Water → Methyl Methacrylate

HRID 2165221Notes

Reaction equation

HRID 2165221 reaction equation
[C:1]([O:6][CH2:7][CH2:8][CH2:9][CH3:10])(=[O:5])[C:2]([CH3:4])=[CH2:3].O>C1COCC1>[C:1]([O:6][CH3:7])(=[O:5])[C:2]([CH3:4])=[CH2:3].[C:1]([O:6][CH2:7][CH2:8][CH2:9][CH3:10])(=[O:5])[C:2]([CH3:4])=[CH2:3]

Participants

5

Reactant 2

HCID 962WaterHCID 7354Butyl Methacrylate

Product 2

HCID 6658Methyl MethacrylateHCID 7354Butyl Methacrylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 1 mL (5 mmol) of 1-methoxy-1-trimethylsiloxy-2-methyl-1-propene, and 0.132 mL of tetrabutylammonium m-chlorobenzoate (0.38 M in THF), in 75 mL of THF was prepared. To this was added a mixture of 12.5 g (13.35 mL, 125 mmol) of MMA and 12.5 g (14 mL, 87.9 mmol) of n-butyl methacrylate at a rate such that the temperature remained near 30° C. When the monomer mixture had all been added, and 15 min after the temperature had returned to room temperature, a sample removed for NMR analysis showed no residual monomers. GPC analysis showed Mn 5390, Mw 5990, D=1.11 (theory Mn=5252). Then 5 g (20 mmol) of bis(trimethylsilyl) vinylphosphonate (prepared from the reaction of bromotrimethylsilane with diethyl vinylphosphonate) was added, followed by 4 additions of 200 μL TASHF2 (0.1 M in propylene carbonate). A sample was removed for analysis. NMR analysis showed residual vinylphosphonate. GPC analysis showed Mn 5840, Mw 6240, D=1.067. The polymer was precipitated with hexane to give a gummy polymer. This was redissolved in the minimum amount of THF and reprecipitated with hexane to yield 23.6 g of copolymer. NMR analysis showed 1.35 MMA units per butyl methacrylate unit (theory 1.42:1). The copolymer was dissolved in 70 mL of THF and treated with 5 mL of water and stirred 1.5 hr. After precipitation with 1:1 methanol:water, the resulting polymer (205 g) was dissolved in 50 mL of THF and treated with 5 mL of water and 0.5 g of p-toluenesulfonic acid and stirred for 2 hrs. Precipitation with aqueous methanol gave copoly(methyl methacrylate, n-butyl methacrylate) with a terminal phosphonic acid group.

Workup

  1. customAfter precipitation with 1:1 methanol
  2. dissolutionwater, the resulting polymer (205 g) was dissolved in 50 mL of THF
  3. additiontreated with 5 mL of water and 0.5 g of p-toluenesulfonic acid
  4. stirringstirred for 2 hrs
  5. customPrecipitation with aqueous methanol

Sources & evidence

ORD record
ord-404d7995255844e987a127620128d471
Source dataset
uspto-grants-1990_07
Patent number
US04939211

Reaction notes

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