Monomers, vinyl hydrophilic

Uses Reaction rate accelerator copolymerizes readily with most other vinyl monomers modifies hydrophilic properties in systems incl. adhesives, coatings, cosmetics, textiles, syn. fibers, textile sizes, protective colloids, lube oil additives reactive diluent in UV- and electron beam-curable systems (coatings, inks, adhesives) aids pigment disp. (inks) intermediate for modified phenolic resins of interest as plasticizers, dye intermediates, textile assistants... 

PVA polymers hydrolyzed between 70 and 90% are actually copolymers containing a hydrophobic monomer (vinyl acetate) and a hydrophilic monomer (vinyl alcohol) and are thus polyampholytic. Thus, these polymers lower the surface tension of water (Fig. 16). Consequently, PVA polymers of this type have found commercial usefulness as oil-in-water emulsion stabilizers, particularly in personal care applications. The PVA helps to thicken the continuous phase of these emulsions and aids in suspending the oil droplets in the emulsion. 

The Smith-Ewart expression (eq. 1) accurately predicts the particle number for hydrophobic monomers like styrene and butadiene (21), but fails to predict the particle number (22) for more hydrophilic monomers like methyl methacrylate and vinyl acetate. A new theory based on homogeneous particle... 

Vinyl acetate is another monomer used in latex manufacture for architectural coatings. When copolymerized with butyl acrylate, it provides a good balance of cost and performance. The interior flat latex paint market in North America is almost completely dominated by vinyl acetate—acryHc copolymers. Vinyl acetate copolymers are typicaHy more hydrophilic than aH-acryHc polymers and do not have the same ultraviolet light resistance as acryHcs as a result. 

Partially hydrolyzed poly(vinyl alcohol) grades are preferred because they have a hydrophobic /hydrophilic balance that make them uniquely suited for emulsion polymerization. The compatibUity of the residual acetate units with the poly(vinyl acetate) latex particles partly explains the observed stabilization effect. The amount of PVA employed is normally 4—10% on the weight of vinyl acetate monomer. The viscosity of the resulting latex increases with increasing molecular weight and decreasing hydrolysis of the PVA (318). 

Because of the many choices of hydrophilic monomers, cross-linkers, and hydrophobic monomers, a large number of formulations have been developed and manufactured into hydrogel lenses. The water content of these hydrogel lenses ranges from about 38%, for HEMA-based lenses, to 80%, for poly(vinyl alcohol) and partially hydrolysed acrylonitrile lenses. Table 2 gives a representative Hst of FDA approved hydrogel materials available to the consumer in the early 1990s. 

The successful development of eye contact lenses led in turn to a demand for soft contact lenses. Such a demand was eventually met by the preparation of copolymers using a combination of an acrylic ester monomer such as methyl methacrylate, a cross-linkable monomer such as a dimethacrylate, and a monomer whose homopolymer is soluble or highly swollen in water such as N-vinyl pyrrolidone. Such copolymers swell in water (hence the term hydrophilic), the degree of swelling being controlled by the specific type and amount of the monomers used. In use the lens is swollen to equilibrium in water, a typical soft lens having a water content of about 75%. 

MAIs may also be formed free radically when all azo sites are identical and have, therefore, the same reactivity. In this case the reaction with monomer A will be interrupted prior to the complete decomposition of all azo groups. So, Dicke and Heitz [49] partially decomposed poly(azoester)s in the presence of acrylamide. The reaction time was adjusted to a 37% decomposition of the azo groups. Surface active MAIs (M, > 10 ) consisting of hydrophobic poly(azoester) and hydrophilic poly(acrylamide) blocks were obtained (see Scheme 22) These were used for emulsion polymerization of vinyl acetate—in the polymerization they act simultaneously as emulsifiers (surface activity) and initiators (azo groups). Thus, a ternary block copolymer was synthesized fairly elegantly. 

The performance of secondary alkanesulfonates in applications as emulsifiers in the widespread emulsion polymerization of vinyl monomers can be assessed by their hydrophilic-lipophilic balance (HLB) numbers. The HLB numbers can... 

Figure 14.6.6 The molecular structure of the hydrophilic nonionic monomer A -vinyl-2-pyrrolidinone (NVP).

A study on the process of the uncatalyzed polymerization was made. The conclusion was as follows (1) The hydrophilic macromolecules form hydrophobic areas (HA) in the water phase (2) Into the HA, vinyl monomers are incorporated (3) Then, the radical polymerization starts in the HA. A new concept was proposed ... 

Because of the repulsion of the cyanide groups the polymer backbone assumes a rod-like conformation. The fibers derive their basic properties from this stiff structure of PAN where the nitrile groups are randomly distributed about the backbone rod. Because of strong bonding between the chains, they tend to form bundles. Most acrylic fibers actually contain small amounts of other monomers, such as methyl acrylate and methyl methacrylate. As they are difficult to dye, small amounts of ionic monomers, such as sodium styrene sulfonate, are often added to improve their dyeability. Other monomers are also employed to improve dyeability. These include small amounts (about 4%) of more hydrophilic monomers, such as -vinyl-2-pyrrolidone (Equation 6.69), methacrylic add, or 2-vinylpyridine (Equation 6.70). 

PAN has a solubility parameter of about 11 H and is soluble only in polar solvents, such as dimethylacetamide (DMAc). Because of PAN s high polarity, its fibers are difficult to dye. This difficulty has been overcome by producing copolymers of acrylonitrile with small amounts (4%) of more-hydrophilic monomers, such as jV-vinyl-2-pyrrolidone (left), methacrylic acid (center), or 2-vinylpyridine (right), which have the following structures ... 

Polyurethane hydrogels derived from UV curable urethane prepolymer and hydrophilic monomers were prepared and their properties were evaluated. The urethane prepolymer used in this study contained well-defined hard segments centered with a polyether-based soft segment and end-capped with methacrylate groups. The hydrophilic monomers studied were 2-hydroxyethyl methacrylate (HEMA), N-vinyl pyrrolidone, and glycerol methacrylate. Methacryloxypropyl tris(trimethysiloxy) silane (TRIS) was also used in some cases to modify properties. All compositions were UV... 

This paper describes a method for improving hydrophilicity by using radiation-induced grafting of flexible polyurethane (polyether) foam with polar vinyl monomers. By this procedure, the normally hydrophobic material can be converted into a remarkably water-wettable sponge. 

The preparation of cellulose copolymers with vinyl monomers, which have functional groups that are hydrophilic in nature, has given textile products with improved soil release properties. For example, as shown in Figure 5, crosslinked cellulose-poly (methacrylic acid) copolymer fabrics exhibited both increased oily and aqueous soil release during washing compared with the crosslinked control fabrics. However, for oily soil, when softeners were added to the wash water, this improvement in soil release decreased. Crosslinked cellulose-poly (hydroxyethyl methacrylate) copolymer fabrics exhibited no improvement in oily soil release and only slight improvement in aqueous soil release compared... 

The free radical polymerization of DADMAC (M,) with vinyl acetate (M2) in methanol proceeds as a nonideal and nonazeotropic copolymerization with monomer reactivity ratios rx=1.95 and r2=0.35 were obtained [75]. The resulting low molar mass copolymers were reported to be water soluble over their whole range of composition. Modification of the vinyl acetate unit by hydrolysis, ace-talization, and acylation resulted in DADMAC products with changed hydrophilic or polyelectrolyte properties [75]. For the copolymerization of DADMAC and AT-methyl-AT-vinylacetamide (NMVA) a nearly ideal copolymerization behavior could be identified [45]. The application properties of the various copolymer products will be discussed in Sect. 8. 

Most dispersion polymerizations in C02, including the monomers methyl methacrylate, styrene, and vinyl acetate, have been summarized elsewhere (Canelas and DeSimone, 1997b Kendall et al., 1999) and will not be covered in this chapter. In a dispersion polymerization, the insoluble polymer is sterically stabilized as colloidal polymer particles by the surfactant that is adsorbed or chemically grafted to the particles. Effective surfactants in the dispersion polymerizations include C02-soluble homopolymers, block and random copolymers, and reactive macromonomers. Polymeric surfactants for C02 have been designed by combining C02-soluble (C02-philic) polymers, such as polydimethylsiloxane (PDMS) or PFOA, with C02-insoluble (C02-phobic) polymers, such as hydrophilic or lipophilic polymers (Betts et al., 1996, 1998 Guan and DeSimone, 1994). Several advances in C02-based dispersion polymerizations will be reviewed in the following section. 

Janssen et al. [144] focused their work on ozonization of polyvinyl lactam, grafting with hydrophilic methacrylic monomers for applications in the field of contact lenses and other products used in the medical domain. The most studied polymer remains the poly-N-vinyl pyrrolidone which is ozonized either in solid state or in aqueous solution. This activation step leads to three hydroperoxides per chain but also to chain scissions. The resulting product is formulated with different mixtures of methacrylic and dimethacrylic monomers to graft them onto activated polymer by UV initiation. Using dimethacrylic monomers lead to perfect cross-linked polymers presenting excellent resistance to solvents. Unfortunately, the mechanisms of action of ozone onto polyvinyl lactams do not seem to have been studied in detail. 

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