Crosslinking catalyzed

Fig. 2. Relaxation modulus G(t) of a set of polydimethylsiloxane samples with increasing extent of crosslinking plotted against time of crosslinking. The linear PDMS chains (Mn 10 000, polydis-persity index 2) were endlinked with a four-functional silane crosslinker catalyzed by a platinum compound. Samples with different extent of reaction were prepared by poisoning the reaction at different times. The actual extent of reaction was not determined. Two of the samples are clearly before the gel point (LST) and two beyond. The third sample is very close to the gel point. Data of Chambon and Winter [5] evaluated by Baumgartel and Winter [8]...

Figure 1. Comparison of crosslinking catalyzed by added acid and photogenerated acid for crosslinker 1.

Other crosslinking reactions may be triggered by a catalyzed reaction between different units of a copolymerized functional monomer, such as A -methylol acrylamide or a copolymerized silane compound [86]. 

Scheme 11. Basic crosslinking reaction by hydrosilylation catalyzed by a platinum complex.

Recently, a two-part cross-catalyzed system has been developed that takes advantage of both the acceleration abilities of resorcinol resin and ester [179], The term cross-catalyzed is applied because the phenolic resin contains an accelerator-crosslinker for the resorcinol resin while the resorcinol resin carries an accelerator for the PF, in addition to itself being capable of improving PF cure speed. In each part, the resin carrier for the accelerator is not susceptible to acceleration by the material contained. It is only when the systems are mixed that the accelerators are activated. This system is faster and lower in cost than most of the resorcinol accelerators and gives better bonds (in wood products) than the ester cure alone [179], Another variant of the resorcinol approach utilizes resorcinol-glutaraldehyde resins [180-182],... 

The acid-catalyzed reaction occurs by an electrophilic substitution where formaldehyde is the electrophile. Condensation between the methylol groups and the benzene rings results in the formation of methylene bridges. Usually, the ratio of formaldehyde to phenol is kept less than unity to produce a linear fusible polymer in the first stage. Crosslinking of the formed polymer can occur by adding more formaldehyde and a small amount of hexamethylene tetramine (hexamine. 

Used for crosslinking novolacs or catalyzing resole syntheses, HMTA is prepared by reacting formaldehyde with ammonia (Fig. 7.5). The reaction is reversible at high temperatures, especially above 250°C. HMTA can also be hydrolyzed in the presence of water. 

Resole resins are generally crosslinked under neutral conditions between 130 and 200° C or in the presence of an acid catalyst such as hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, and phenolsulfonic acid under ambient conditions.3 The mechanisms for crosslinking under acidic conditions are similar to acid-catalyzed novolac formation. Quinone methides are the key reaction intermediates. Further condensation reactions in resole resin syntheses under basic conditions at elevated temperatures also lead to crosslinking. 

Initiation of stannous octoate-catalyzed copolymerization of e-caprolactone with glycerol was used to prepare a series of trifunctional hydroxy-end blocked oligomers, which were then treated with hexane-1,6-diisocyanate to form elastomeric polyesterurethanes with different crosslink densities (49). Initiation of e-caprolactone polymerization with a hydroxypropyl-terminated polydimethylsiloxane in the presence of dibutyl tin dilaurate has been used to prepare a polyester-siloxane block copolymer (Fig. 4) (50). 

Because this diketene acetal is so susceptible to cationic polymerization, acids cannot be used to catalyze its condensation with diols because the competing cationic polymerization of the diketene acetal double bonds leads to a crosslinked product. Linear polymers can, however, be prepared by using iodine in pyridine (11). Polymer structure was verified by 13c nmR spectroscopy as shown in Fig. 

A new crosslinkable polymer was synthesized by the SBP-catalyzed polymerization of cardanol. When HRP was used as catalyst for the cardanol polymerization, the reaction took place in the presence of a redox mediator (phe-nothiazine derivative) to give the polymer. Fe-salen efficiently catalyzed the polymerization of cardanol in organic solvents (Scheme 29). " The polymerization proceeded in 1,4-dioxane to give the soluble polymer with molecular weight of several thousands in good yields. The curing of the polymer took place in the presence of cobalt naphthenate catalyst at room temperature or thermal treatment (150°C for 30 min) to form yellowish transparent films ( artificial urushi ... 

D. Craig and S. A. Holditch. The degradation of hydroxypropyl guar fracturing fluids by enzyme, oxidative, and catalyzed oxidative breakers Pt 2 Crosslinked hydroxypropyl guar gels Topical report (January-April 1992). Gas Res Inst Rep GRI-93/04192, Gas Res Inst, December 1993. 

As part of our continuing study of the peroxide-catalyzed reactions of MAH with saturated polyolefins, the present investigation was undertaken to determine the extent of crosslinking and/or degradation which accompanies the EPR-MAH reaction. The gel content, presumably indicative of crosslinking, was determined by extraction with cyclohexane at room temperature (22 C) for 60 hr. 

Stearamide is one of many electron donors which donate an electron to the cationic moiety in excited MAH or in propagating -MAH chains. This results in the inhibition of the homopolymerization of MAH and decreases the crosslinking of polyethylene and the degradation of polypropylene which accompany the peroxide-catalyzed reaction of MAH with these polyolefins (8,9). ... 

Thus, Andrianov et al. (26) attempted to catalyze polymerization of a number of alkyl and alkyl/aryl cyclosilazanes using catalytic amounts of KOH or other strong bases at temperatures of up to 300°C. In general, the reactions proceed with evolution of NHj, hydrocarbons and the formation of intractable, crosslinked, brittle products even at low temperatures. Contrary to what is observed with cyclotri-siloxanes, no evidence was found for the formation of linear poly-silazanes. Copolymerization of mixtures of cyclosilazanes and cyclosiloxanes gave somewhat more tractable polymers with less evolution of hydrocarbons or ammonia, however very little was done to characterize the resulting materials. 

The ubiquitous hydrosilation reaction, popular especially in silicone manufacturing,132 has been utilized by Houser and Keller for the synthesis of the networked polymers (104) (Fig. 64) from the reaction of the l,7-bis(vinyltetramethyldisiloxyl)-w-carborane monomer with the polymeric crosslinker, poly(methylhydrosiloxane).133 The reactions were catalyzed by the Speier s catalyst, H2PtCl6. Three samples were... 

Polysilazanes that can serve as precursors for silicon carbonitride have been prepared using a Ru3(CO)i2-catalyzed Si-H/N-H dehydrogenative coupling process by workers at SRI [21]. Thus the ammonolysis product of CH3SiHCl2, whose composition approximates [CH3Si(H)NH]n, could be crosslinked by heating at 40 °C with a catalytic quantity of Ru3(CO)i2. Other polysilazanes were prepared by this procedure ... 

Purify the reduced IgG from excess 2-mercaptoethylamine and reaction by-products by dialysis or gel filtration using a desalting resin. All buffers should contain 1-10 mM EDTA to preserve the free sulfhydryls from metal-catalyzed oxidation. The sulfhydryl-containing half antibody now may be used in conjugation protocols that use —SH-reactive heterobifunctional crosslinkers (Chapter 5, Section 1). 

Dissolve the thiol-containing proteins to be crosslinked in 50 mM sodium phosphate, pH 6.5-7.5, containing 10 mM EDTA to prevent metal-catalyzed sulfhydryl oxidation. 

Figure 28.21 The reactions of R u (11) pby 3 + are catalyzed by light at 452 nm that begins by forming an excited state intermediate. In the presence of persulfate, a sulfate radical is formed concomitant with the oxidative product Ru(III)bpy33+. This form of the chelate is able to catalyze the formation of a radical on a tyrosine phenolic ring that can react along with the sulfate radical either with a nucleophile, such as a cysteine thiol, or with another tyrosine side chain to form a covalent linkage. The result of this reaction cascade is to cause protein crosslinks to form when a sample containing these components is irradiated with light.

Working with polymethyl methacrylate, Sirdesai and Wilkie (36) have shown that certain phosphine-platinum complexes undergo oxidative insertion reactions and thus catalyze crosslinking leading to flame retardance. This catalyst is expensive and not particularly efficient, but serves as a lead. 

In the present study we use the acid catalyzed crosslinking reaction directly (Scheme 1) as a means to estimate the amount of acid generated in a typical AHR resist. We then use the model proposed by Seligson and coworkers to determine the activation energy of crosslinking for a variety of crosslinking resins as they might be used in a resist formulation. Where... 

Acid Concentration Required for Crosslinking Resist Films. The strong acid catalyzed reaction of methylated melamine 1 with novolak in a film was studied first in order to estimate the amount of acid generated in experimental AHR resists upon exposure. Incremental amounts of a 1% solution of p-toluenesulfonic acid (pTSA) were added to a resist solution which contained no RSAG. The solutions were coated onto wafers and subjected to a typical bake cycle. The dissolution rate... 

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