Hydroxymethyl monomers

Attempts to use other hydroxymethyl monomers such as allyl alcohol, 2-methylallyl alcohol, and 2-chloroallyl alcohol for isomerizational copolymerizations with methyl acrylate gave mixed results due to the poor copolymerization rate constants of these olefins and the ability of acrylic radicals to abstract hydrogen atoms from allyl alcohols. 

The second example is interesting because the hydroxymethyl monomer is oligomerized thus reducing its volatility before blending with polyester resins (Figure 11). It is also reported to copolymerize with the polyester on blending. 

Luo Y, Zhang S, Ma Y et al (2013) Microporous oiganic polymers synthesized by self-condensation of aromatic hydroxymethyl monomers. Polym Chem 4 1126-1131... 

J.M.J. Frechet (C. J. Hawker, 1990) replaced the divergent synthesis by a convergent growth of a dendritic polymer. The repeatedly employed monomer, 5-hydroxymethyl-l, 3-benzenediol, was 1,3-O-dibenzylatcd with 3,5-bis(benzyloxy)benzyl bromide. The resulting benzyl alcohol containing 7 benzene rings was converted to the benzyl bromide which was... 

The reaction conditions can be varied so that only one of those monomers is formed. 1-Hydroxy-methylurea and l,3-bis(hydroxymethyl)urea condense in the presence of an acid catalyst to produce urea formaldehyde resins. A wide variety of resins can be obtained by careful selection of the pH, reaction temperature, reactant ratio, amino monomer, and degree of polymerization. If the reaction is carried far enough, an infusible polymer network is produced. 

Some of the typical conditions of polycondensations used for aliphatic and aromatic monomers are not suitable for furan derivatives, e.g., the melt polycondensation of 2,5-furan dicarboxylic acid chloride with 2,5-b/s(hydroxymethyl) furan at about 80 °C only yields a black insoluble product5. The hydrochloric acid liberated in the reaction is clearly responsible for the charring of the furanic diol which like its simpler homologue furfuryl alcohol, resinifies rapidly in acidic media (see below). 

This aliphatic hyperbranched polyester is prepared by the bulk polycondensation of 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) as AB2 monomer and 1,1,1-tris(hydroxymethyl)propane (TMP) as B3 core molecule, according to a procedure... 

More recently, the reaction advancement of resole syntheses (pH = 8 and 60°C) was monitored using high-performance liquid chromatography (HPLC), 13C NMR, and chemical assays.55,56 The disappearance of phenol and the appearances of various hydroxymethyl-substituted phenolic monomers and dimers have been measured. By assessing the residual monomer as a function of reaction time, this work also demonstrated the unusually high reactivity of 2,6-dihydroxymethyl-phenol. The rate constants for phenolic monomers toward formaldehyde substitution have been measured (Table 7.6). 

Thermal degradation below 300°C in inert atmospheres produces only small amounts of gaseous products. These are mostly unreacted monomers or water, which are by-products eliminated from condensation reactions between hydroxymethyl groups and reactive ortho or para positions on phenolic rings. A small... 

Tris(hydroxymethyl)propane (TMP) TNT-based condensation monomers, 297 Toluene diamine (TDA), 222 Toluene diisocyanate (TDI), 200, 219 dimer of, 240... 

The blend is partially crosslinked with a vinyl monomer when dissolved in an organic aprotic solvent and has a pH of 5.0 or lower. The first block copolymer is prepared by polycondensing a bis-hydroxyalkyl ether, such as dipropylene glycol, diethylene glycol, and the like, with propylene oxide. Next, the resulting propoxylated diol is reacted with ethylene oxide to produce the block copolymer. The second copolymer is prepared by polycondensing 2-amino-2-hydroxymethyl-1,3-propanediol, commonly known as TRIS, with... 

Alkyl 2-(hydroxymethyl)acrylates are versatile functionalized monomers and synthetic building blocks. Conventional preparations employ the Baylis-Hillman reaction which involves the addition of formaldehyde to the parent acrylate ester, catalyzed by l,4-diazabicyclo[2.2.2]octane (DABCO). These reactions typically take several days at room temperature, but can be achieved within minutes in the CMR and MBR (Scheme 2.4). Rapid heating under pressure prevents loss of formaldehyde. Subsequent cooling limits hydrolysis of the product, as well as dimerization and polymerization [33],... 

Al-Hydroxymethyl methacrylamide, copolymerization with acrylic monomers, l 380t Hydroxymethylphenols, 12 111 Hydroxy-naphthoic acid (HNA),... 

Of equally high industrial potential as intermediate chemicals are the various HMF-derived products for which well-worked-out, large-scale adaptable production protocols are available. Of these, the 5-hydroxymethyl-furoic acid, the 2,5-dicar-boxylic acid, the 1,6-diamine, and the respective 1,6-diol (framed in Scheme 2.12) are the most versatile intermediate chemicals of high industrial potential, as they represent six-earbon monomers that could replace adipic acid, alkyldiols, or hexamethy-lenediamine in the production of polyamides and polyesters. 

Solutions of the nickel(O) and palladium(O) complexes of 1,3,5-triaza-7-phosphaadamantane, PTA (82) and tris(hydroxymethyl)phosphine (98) in water catalyze the oligomerization and telomerization of 1,3-butadiene at 80 °C. Although high yields and good selectivities to octadienyl products (87 %) were obtained, the complexes (or the intermediate species formed in the reaction) dissolve sufficiently in the organic phase ofthe monomer and the products to cause substantial metal leaching [17],... 

More recently two different araroaches have given successful results in the preparation of similar structures. One of these was based on the use of a single monomer, viz. 5-hydroxymethyl-2-ethyl furanaciylate 16. This compound is readily obtained from HMF (29) and polymerizes in bulk or in solution by transesterification under mild catalytic conditions and at temperatures below 100°C (30). The polymers crystallize during the synthesis and precipitate out of the reaction medium. They possess the regular structure 22 and melt at about 180°C ... 

NiMMO is also synthesized by the selective nitration of the hydroxyl group present in 3-hydroxymethyl-3-methyloxetane (HyMMO) using N2Os. In order to aid scale-up of the monomer, NiMMO is now routinely made in a flow nitration system giving excellent yields and purity in dichloromethane solution which can be directly polymerized [124]. The resulting monomer (NiMMO), on cationic polymerization, yields a pale yellow viscous liquid [97,... 

The synthesis of AMO involves treatment of 3,3-bis(chloromethyl) oxetane (BCMO) with sodium azide in the DMF medium at 85 °C for 24 h. Similarly, AMMO which is a monofunctional analog of AMO is synthesized by the azidation of chloro/tosylate product of 3-hydroxymethyl-3-methyl oxetane (HyMMO) with sodium azide in DMF medium at elevated temperatures. These energetic monomers are readily polymerized to liquid curable prepolymers with the help of boron trifluoride etherate/l,4-butanediol initiator system and the outlines of synthesis [147-150] of poly(BAMO) [Structure... 

N 13 59% oxygen-rich monomer no props are reported except 1R spectrum was prepd by reaction of ethyl methyl ketone with formaldehyde, hydrogenation of the product with Gi chromite catalyst, acetylation to the triacetate, pyrolysis, deacerylation, and nitration of 3,3"bis(hydroxymethyl) -butene-1. The subject compd was synthesized as a binder constituent, which might be polymer-... 

Finally, poly(orthoesters) may be prepared (79USP4136252) from monomers such as 2-ethoxy-4-hydroxymethyl-1,3-dioxolane (91 Scheme 25), and find use in areas such as controlled release of drugs and other beneficial agents due to their slow and controlled degradation in aqueous biological environments. 

As an illustrative example, the monomers used for the preparation of a typical polyacrylamide support (Pepsyn) and its schematic representation are sketched in Figure 2.6. The ester functionality, obtained by copolymerization with A-acryloylsarco-sine methyl ester, can be used as the attachment point for a suitable linker. This can be achieved by aminolysis with ethylenediamine, followed by acylation of the resulting primary amine with 3-(4-hydroxymethyl)phenylpropionic acid [163] or other linkers. Similar supports have been prepared by copolymerization of protected allylamine [37] or lV-(acryloyl)-l,3-diaminopropane [173] with V,lV-dimethylacrylamide and... 

The continuous and batch microwave reactors have been particularly useful for heating reactions in which thermally labile products are formed. For example, alkyl 2-(hydroxymethyl)acrylates have considerable potential as functionalised monomers and synthons128. Published syntheses at ambient temperature, however, required several days and were not conducive to scale-up129-133. The microwave procedure involved a modified Baylis-Hillman reaction, in which the parent acrylate derivative was reacted with formalin in the presence of 1,4-diazabicyclo [2.2.2] octane (DABCO). Preparations from starting acrylates, including methyl, ethyl and n-butyl esters, were easily achieved within minutes with multiple passes through the CMR, at ca. 160-180°C (Scheme 9.16). Rapid cooling was required to limit hydrolysis, dimerisation and polymerisation. Yields... 

Ku sefog lu, S.H., Kress, A.O. and Mathias, L.J., Functional methacrylate monomers simple synthesis of alkyl a-(hydroxymethyl) acrylates, Macromolecules, 1987, 20, 2326. 

Mathias, L.J., Warren, R.M. and Huang, S., tert-Butyl a-(hydroxymethyl)acrylateand its ether dimer multifunctional monomers giving polymers with easily cleaved ester groups, Macromolecules, 1991, 24, 2036. 

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