Ammonia → alpha-Methylene-gamma-Butyrolactone Butadiene Acrylic Acid

HRID 83954

Reaction equation

HRID 83954 reaction equation
O.[OH:2][CH2:3]S([O-])=O.[Na+].[C:8](ON(OC(=O)C)CCN(OC(=O)C)OC(=O)C)(=O)[CH3:9].[Na].[Na].[Na].[Na].[CH2:32]=[CH:33][CH:34]=[CH2:35].[CH2:36]=[C:37]1[CH2:42]CO[C:38]1=[O:39].C(O)(=[O:46])C=C.C1(S(OCCCCCCCCCCCC)(=O)=O)C=CC=CC=1.[Na].CC(C(C(C(S)(C)C)(C)C)(C)C)C.S(OOS([O-])(=O)=O)([O-])(=O)=O.[Na+].[Na+].N>>[CH2:36]=[C:37]1[CH2:42][CH2:3][O:2][C:38]1=[O:39].[CH2:32]=[CH:33][CH:34]=[CH2:35].[C:3]([OH:2])(=[O:46])[CH:8]=[CH2:9]

Participants

11

Reactant 10

HCID 222AmmoniaHCID 962Water4×HCID 6581Acrylic AcidHCID 78451,3-ButadieneHCID 32793Tert-dodecanethiolHCID 62655Sodium PersulfateHCID 68352alpha-Methylene butyrolactoneHCID 23689980Sodium Formaldehyde Sulfoxylate2×HCID 57371080Sodium dodecylbenzene sulphonateHCID 86664981Tetrasodium ethylenediamine tetraacetate

Product 1

HCID 86664980alpha-Methylene-gamma-Butyrolactone Butadiene Acrylic Acid

Conditions

Temperature
80 °C

Procedure

A 150 mL round bottom flask with a magnetic stir bar is charged with 17 g (0.943 mol) of water, 0.01 g (6.49×10−5 mol) of sodium hydroxymethylsulfinate and 0.001 g (2.63×10−6 mol) of tetrasodium ethylene diamine tetraacetate. The reactor is heated to 80° C. under nitrogen. After 5 minutes at 80° C., 8 g of a monomer pre-emulsion consisting of 26.5 g (0.490 mol) of butadiene, 18.5 g (0.189 mol) of α-methylene-γ-butyrolactone, 1.5 g (2.50×10−2 mol) of acrylic acid, 1.332 g (3.82×10−3 mol) of sodium dodecyl benzenesulfonate (15% aqueous solution), 0.25 g (1.24×10−3 mol) of tert-dodecylmercaptan and 22 g (1.22 mol) of water is added by cannula over 3 minutes. Additionally, 1 g of an aqueous mixture consisting of 0.25 g (4.20×10−3 mol) of sodium persulfate and 7 g (0.389 mol) of water is added over 2 minutes. After stirring for 20 minutes at 80° C., the remainder of the monomer pre-emulsion and aqueous mixture is added uniformly over 300 minutes. When all additions were completed, the polymerization is allowed to stir for an additional 7 hours at 80° C. Upon completion, steam is passed through the mixture under reduced pressure and a solution of 0.25 g (1.62×10−3 mol) of sodium hydroxymethylsulfinate in 1 g (5.55×10−2 mol) of water is added slowly, with stirring. The pH of the dispersion is brought to 7 with 10% strength aqueous ammonia before the dispersion is dried under vacuum at elevated temperature for isolation.

Workup

  1. additionis added by cannula over 3 minutes
  2. additionis added over 2 minutes
  3. additionthe remainder of the monomer pre-emulsion and aqueous mixture is added uniformly over 300 minutes
  4. stirringto stir for an additional 7 hours at 80° C
  5. stirringwith stirring
  6. customis dried under vacuum at elevated temperature for isolation

Sources & evidence

ORD record
ord-6b1b3ec280464829a4233e45fed7bdff
Source dataset
uspto-grants-2014_09
Patent number
US08846817B2

Linked notes

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