Resin Novolak

Novolak photoresist Novolak process Novolak resin... 

Strong-Acid Catalysts, Novolak Resins. PhenoHc novolaks are thermoplastic resins having a molecular weight of 500—5000 and a glass-transition temperature, T, of 45—70°C. The phenol—formaldehyde reactions are carried to their energetic completion, allowing isolation of the resin ... 

The typical acid catalysts used for novolak resins are sulfuric acid, sulfonic acid, oxaUc acid, or occasionally phosphoric acid. Hydrochloric acid, although once widely used, has been abandoned because of the possible formation of toxic chloromethyl ether by-products. The type of acid catalyst used and reaction conditions affect resin stmcture and properties. For example, oxaUc acid, used for resins chosen for electrical appHcations, decomposes into volatile by-products at elevated processing temperatures. OxaUc acid-cataly2ed novolaks contain small amounts (1—2% of the original formaldehyde) of ben2odioxanes formed by the cycli2ation and dehydration of the ben2yl alcohol hemiformal intermediates. 

Alkaline Catalysts, Resoles. Resole-type phenoHc resins are produced with a molar ratio of formaldehyde to phenol of 1.2 1 to 3.0 1. For substituted phenols, the ratio is usually 1.2 1 to 1.8 1. Common alkaline catalysts are NaOH, Ca(OH)2, and Ba(OH)2. Whereas novolak resins and strong acid catalysis result in a limited number of stmctures and properties, resoles cover a much wider spectmm. Resoles may be soHds or Hquids, water-soluble or -insoluble, alkaline or neutral, slowly curing or highly reactive. In the first step, the phenolate anion is formed by delocali2ation of the negative charge to the ortho and para positions. 

Novolak Resins. In a conventional novolak process, molten phenol is placed into the reactor, foHowed by a precise amount of acid catalyst. The formaldehyde solution is added at a temperature near 90°C and a formaldehyde-to-phenol molar ratio of 0.75 1 to 0.85 1. For safety reasons, slow continuous or stepwise addition of formaldehyde is preferred over adding the entire charge at once. Reaction enthalpy has been reported to be above 80 kj /mol (19 kcal/mol) (29,30). The heat of reaction is removed by refluxing the water combined with the formaldehyde or by using a small amount of a volatile solvent such as toluene. Toluene and xylene are used for azeotropic distillation. FoHowing decantation, the toluene or xylene is returned to the reactor. 

The reaction is completed after 6—8 h at 95°C volatiles, water, and some free phenol are removed by vacuum stripping up to 140—170°C. For resins requiring phenol in only trace amounts, such as epoxy hardeners, steam distillation or steam stripping may be used. Both water and free phenol affect the cure and final resin properties, which are monitored in routine quaHty control testing by gc. OxaHc acid (1—2 parts per 100 parts phenol) does not require neutralization because it decomposes to CO, CO2, and water furthermore, it produces milder reactions and low color. Sulfuric and sulfonic acids are strong catalysts and require neutralization with lime 0.1 parts of sulfuric acid per 100 parts of phenol are used. A continuous process for novolak resin production has been described (31,32). An alternative process for making novolaks without acid catalysis has also been reported (33), which uses a... 

In the post-dispersion process, the soHd phenoHc resin is added to a mixture of water, cosolvent, and dispersant at high shear mixing, possibly with heating. The cosolvent, frequently an alcohol or glycol ether, and heat soften the resin and permit small particles to form. On cooling, the resin particles, stabilized by dispersant and perhaps thickener, harden and resist settling and agglomeration. Both resole and novolak resins have been made by this process (25). 

In some resole appHcations, such as foam and foundry binders, a rapid cure of a Hquid resin is obtained at RT with strong acid. The reactions proceed in the same manner as those of novolak resin formation. Methylol groups react at ortho and para phenoHc hydrogen to give diphenyknethane units (41). 

Novolaks. Novolak resins are typically cured with 5—15% hexa as the cross-linking agent. The reaction mechanism and reactive intermediates have been studied by classical chemical techniques (3,4) and the results showed that as much as 75% of nitrogen is chemically bound. More recent studies of resin cure (42—45) have made use of tga, dta, gc, k, and nmr (15). They confirm that the cure begins with the formation of benzoxazine (12), progresses through a benzyl amine intermediate, and finally forms (hydroxy)diphenyknethanes (DPM). 

Spectroscopy. Infrared spectroscopy (48) permits stmctural definition, eg, it resolves the 2,2 - from the 2,4 -methylene units in novolak resins. However, the broad bands and severely overlapping peaks present problems. For uncured resins, nmr rather than ir spectroscopy has become the technique of choice for microstmctural information. However, Fourier transform infrared (ftir) gives useful information on curing phenoHcs (49). Nevertheless, ir spectroscopy continues to be used as one of the detectors in the analysis of phenoHcs by gpc. 

Color intensity and permanence are improved by metal carboxylate salts, especially 2inc salts (83), which cataly2e the dye development and stabili2e the dye in its colored form. The substituted novolak resin, along with extender and binder, can be apphed to the receiving sheet as a solution or aqueous dispersion. Aqueous dispersions are probably the most widely used they are manufactured by the resin suppher or the user from the base resin. 

Both cold- and warm-coating processes employ solutions of phenoHc resins. The principal process used for foundry resins is the hot-coating process. It is the fastest, least expensive, and safest process, and it requires no volatile removal. The sand is heated to 135—170°C in a muller, and soHd novolak resin in flake form is added, which melts quickly and coats the sand. A lubricant may be added at this point. After one minute of mulling, the batch is cooled by adding water, which evaporates rapidly. 

Fibers. The principal type of phenoHc fiber is the novoloid fiber (98). The term novoloid designates a content of at least 85 wt % of a cross-linked novolak. Novoloid fibers are sold under the trademark Kynol, and Nippon Kynol and American Kynol are exclusive Hcensees. Novoloid fibers are made by acid-cataly2ed cross-linking of melt-spun novolak resin to form a fuUy cross-linked amorphous network. The fibers are infusible and insoluble, and possess physical and chemical properties that distinguish them from other fibers. AppHcations include a variety of flame- and chemical-resistant textiles and papers as weU as composites, gaskets, and friction materials. In addition, they are precursors for carbon fibers. 

PyrogaUol has been cited for use in photosensitive compositions. It is used in the form of sulfonate esters of quinonediazides which hydrolyze when exposed to actinic light to Hberate the acid which, in turn, catalyzes further reaction of novolak resins (60). 

Segments. Segments for heavy-duty use such as for medium-sized tmcks ate produced by a dry-mix process. The fiber, modifiers, and a dry novolak resin are mixed in an appropriate mixer. The blend is then formed into about a 60 by 90 cm preform (or briquet) at 3—4 MPa (400—600 psi). The briquets are hot-pressed for 3—10 min at 140—160°C and then cooled. The resin is only partially cured at this point to be thermoplastic when subsequently reheated for bending. The hot-pressed preforms are then cut to desired size and bent at 170—190°C and cured in curved molds for 4—8 h at 220—280°C. Final grinding produces the finished segments. 

In the 1960s, CIBA Products Co. marketed and manufactured glycidylated o-cresol novolak resins, which had been developed by Koppers Co. as high temperature-resistant polymers. Dow offered glycidylated phenol novolak resins, SheU introduced polyglycidyl ethers of tetrafunctional phenols, and Union Carbide developed a triglycidyl p- am in oph en o1 resin. 

The epoxy cresol—novolak resins (2) are prepared by glycidylation of o-cresol—formaldehyde condensates in the same manner as the phenol—novolak resins. The o-cresol—formaldehyde condensates are prepared under acidic conditions with formaldehyde—o-cresol ratios of less than unity. 

The (9-cresol novolaks of commercial significance possess degrees of polymerization, n, of 1.7—4.4 and the epoxide functionaUty of the resultant glycidylated resins varies from 2.7 to 5.4. Softening points (Durran s) of the products are 35—99°C. The glycidylated phenol and o-cresol—novolak resins are soluble in ketones, 2-ethoxyethyl acetate, and toluene solvents. The commercial epoxy novolak products possess a residual hydrolyzable chlorine content of <0.15 wt% and a total chlorine content of ca 0.6 wt % (Table 2). 

Table 2. Typical Properties of Epoxy Cresol—Novolak Resins ...

Epoxy Phenol—Novolak Resins. Epoxy phenol—novolak resins [9003-36-5] are represented by the general idealized stmcture (3) whereby multifunctional products are formed containing a phenoHc hydroxyl group per phenyl ring in random para—para, ortho—para, and ortho—ortho combinations. 

The thermal stabiUty of epoxy phenol—novolak resins is useful in adhesives, stmctural and electrical laminates, coatings, castings, and encapsulations for elevated temperature service (Table 3). Filament-wound pipe and storage tanks, liners for pumps and other chemical process equipment, and corrosion-resistant coatings are typical appHcations using the chemically resistant properties of epoxy novolak resins. 

Epoxy Phenol Novolak Resins. Acute oral studies indicate low toxicity for these resins (49). Eye studies indicate only minor irritation in animals (49). The EPN resins have shown weak skin-sensitizing potential in humans. 

The novolak resins themselves contain no reactive methylol groups and do not form cross-linked structures on heating. If, however, they are mixed with compounds capable of forming methylene bridges, e.g. hexamethylenetetramine or paraformaldehyde, they cross-link on heating to form infusible, thermoset structures. 

In the case of novolak resins the distillation is normally carried out without the application of vacuum. Thus, as the reaction proceeds and the water is driven off, there is a rise in the temperature of the resin which may reach as high as 160°C at the end of the reaction. At these temperatures the fluid is less viscous and more easily stirred. In cases where it is important to remove the volatiles present, a vacuum may be employed after the reaction has been completed, but for fastcuring systems some of the volatile matter (mainly low molecular weight phenolic bodies) may be retained. 

Between 10 and 15 parts of hexa are used in typical moulding compositions. The mechanism by which it cross-links novolak resins is not fully understood but it appears capable of supplying the requisite methylene bridges required for cross-linking. It also functions as a promoter for the hardening reaction. 

The PE fibres are produced by melt spinning a novolak resin of molecular weight ca 1000 and then cross-linking the molecules by exposure to gaseous formaldehyde at 100-150°C for 6-8 h or with a formaldehyde solution. The fibres were introduced under the tradename Kynol by American Kynol Inc., a subsidiary of Carborundum AG. 

This molecule has a functionality of four. Commercial epoxide-novolak resins have functionalities between 2.5 and 6. 

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