Acrylic acid Adhesion

Figure 4.5 Peel energies for etched polyolefin substrates bonded with a poly(acrylic acid) adhesive as a function of etch time in chromic acid solution [40].

Acrylic acid polymers Acrylic adhesives Acrylic anhydride Acrylic copolymer Acrylic-cotton blends Acrylic elastomers... 

Extension of the chlorosulfonation technology to base resins other than polyethylene, where value can be added, seems a logical next step. Polypropylene and ethylene copolymers containing additional functionaUty, ie, maleic anhydride graft, vinyl acetate, acrylic acid, etc, have been chlorinated and chlorosulfonated to broaden the appHcation base, particularly in coatings and adhesives (9,10). 

Mangipudi et al. [63,88] reported some initial measurements of adhesion strength between semicrystalline PE surfaces. These measurements were done using the SFA as a function of contact time. Interestingly, these data (see Fig. 22) show that the normalized pull-off energy, a measure of intrinsic adhesion strength is increased with time of contact. They suggested the amorphous domains in PE could interdiffuse across the interface and thereby increase the adhesion of the interface. Falsafi et al. [37] also used the JKR technique to study the effect of composition on the adhesion of elastomeric acrylic pressure-sensitive adhesives. The model PSA they used was a crosslinked network of random copolymers of acrylates and acrylic acid, with an acrylic acid content between 2 and 10%. 

There have been other approaches to obtaining rubber/metal adhesion besides primers or additives consisting of phenolics or epoxies plus halogenated elastomers. For example, carboxylated polymers (olefins and diolefins copolymerized with acrylic acid monomers) have shown excellent adhesion to metals. Very little carboxyl is necessary, and polymers with carboxyl contents as low as 0.1% show good adhesion when laminated to bare steel. When these materials possess... 

Acrylic acid, the main precursor to acrylic adhesives had been synthesized in the mid 1800s and the first acrylic acid esters were made and characterized at the turn of the century [62]. The first commercial launch of acrylic polymers in the form of poly(methylmethacrylate) took place in 1927 when the German company Rohm and Haas AG introduced this new plastic to the market. Soon after, other companies such as BASF introduced acrylic dispersions. 

Fig. 7. Room temperature adhesive holding power as a function of acrylic acid content.

While polar monomers are usually beneficial in acrylic PSA formulations, there are times when their presence is deleterious. Examples of this may be the use of acrylic acid containing adhesives for electronic applications, for adhering to some metallic surfaces, or for application to paper used in books. Higher levels of acrylic acid not only increase the acidity of the PSA but they also increase the moisture uptake in the adhesive making dissociation of the acid easier. This can increase corrosion problems in the electronic or metal applications, or severe discoloration and degradation of paper with time. The latter is often a significant concern to librarians who deal with repair and archival restoration of books. In applications such as these, acid-free adhesives are more desirable, or at the very least the amount of acid has to be low and caution has to be taken to fully incorporate the monomer into the PSA. 

For some applications, such as for repulpable type PSAs, it may be advantageous to incorporate high levels of acrylic acid because this makes the polymer more hydrophilic. At the same time, high levels of acid also improve the water-dispersibility of the adhesive, especially at higher pH where the acid groups are converted to the more water-soluble neutralized salt form. Since the high level of acid increases the of the resulting polymer, a non-tacky material results. To make the adhesive pressure sensitive, the polymer can be softened with water-dispersible or soluble plasticizers, such as polyethers [68]. 

Specialty waxes include polar waxes for more polar adhesive systems. Examples would be castor wax (triglyceride of 12-hydroxy stearic acid) or Paracin wax N- 2 hydroxy ethyl)-12-hydroxy stearamide) which are used in polyester, polyamide, or with high VA EVA copolymer-based systems. Other common polar waxes are maleated polyethylenes, which are used to improve the specific adhesion of polyethylene-based adhesives, and low molecular weight ethylene copolymers with vinyl acetate or acrylic acid, which are used to improve low temperature adhesion. High melting point isotactic polypropylene wax (7 155°C) and highly refined paraffin wax (7,n 83°C) are used where maximum heat resistance is critical. Needless to say, these specialty waxes also command a premium price, ranging from 2 to 5 times that of conventional paraffin wax. 

Acrylic acid and its esters are used to produce acrylic resins. Depending on the polymerization method, the resins could he used in the adhesive, paint, or plastic industry. 

Aqueous, removable, pressure-sensitive adhesive compositions, useful for high-performance applications, comprise a mixture of a copolymer of alkyl (meth)acrylate and N-substituted (poly)amide of (meth)acrylic acid and a copolymer of alkyl (meth)acrylate and ethylenically unsaturated carboxylic acid, where at least one of the copolymers is an emulsion copolymer. Polyoxyalkyl-enes and phosphate esters may be used as surfactants [234]. 

Polystyrene-PDMS block copolymers4l2), and poly(n-butyl methacrylate-acrylic acid)-PDMS graft copolymers 308) have been used as pressure sensitive adhesives. Hot melt adhesives based on polycarbonate-PDMS segmented copolymers 413) showed very good adhesion to substrates with low surface energies without the need for surface preparation, such as etching. 

Solutions of different carboxylic acids (fiimaric acid [FA], maleic acid, acrylic acid, succinic acid, and malonic acid) in ethanol have been effectively used as primers to increase the adhesion of synthetic vulcanized SBRs. The increase in the adhesion properties of SBR treated with carboxylic acid is attributed to the elimination of zinc stearate moieties and the deposition of acid on the rubber which migrates into the solvent-borne polyurethane adhesive layer once the adhesive joint is formed. The nature of the carboxylic acid determines the rate of diffusion into the adhesive and the extent of rubber-adhesive interfacial interaction. 

The polyelectrolyte cements are modern materials that have adhesive properties and are formed by the cement-forming reaction between a poly(alkenoic acid), typically poly(acrylic acid), PAA, in concentrated aqueous solution, and a cation-releasing base. The base may be a metal oxide, in particular zinc oxide, a silicate mineral or an aluminosilicate glass. The presence of a polyacid in these cements gives them the valuable property of adhesion. The structures of some poly(alkenoic acid)s are shown in Figure 5.1. 

The main line of development now lies with its successor, the glass-ionomer cement, which uses a similar glass, but in which phosphoric acid is replaced by poly(acrylic acid) this cement is more resistant to acid erosion and staining and has the great advantage of adhesion to tooth material. 

Good bonding was obtained to several substrates under aqueous conditions. Values obtained were 41 to 10-3 MPa to composite resins, and 9-8 to 15-6 MPa to stainless steel (Table 9.6). They were also reported as adhering to porcelain. No adhesion was obtained to untreated dentine or enamel. The cements could be bonded to enamel etched with add (3-5 MPa) and to dentine conditioned with poly(acrylic acid) (10 MPa). 

Not all modified starches are suitable for removal by aqueous dissolution alone. Such modifications of natural starches are carried out to reduce solution viscosity, to improve adhesion and ostensibly to enhance aqueous solubility. Commercial brands vary [169], however, from readily soluble types to those of limited solubility. Indeed, some may be as difficult to dissolve as potato starch if they have been overdried. It is thus very important to be sure of the properties of any modified starch present. If there are any doubts about aqueous dissolution, desizing should be carried out by enzymatic or oxidative treatment. Even if the size polymer is sufficiently soluble, it is important to ensure that the washing-off range is adequate. Whilst the above comments relate to modified starches, other size polymers such as poly(vinyl acetate/alcohol) and acrylic acid copolymers vary from brand to brand with regard to ease of dissolution. 

The poor adhesion of carboxymethylcellulose to synthetic fibres means that where such fibres are present, it can only be effective in combination with a synthetic size polymer (Table 10.6). This needs to be taken into account when considering suitable desizing procedures. If this cellulose derivative is to be used in conjunction with an electrolyte-sensitive acrylic acid copolymer, it is advisable to choose a salt-free carboxymethylcellulose. 

The potential of using extrinsic (fluorescent) probes for monitoring the initial stages of oxidation was explored for the photo-oxidation of a UV-cured aliphatic polyurethane-acrylate-based adhesive [68]. The two probes investigated were p-dimethylamino salicylic acid (p-DASA) and 2, 7 -difluorescein (Oregon Green... 

Both acrylic acid and methacrylic acid polymerise to give water soluble hard resins. The viscous solutions so formed have been used as emulsifying agents, adhesives and as thickening agents for inks and dyes. Polymers of esters of these acids are of greater commercial importance. Esters can be prepared from cyanhydrins by reaction with an alcohol ... 

In a previous section, the effect of plasma on PVA surface for pervaporation processes was also mentioned. In fact, plasma treatment is a surface-modification method to control the hydrophilicity-hydrophobicity balance of polymer materials in order to optimize their properties in various domains, such as adhesion, biocompatibility and membrane-separation techniques. Non-porous PVA membranes were prepared by the cast-evaporating method and covered with an allyl alcohol or acrylic acid plasma-polymerized layer the effect of plasma treatment on the increase of PVA membrane surface hydrophobicity was checked [37].The allyl alcohol plasma layer was weakly crosslinked, in contrast to the acrylic acid layer. The best results for the dehydration of ethanol were obtained using allyl alcohol treatment. The selectivity of treated membrane (H20 wt% in the pervaporate in the range 83-92 and a water selectivity, aH2o, of 250 at 25 °C) is higher than that of the non-treated one (aH2o = 19) as well as that of the acrylic acid treated membrane (aH2o = 22). 

Control of fiber friction is essential to the processing of fibers, and it is sometimes desirable to modify fiber surfaces for particular end-uses. Most fiber friction modifications are accomplished by coating the fibers with lubricants or finishes. In most cases, these are temporary treatments that are removed in final processing steps before sale of the finished good. In some cases, a more permanent treatment is desired, and chemical reactions are performed to attach different species to the fiber surface, e.g. siliconized slick finishes or rubber adhesion promoters. Polyester s lack of chemical bonding sites can be modified by surface treatments that generate free radicals, such as with corrosive chemicals (e.g. acrylic acid) or by ionic bombardment with plasma treatments. The broken molecular bonds produce more polar sites, thus providing increased surface wettability and reactivity. 

The important role Transmission Electron Microscopy (TEM) can play in this process is demonstrated on the development of an oxidation catalyst for the production of acrylic acid. Acrylic acid is produced by BASF in quantities of several 100.000 tons per year in a two step gas phase oxidation process starting from propene, which is oxidised to acrolein in the first step and then further oxidised to acrylic acid in a second step, each step requiring a special developed catalyst. Acrylic acid is used as a base material for the production of superabsorbents for nappies, dispersions and emulsions for adhesives and construction materials. 

The failure in increasing residence time of mucoadhesive systems in the human intestinal tract has led scientists to the evaluation of multifunctional mucoadhesive polymers. Research in the area of mucoadhesive drug delivery systems has shed light on other properties of some of the mucoadhesive polymers. One important class of mucoadhesive polymers, poly(acrylic acid) derivatives, has been identified as potent inhibitors of proteolytic enzymes [72-74]. The interaction between various types of mucoadhesive polymers and epithelial cells has a direct influence on the permeability of mucosal epithelia by means of changing the gating properties of the tight jrmctions. More than being only adhesives, some mucoadhesive polymers can therefore be considered as a novel class of multifunctional macromolecules with a number of desirable properties for their use as delivery adjuvants [72,75]. 

Acrylic acid and its salts are raw materials for an important range of esters, including methyl, ethyl, butyl, and 2-ethylhexyl acrylates. The acid and its esters are used in polyacrylic acid and salts (32%, including superabsorbent polymers, detergents, water treatment chemicals, and dispersants), surface coatings (18%), adhesives and sealants (15%), textiles and non-wovens (12%), plastic modifiers (5%), and paper coating (3%). 

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