR 1 ) z (VI)
wherein
R 7 is a z-valent radical of an alkane or a z-valent radical of a heteroalkane; and
z is an integer in a range of 3 to 10.
8. The polymeric sorbent of claim 1 , the polymeric sorbent further comprising an acid-base dye.
9. A method of sorbing an aldehyde on a polymeric sorbent, the method comprising:
providing a polymeric sorbent of claim 1 ;
sorbing the aldehyde on the polymeric sorbent, the aldehyde being of Formula (I)
R 2 —(CO)—H (I)
wherein R 2 is hydrogen, alkyl, vinyl, or aryl and wherein the molecular weight of the aldehyde of Formula (I) is no greater than 200 grams/mole.
10. The method of claim 9 , wherein R 2 is hydrogen or methyl.
11. The method of claim 9 , wherein the polymeric sorbent sorbs an amount of aldehyde in a range of 0.5 to 12 millimoles per gram based on a weight of the polymeric sorbent.
12. The method of claim 9 , wherein the polymeric sorbent has a BET specific surface area equal to at least 25 m 2 /gram.
13. The method of claim 9 , wherein the polymeric sorbent comprises an acid-base dye and wherein the acid-base dye changes color when the aldehyde sorption capacity of the polymeric sorbent is reached or is close to being reached.
14. A composition comprising:
(a) a polymeric sorbent of claim 1 ; and
(b) an aldehyde sorbed on the polymeric sorbent, the aldehyde being of Formula (I)
R 2 —(CO)—H (I)
wherein R 2 is hydrogen, alkyl, vinyl, or aryl and wherein the molecular weight of the aldehyde of Formula (I) is no greater than 200 grams/mole.
15. A method of forming a polymeric sorbent, the method comprising:
(a) providing a precursor polymeric material having maleic anhydride monomeric units and comprising a polymerized product of a polymerizable composition comprising
(1) 8 to 65 weight percent maleic anhydride based on the total weight of monomers in the polymerizable composition;
(2) 30 to 85 weight percent divinylbenzene based on the total weight of monomers in the polymerizable composition; and
(3) 0 to 20 weight percent of a styrene-type monomer based on the total weight of monomers in the polymerizable composition, wherein the styrene-type monomer is styrene, an alkyl-substituted styrene, or a combination thereof; and
(b) reacting the precursor polymeric material with a nitrogen-containing compound that is selected from ammonia, a compound having a single primary amino group (—NH 2 ), or a compound having at least two amino groups of formula —NHR where R is hydrogen or alkyl to form the polymeric sorbent, wherein at least 50 mole percent of the nitrogen-containing compound is added based on total moles of maleic anhydride monomeric units in the precursor polymeric material and wherein the polymeric sorbent has a covalently attached nitrogen-containing group.