Mechanism study of the base-catalyzed ether formation involving α-(hydroxymethyl)acrylates

Colletti, Ronald F.; Halley, Robert J.; Mathias, Lon J.

doi:10.1021/ma00008a051

Cited by 13 publications

(9 citation statements)

References 1 publication

(1 reference statement)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We have been exploring the rich chemistry of the family of a-(hydroxymethyl)acrylates (1 in Figure 1) obtained from the inexpensive starting materials alkyl acrylates and paraformaldehyde.1-3 The ether dimers (2) can be obtained in excellent yields without isolation of the a-(hydroxymethyl)acrylates and were found, under radical conditions, to give novel cyclopolymers containing tetrahydropyran units in the polymer backbone.4-3 We also reported that a-(chloromethyl)acrylate (3) obtained by treating the a-(hydroxymethyl)acrylate with excess thionyl chloride can be converted to a variety of functional derivatives. [7][8] As shown in an earlier study on cyclopolymerization of a,a'-dimethylenepimelates (4)9-11 and in a more recent study on cyclopolymerization of 2,4'5-12'13 diacrylates having the general formula shown in Figure 2 are excellent cyclomonomers, giving high polymerization rates, high cyclization efficiencies, low polymerization shrinkages, and high thermal stabilities for the resulting cyclopolymer.…”

Section: Introductionmentioning

confidence: 99%

New dicyano-containing cyclopolymers having high stereoregularity derived from dimethacrylmalononitrile

Tsuda¹,

Mathias²

1993

Macromolecules

Self Cite

View full text Add to dashboard Cite

Section: Introductionmentioning

confidence: 99%

New dicyano-containing cyclopolymers having high stereoregularity derived from dimethacrylmalononitrile

Tsuda¹,

Mathias²

1993

Macromolecules

Self Cite

View full text Add to dashboard Cite

“…A study with deuteriumlabeled EHMA proved this mechanism in the case of EHMA. 17 We believe that HMVK behaves similarly, but the etherification reaction goes even faster and at lower temperatures.…”

Section: Resultsmentioning

confidence: 85%

New monomers and polymers derived from ?-hydroxymethyl methyl vinyl ketone

eri

2000

J. Appl. Polym. Sci.

View full text Add to dashboard Cite

2-Hydroxymethyl-but-1-ene-3-one [␣-hydroxymethyl methyl vinyl ketone (HMVK)] was synthesized from methyl vinyl ketone using paraformaldehyde and a tertiary amine catalyst. Free-radical polymerization of this monomer created transparent, tough polymers that were insoluble in organic solvents. HMVK was converted to trimethylsilyl, acetate, and chloride derivatives. When the hydroxyl group was thus protected or removed, all these monomers could be free radically polymerized in bulk to make soluble polymers. The chlorination reaction is complicated by the formation of 1,1-bischloromethylacetone, which dehydrohalogenated unexpectedly to the desired ␣-chloromethyl methyl vinyl ketone. HMVK will self-condense to an ether dimer in the presence of a catalytic acid. This reagent is capable of crosslinking many alkene monomers through hydrolytically stable ether bonds.

show abstract

“…Of the other products present, there was an elevated concentration of extended dienes (1,8-, 1,10-, etc. ), which result from the coupling of multiple formaldehyde units to the acrylate prior to condensation . Formation of these unstable acetal-fused dienes is favored during the early stages of the formaldehyde−acrylate reaction and with additional reaction time, they convert to the stable products 1 and 2 .…”

Section: Resultsmentioning

confidence: 99%

“…The amine-catalyzed coupling reaction between acrylates and formaldehyde or paraformaldehyde provides α-hydroxymethyl acrylates 1 (Scheme 1) . The amine catalyst also promotes condensation between α-hydroxymethyl acrylates to form the ether-linked dienes 2 , which can be termed oxybis(methacrylates). − The 1,6-diene configuration in 2 provides a facile route for cyclopolymerization. Our primary interest in these novel monomers stems from the observation that highly converted polymers can be obtained with considerably less polymerization shrinkage than would be expected with conventional dimethacrylate monomers. − Additional potential advantages associated with the oxybis(methacrylate) monomers include low volatility and high polymeric glass transition temperatures.…”

Section: Introductionmentioning

confidence: 99%

Polymer-Supported Quinuclidinyl Catalysts for Synthesis of Cyclopolymerizable Monomers via the Aldehyde−Acrylate Coupling Reaction

1997

View full text Add to dashboard Cite

With an appropriate amine catalyst, formaldehyde addition to acrylates results in α-hydroxymethyl acrylate intermediates that undergo a further condensation reaction to provide ether-linked 1,6-diene monomers capable of efficient cyclopolymerization. While 1,4-diazabicyclo[2.2.2]octane (DABCO) is an effective catalyst in the synthesis of these cyclopolymerizable monomers, a series of polymer-supported amine catalysts were prepared and evaluated in an effort to further simplify this process. 3-Quinuclidinol was reacted with methacrylic anhydride to give the functionalized methacrylate monomer, which was copolymerized with methyl methacrylate and triethylene glycol dimethacrylate. Various polymerization techniques (bulk, solution, and suspension) were used to produce the cross-linked polymeric catalysts. Supports with mole fractions of catalyst ranging from 20% to 98% were examined. In reactions with ethyl acrylate and paraformaldehyde, certain polymer-supported catalysts gave near quantitative conversion to products. The rate of reaction with the polymeric catalysts was less than that of reactions with DABCO or other nonpolymeric model catalysts; however, after reaction times of 20 h, product yields and distributions were quite similar. With the polymeric catalysts, product isolation required only simple filtration or a solvent wash rather than an aqueous extraction step. This technique was also applied to the preparation of cyclopolymerizable resins containing multifunctional oligomers.

show abstract

Mechanism study of the base-catalyzed ether formation involving α-(hydroxymethyl)acrylates

Cited by 13 publications

References 1 publication

New dicyano-containing cyclopolymers having high stereoregularity derived from dimethacrylmalononitrile

New dicyano-containing cyclopolymers having high stereoregularity derived from dimethacrylmalononitrile

New monomers and polymers derived from ?-hydroxymethyl methyl vinyl ketone

Polymer-Supported Quinuclidinyl Catalysts for Synthesis of Cyclopolymerizable Monomers via the Aldehyde−Acrylate Coupling Reaction

Contact Info

Product

Resources

About