Cross-linkers

We also need to take into account that in some gas sensor applications, where the swelling effect plays a major role, the use of cross-hnkers can be limited. Cross-linking increases the strength of the cross-linked material but decreases its flexibility and increases its brittleness. Most chemical cross-linking is not easily reversible. 

The application of cross-linker can produce other effects as well. For example, Matsuguchi et al. (2003) analyzed the influence of cross-linker on the characteristics of QCM-based SO sensors and found that sensors with cross-linked structure had lower sorption ability but faster sorption/desorption rates. The latter is known to be very important for sensors designed for in situ measurements. In the case of poly(styrene-co-chloromethyl styrene), the use of the cross-linked structure clearly increased the sensitivity to NOj of piezoelectric devices (Matsuguchi et al. 2005). 

However, this effect was observed only at a certain concentration of cross-linker. Larger concentrations of cross-linkers did not increase sensitivity. 

During the activation of the initiator consisting of a heterocyclic, aryl substituted, or aryl-ring fused sulfonium salt, a carbon-sulfur bond is broken via a ring-opening reaction, leading to formation of a sulfide and a carbocation (carbenium ion) within the same molecule. The functionality of 

It should be noted that, since the activation does not lead to fragmentation of the initiator molecule into smaller molecules, no molecular sulfur-containing decomposition products form that would otherwise evaporate or migrate from the polymer causing bad smells. 

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Cross-linked starches Cross-linkers Cross-linking... 

Poly(acrylic acid) and Poly(methacrylic acid). Poly(acryHc acid) (8) (PAA) may be prepared by polymerization of the monomer with conventional free-radical initiators using the monomer either undiluted (36) (with cross-linker for superadsorber appHcations) or in aqueous solution. Photochemical polymerization (sensitized by benzoin) of methyl acrylate in ethanol solution at —78° C provides a syndiotactic form (37) that can be hydrolyzed to syndiotactic PAA. From academic studies, alkaline hydrolysis of the methyl ester requires a lower time than acid hydrolysis of the polymeric ester, and can lead to oxidative degradation of the polymer (38). Po1y(meth acrylic acid) (PMAA) (9) is prepared only by the direct polymerization of the acid monomer it is not readily obtained by the hydrolysis of methyl methacrylate. 

Small amounts of specially functionalized monomers are often copolymerized with acryUc monomers in order to modify or improve the properties of the polymer. These functional monomers can bring about improvements either directiy or by providing sites for further reaction with metal ions, cross-linkers, or other compounds and resins. Table 9 Hsts some of the more common functional monomers used in the preparation of acryUc copolymers. 

Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

Fillers (qv) are occasionally used in flexible slab foams the two most commonly used are calcium carbonate (whiting) and barium sulfate (barytes). Their use level may range up to 150 parts per 100 parts of polyol. Various other ingredients may also be used to modify a flexible foam formulation. Cross-linkers, chain extenders, ignition modifiers, auxiHary blowing agents, etc, are all used to some extent depending on the final product characteristics desired. 

Preformed Two-Piece Metal Containers. Ink vehicles for letterset printing of two-piece aluminum or steel containers are mainly based on special polyester vehicles used in conjunction with melamine cross-linkers. Short cycle ovens which dry inks in 1—5 seconds are now used and operate at temperatures as high as 350 °C. The rheology of these inks must be adjusted to the unique geometry of the press. Desired rheological properties are achieved by the use of additives as weU as extender pigments. 

The organic and aqueous phases are prepared in separate tanks before transferring to the reaction ketde. In the manufacture of a styrenic copolymer, predeterrnined amounts of styrene (1) and divinylbenzene (2) are mixed together in the organic phase tank. Styrene is the principal constituent, and is usually about 90—95 wt % of the formulation. The other 5—10% is DVB. It is required to link chains of linear polystyrene together as polymerization proceeds. DVB is referred to as a cross-linker. Without it, functionalized polystyrene would be much too soluble to perform as an ion-exchange resin. Ethylene—methacrylate [97-90-5] and to a lesser degree trivinylbenzene [1322-23-2] are occasionally used as substitutes for DVB. 

Formulations for acryHc copolymers involve monomers such as acryHc acid [79-10-7], methacrylic acid [79-14 ], or esters of these acids. Formation of a copolymer from a methylmethacrylate ester (3), where DVB serves as the cross-linker, gives the stmctures ... 

The point at which two polymeric chains are joined together by a cross-linker such as divinylbenzene, or sites where tertiary hydrogens are located in the stmcture, are other locations for oxidative attack. In both cation- and anion-exchange resins, oxidative attack results in the removal of cross-linking. 

Organic cross-linkers, which include glyoxal (48) and formaldehyde (qv), have also been used. Use of hypohaUte salts (49) and epichlorohydrin (50) promotes gel stabiUty. Phenol—formaldehyde cross-linking systems have been used to produce stable acrylamide copolymer gels at temperatures above 75°C and brine hardness levels above 2000 ppm (51). 

Cross-linked xanthan gums have also been used to reduce the permeabiUty of thief 2ones. Trivalent chromium is the preferred cross-linker (54). Cross-linker effectiveness is less at high salinity. However, Cr(III) has been used ia the field at salinities as great as 166,000 ppm total dissolved soHds (55). 

Displacement of a volatile with a nonvolatile alcohol is an important reaction for curing paint films with amino cross-linkers and amino resias on textile fabrics or paper. FoUowiag is an example of a methoxymethyl group on an amino resia reacting with a hydroxyl group of a polymer chain. 

Fig. 9. A de novo designed P sheet protein, betabellin, formed by the dimerization of two identical four-stranded -sheets and a disulfide linking the two sheets. This model is for betabeUins 9 and later progenies the earher betabeUins contained a two-armed cross-linker connecting the sheets (51).

Fig. 10. Generalized formulation design outline for radiation-curable coatings and adhesive systems. The cross-linker is a multifimctional unsaturated cross-linking agent or oligomer, rj = viscosity CR = cure rate S = shrinl ge H = hardness F = flexibility A = adhesion 7 = surface energy ...

Moisture-Curing Silicones. The formulation of moisture-curing sHicones includes a sHicone polymer, filler, a moisture-reactive cross-linker, and sometimes a catalyst. The most common sHicone polymer used in sealant formulations is an alternating sHicon—oxygen backbone with methyl groups attached to the sHicon such as the sHicone polymer (1). 

The moisture-reactive cross-linkers used in sihcones are of the form R Si(OR )4 where n = 0 or 1 and R may be any organic group, such as methyl, ethyl, or vinyl. R also varies acetoxy, alkoxy, oxime, and propenoxy are among the most typical. Common cross-linkers are hsted in Table 1, and a typical formulation for a one-part sihcone sealant is given in Table 2. 

Table 1. Common One-Part Silicone Cross-Linkers and Their Leaving Groups...

Cure system Cross-linker CAS Registry Number Leaving group... 

Some of the sihcone cross-linkers are reactive enough on their own to cute a sihcone sealant without the use of a catalyst. Most, however, requite a catalyst, usually a tin carboxylate or an organotitanate. 

The cure rate of a sihcone sealant is dependent on the reactivity of the cross-linker, catalyst type, catalyst level, the diffusion of moisture into the sealant, and the diffusion of the leaving group out of the sealant. For one-part sealants, moisture diffusion is the controlling step and causes a cured skin to form on the exposed sealant surface and progress inward. The diffusion of moisture is highly dependent on the temperature and relative humidity conditions. 

Unfortunately, because self-condensation of silanols on the same silicone can occur almost spontaneously, the reaction of disdanol or trisilanol compounds with telechelic sdanol polymers to form a three-dimensional network is not feasible. Instead, the telechelic polymers react with cross-linkers containing reactive groups such as alkoxysdanes, acyloxysdanes, silicon hydrides, or methylethyloximesilanes, as in the reactions in equations 18—21 (155). 

Relative hydrolysis and condensation rate studies of multifunctional silanes, Si(OR), under acidic and basic catalysis showed that the first (OR) group hydroly2es much more readily than subsequent groups (195). Sdanol—sdanol condensation is much slower than sdanol—alkoxysilane condensation, even if the alkoxysilane is monofunctional, thus suggesting that chain extension is insignificant ia the presence of a cross-linker (196—199). 

Condensation cure can also be carried out ia emulsions (200—209). In this case, the cross-linker and polydimethylsiloxanediol are emulsified usiag anionic, cationic, or nonionic surfactants ia water, and a condensation catalyst such as dibutyltin dilaurate is added. The polymer can then undergo cross-linking, forming a continuous film when the water is evaporated. 

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