MXPA97008801A - Compositions of phenolic resins with improved resistance to impa - Google Patents

Abstract

The phenolic siloxane compositions are described which are prepared by, 1) the combination of the phenol with an aldehyde and a silicone intermediate with alkoxy or silanol functional group, 2) the combination of a phenolic novolak resin with a formaldehyde donor and a silicone intermediate with alkoxy or silanol functional group, or 3) the combination of a phenolic resole resin with a silicone intermediate with alkoxy or silanol functional group. Catalysts may optionally be added to facilitate formation of a phenolic resin, condensation of the phenolic resin and hydrolysis and / or condensation of the silicone intermediate. The resulting composition comprises an IPN of siloxane polymers and phenolic polymers, and has resistance to flame, heat and chemicals, equal to or exceeds that of conventional phenolic resins, and has impact resistance, tensile strength, modulus and improved density

Description

COMPOSITIONS OF PHENOLIC RESINS WITH IMPROVED IMPACT RESISTANCE Field of the Invention The present invention relates in general to phenolic resin compositions, useful in the provision of fire resistance, together with low smoke emission and low smoke toxicity, heat resistance, chemical resistance and good abrasion and wear resistance in numerous applications. More particularly, the present invention relates to the siloxane-modified phenolic compositions which, in addition to the excellent fire and heat resistance properties, etc., described above, provide improved impact strength and stiffness, improved residual strength after exposure to fire, improved bending mode and improved elasticity in phenolic foam.

Background of the Invention Phenolic resins are the oldest of the synthetic materials, which are first formed by catalyzed reaction between phenol and REF: 26104 formaldehyde. Phenolic resins are in general, but not exclusively, thermosetting by nature and are characterized by their excellent properties of resistance to heat, flame and chemicals, good electrical properties, good resistance to moisture and oxygen, excellent adhesion to a wide variety of substrates, and low production cost. The properties have led to the widespread use of phenolic resins in applications such as bonding wood and fiber, bonded and coated abrasives, friction elements, binders for sand molds and foundry cores, structural and contact adhesives, industrial and decorative laminates , composite materials, molding compounds and coatings, to name a few. Although cured phenolic resins have excellent physical properties of resistance to heat, flame and chemicals, phenolic resins inherently hard and brittle, and therefore have little resistance to impact and flexibility. Phenolic resins produced by the reaction of phenol and formaldehyde catalyzed by base, for example, phenolic resole, show a brittleness that is caused by a high density of crosslinking that exists throughout the polymer structure, by virtue of the large number of Ethylol groups participating in the ethyllation reactions. The fragility and lack of flexibility of such cured phenolic resins prevents their use in applications where it is desired that the structure formed by such resin, or substrate coated with such a resin, be flexible or impact resistant to some degree. Substrates coated with such phenolic resins that are subject to some degree of flexion or impact, lose the heat, flame and chemical resistance, provided by the coating, because such bending or impact causes the brittle coating to break or crack and leave the underlying substrate unprotected. The industry has sought for decades improved resistance to the impact of phenolic compositions. Techniques for forming phenolic resin compositions having improved flexibility when compared to phenol resin alone are known. An example of this type is by incorporating wood powder, or other reinforcing ingredient, and pigment with other additives to provide a moldable thermosetting phenolic composition having improved flexibility. However, the incorporation of such reinforcing ingredients and additives to form such a phenolic composition have the effect of reducing the resistance to heat, flame and chemical products, provided by the phenolic resin alone. Accordingly, the ability to provide a flexible phenolic composition according to the prior art represented a compromise between heat, flame and chemical resistance and increased flexibility. In applications where flexibility and high degree of heat resistance, to the flame and to the chemical products is required, such technique is not practical. Yet another technique for forming a phenolic resin having improved flexibility is by internal plasticization. In this technique a percentage of the methylol groups are cased, for example, they are esterified, by the addition of an alcohol such as butanol. The alcohol reacts preferably with the methylol groups to give butoxy side chains to the resoles. The use of such a technique reduces the high density of crosslinking and improves the flexibility of the phenolic resin, cured, resulting, by decreasing the functionality of the resin. However, the improved flexibility acquired through the technique is at the expense of the reduced resistance to heat, flame and chemicals, for the resulting cured phenolic resin. Accordingly, such a technique is not useful to provide a phenolic resin that is flexible and has a high degree of resistance to heat, flame and chemicals. In addition, phenolic resins that are used to make molding compounds, laminates and composite materials often contain high levels of trapped water. When heat is applied to such resols during the curing process the water evaporates, leaving microvoids in the cured article, which can decrease the tensile strength and flexural modulus of the phenolic resole resin, cured, resulting, contributing in addition to the fragility and non-flexibility of the cured phenolic resole resin. These microvoids can also lead to increased moisture absorption, via a porous surface structure, and reduced chemical resistance of the cured phenol resin. Therefore, it is desirable that a phenolic resin composition is prepared which exhibits physical properties of good flexibility and impact resistance, without reducing the properties to heat, flame and chemicals, inherent in the phenolic resin. It is also desirable that the phenolic resin composition shows decreased water retention, during formation and, thereby, shows reduced formation of microvoids during cure.

Brief Description of the Invention Thus, in the practice of this invention, there are provided, the phenolic compositions prepared by the use of a sufficient amount of silicone intermediate to form phenolic siloxane compositions having improved properties of flexibility and impact resistance, in the composition cured, when compared to conventional phenolic compositions that do not contain siloxane. A first embodiment of the phenolic siloxane composition is prepared by the combination of a phenol or substituted phenol with a silicone intermediate with an alkoxy or silanol functional group and an aldehyde. A second embodiment is prepared by combining a phenolic novolak resin with a silicone intermediate with alkoxy or silanol functional group, and a formaldehyde donor. A third embodiment is prepared by combining a phenolic resole resin with a silicone intermediate with alkoxy or silanol functional group. The ingredients in each of the embodiments react to form a polymer network of interpenetration of the siloxane polymer and the phenolic polymer, wherein the phenolic polymer includes Si-0 groups in its backbone. In the first embodiment, a catalyst selected from the group including acids and bases is used to facilitate the formation of a desired phenolic novolak or phenolic resole resin from the phenol, or the substituted phenol and aldehyde ingredients. If desired, a catalyst may be used in the first, second or third embodiments to facilitate the condensation of the newly formed phenolic resin, or the initial material of the phenolic resin, and may include acids, bases and formaldehyde donors, depending on if the phenolic resin formed used as an initial material is a phenolic resole resin or phenolic novel lacquer. If desired, a sufficient amount of catalyst can be used in the first, second or third embodiments to facilitate hydrolysis and / or condensation of silicone intermediate at low temperatures. The catalyst may include organometallic compounds, amine compounds and mixtures thereof. A preferred catalyst is a mixture of an organometallic compound and an amine compound. The phenol, the aldehyde and the silicone intermediate in the first embodiment; the phenolic novolac resin, the formaldehyde donor and the silicone intermediate in the second embodiment; the phenolic resole resin and the silicone intermediate in the third embodiment; and any optionally desired catalysts are blended together to form a phenolic siloxane composition having improved properties of impact resistance, tensile strength, flex modulus, and density when compared to conventional siloxane-containing phenolic resin compositions. . In addition, the phenolic siloxane compositions have equal or better resistance properties to flame, heat and chemicals when compared to conventional phenolic resin compositions that do not contain siloxane.

Brief Description of the Drawings This and other features and advantages will be appreciated as they become better understood with reference to the specification, the claims and the drawings, wherein: Figure 1 is an isometric view of a tube wound or wound by filaments comprising filaments joined by a phenolic siloxane composition prepared according to the principles of this invention; Figure 2 is an isometric view of a strand of steel tube reinforced with filaments, bonded with a phenolic siloxane composition prepared according to the principles of this invention; Figure 3 is a cross-sectional elevation view of a wood composite board comprising a binder of the phenolic siloxane composition prepared according to the principles of this invention; "" • Figure 4 is an isometric view of a piece of foam comprising a phenolic siloxane composition prepared according to the principles of this invention; Figure 5a is an isometric view of a brake liner or coating comprising a phenolic siloxane composition prepared according to the principles of this invention; Figure 5b is an isometric view of a liner or liner for clutch comprising a phenolic siloxane composition prepared according to the principles of this invention; Y Figure 6 is an isometric view of an abrasive wheel comprising a binder of phenolic siloxane composition, prepared according to the principles of this invention.

Detailed Description The phenolic siloxane compositions of this invention are prepared, generally speaking, by the preparation of an ingredient comprising phenol with a sufficient amount of silicone intermediate, and can be prepared in a number of different ways. One such way is by combining phenol with an aldehyde and a silicone intermediate. Another such way is to combine a phenolic novolak resin, already prepared by the reaction of phenol and an aldehyde, with a formaldehyde donor and a silicone intermediate. And another such way to combine a phenolic resole resin, already prepared by the reaction of the phenol, and an aldehyde, with a silicone intermediate. The phenolic siloxane compositions of this invention have improved flexibility properties, and impact strength in the cured composition when compared to conventional phenolic compositions that do not contain siloxane. The phenolic siloxane compositions of this invention can be optionally prepared by using: (1) catalysts to reduce the reaction times and decrease the reaction temperature associated with the formation of a phenolic siloxane composition; (2) additives and modifiers to improve properties such as flow, flexibility, and the like; and (3) the use of pigments and / or fillers to provide a desired color and / or consistency The phenolic siloxane compositions formed, according to the principles of this invention, comprise an interpenetrating polymer network (IPN). IPNs of this invention are composed of chemically dissimilar crosslinking polymer chains, namely, siloxane polymer chains and phenolic polymer chains, which have substantially no chemical linkage between them.The polymer chains of siloxane and phenolic are held together by entanglements of permanent chain It should be understood that the IPNs of this invention do not include compositions having solid particles or solid particles trapped in a liquid or polymeric phase, such as silicon or siloxane particles trapped in a phenolic polymer phase. of the compositions prepared according to the principles of this invention is that the phenolic polymer chain of the IPN includes the siloxane group in its backbone. The siloxane groups are in the uncured prepolymer, when they are prepared in the original synthesis of the phenolic siloxane, for example, which are formed from the combination of the phenol and the aldehyde, and are in the crosslinked polymer, for example, e? - Phenolic and phenolic novolac, in any case. The siloxane groups are in the backbone of the phenolic polymer and do not appear as side groups. It is believed that these groups contribute to the increased flexibility of the phenolic polymer, and make the siloxane-containing phenolic polymer more impact resistant and more flexible than an unmodified phenolic polymer composition, without sacrificing chemical resistance and heat resistance. In a first embodiment, a phenolic siloxane composition is prepared by the combination of phenol or substituted phenol., with an aldehyde and a silicone intermediate. Although phenol is a preferred starting material, substituted phenols such as ortho-cresols, meta-cresols, para-cresols, xylene, nonylphenol, styrene phenols, bromo-phenols, catechol, para-tert-butyl can also be used. -phenol, para-octyphenol, para-nonylphenol, paraphenylphenol, bisphenol A, resocinol, and cashew nut shell liquid, and mixtures of the mimes. The lesson of the use of the phenol or a substituted phenol as the starting material may depend on the economic interests and the availability of the chemical materials, the manufacturing process, or may depend on the properties * desired for the resulting composition. With respect to the aldehyde ingredient, formaldehyde is particularly preferred. Such aldehyde and aldehyde donors other than formaldehyde, which may be combined with the phenol, or substituted phenol, to prepare the phenolic siloxane composition include acetaldehyde, paraldehyde, glyoxal, hexamethylene tetraamine, and furfural. The amount of aldehyde ingredient that is combined with the phenol determines the type of phenolic resin and will be formed by the combination, for example, of whether a phenolic resole siloxane composition or a phenolic novolac siloxane composition will be formed. If a phenolic resole or phenolic novolak is desired, this may depend on the particular properties desired for the phenolic siloxane composition. When the phenol ingredient is combined with a molar excess of aldehyde and a silicone intermediate, the resulting reaction produces a phenolic resole siloxane composition. When the phenol ingredient is combined with a deficient aldehyde molar, the resulting reaction produces a phenolic novolac siloxane composition. With respect to the silicone intermediate, silicone intermediates with alkoxy functional group and silanol functional group can be used to form the compositions of this invention. The silicone intermediates as referred to in this invention are chemical polymeric structures having a backbone -Si-O-, and which are capable of undergoing further reaction, for example, hydrolysis and / or condensation to form a cured polymer structure. A preferred class of siiicor.a intermediary has the formula wherein each R 2 is independently selected from the group consisting of the hydroxyl group, the alkyl, aryl, aryloxy, and alkoxy groups having up to six carbon atoms, wherein each R x is independently selected from the group consisting of hydrogen, alkyl, and aryl groups having up to 12 carbon atoms, and where n is an integer group in the range of 56, selected such that the average molecular weight of the silicone intermediate is from about 150 to about 10,000. It is believed that the molecular weight of the selected silicone intermediate can have an impact on the degree to which an IPN of the phenolic polymer and the siioxane polymer is formed, and the proportion of the siloxane groups that are copolymerized with the phenolic polymer to form a continuous phase. Another group of silicone intermediates can be represented by a silicone material containing a hydroxyl (OH) - and includes those materials having the OH group or group directly coupled to the silicon atom, such as the silanol materials having the formulas general OH R5-Si -OH OH Y R5 R5 HO-Si -O-Si -OH R5 5 wherein each R5 group may comprise a hydrocarbon radical selected from the group including the alkyl, alkenyl, cycloalkyl, aryl, alkaryl or aralkyl radicals, and where neither may be an integer in the range of about one to thirty. Yet another group of silicone materials having OH, are materials that comprise two or more OH groups bonded to a silicon atom, having two or more silicon atoms bonded through divalent organic radicals such as those having the formula general ? « H0-S1 -R7-S ± -0H R € where each group R .; may comprise another OH group or may comprise a hydrocarbon radical selected from a group including the alkyl, cycloalkyl, aryl, alkaryl and alkylaryl radicals, wherein R7 may comprise a divalent organic radical selected from the group including methylene, polyethylene, araliene, polyarylene, cycloalkylene, and polycycloalkylene. Methoxy functional group silicone intermediates, useful in this invention, include but are not limited to: DC-3074, DC-3037 from Do Corning Corporation of Midland, Michigan; SY-231 (approximate molecular weight of 1000) and MSE-100 of Wacker Silicone Corporation; and SR-191 of General Electric. Silicone intermediates with silanol functional group are generally in the range of about 0.5% to 6% by weight of Si-OH. The commercially available silicone intermediates with functional silanol functional group, useful in this invention; include, but are not limited to: Diphenylsilandiol (approximate molecular weight of 216), Wacker Silicones SY-409 (approximate molecular weight 10,000) and SY-430; and the following Dow Corning materials: DC804, DC805, DC806A, DC840, Z-6018, DC-1-2530, DC-6-2230, DC-1-0409, DC-1-0410 and lamination resins 2103, 2104 and 2106.

A first preferred embodiment of a phenolic novolac siloxane composition is prepared by the combination of the phenol, or the substituted phenol, an aldehyde such as formaldehyde, and a silicone intermediate. Based on the weight of the charge of one mole of phenol, the weight of the formaldehyde will vary between 0.75 and 0.90 moles, and the weight of the silicone intermediate will vary between 0.01 and 0.3 moles. The molar ratio of phenol to formaldehyde in a phenolic novolac resin is typically 1: 0.75-0.90. Table 1 shows the typical molar ranges of the silicone intermediates, which have different molecular weights, used to prepare the phenolic novolac siloxane composition.

TABLE 1 TABLE 1 (continued) A first preferred embodiment of a phenolic resole siloxane composition is prepared by the combination of the phenol, or the substituted phenol, an aldehyde such as formaldehyde, and a silicone intermediate. Based on the weight of the charge of one mole of phenol, the weight of the formaldehyde will vary between 1 and 3 moles, and the weight of the silicone intermediate will vary between 0.01 and 0.7 moles. The molar ratio of the phenol to formaldehyde in a phenolic resole resin is typically from 1: 1 to 1: 3. Table 2 shows the typical ranges of the silicone intermediates having different molecular weights, used to prepare the siloxane composition of phenolic resol.

TABLE 2 For each of the above-described embodiments the composition of phenolic novolak and phenolic resole siloxane *, it is desired that a range of about 0.5 to 35 weight percent of the silicone intermediate be used. The first embodiments of the phenolic siloxane composition comprising less than about 0.5 weight percent of the silicone intermediate, can form a composition having good heat, fire and chemical resistance properties, but may have physical properties of reduced flexibility and increased brittleness, when compared to a composition comprising from about 0.5 to 35 weight percent silicone intermediate. The first embodiments of the phenolic siloxane composition comprising more than about 35 weight percent of the silicone intermediate, can form a composition having reduced strength properties to heat, flame and chemicals, but improved flexibility and reduced brittleness when compared to a composition comprising from about 0.5 to 35 weight percent of the silicone intermediate. In preparing the first embodiments of the phenolic siloxane composition, catalysts are used to form either a phenolic novolak prepolymer of desired phenolic resole resin. For example, when the phenolic novolac siloxane composition is formed, a strong acid such as sulfuric acid, sulfonic acid, oxalic acid, or phosphoric acid is used to facilitate the formation of phenolic novolac resin prepolymer. When the phenolic resole siloxane composition is formed, a strong base such as sodium hydroxide, calcium hydroxide, or barium hydroxide is used to facilitate the formation of phenolic resole prepolymer. In the first preferred embodiments, a phenolic novolac siloxane preparation is prepared by use of up to about five percent by weight of acid catalyst, and a phenolic resole siloxane composition is prepared by using about five percent by weight of base catalyst. Catalysts other than, and in addition to those described above may optionally be used in preparation of the first embodiments of the phenolic siloxane composition, to facilitate the condensation of the phenolic resin and the silicone intermediate, by reducing the time and / or of the temperature associated with such reactions. The catalysts useful for facilitating the condensation of the phenolic resin and the silicone intermediate are the same, and "can be used in the same proportion, as those described below, which can optionally be used for the preparation of the second and third modalities. of the phenolic siloxane composition, for example, the phenolic siloxane compositions formed from the initial compositions comprising phenolic novolac resins and phenolic resole resins, respectively The first embodiments of phenolic resole and novolac siloxane compositions The phenolics are first prepared by the combination of the intermediate ingredients phenol and silicone, and then the aldehyde ingredient is added to form an IPN of phenolic polymers, siloxane polymers, and phenolic siloxane polymers, for example, phenolic polymers having Si- group. 0 or in the backbone of the pol phenolic groupers The combination of phenol with the silicone intermediate, before the addition of the aldehyde ingredient, is a key step in the preparation of the first modalities of the composition, because this ensures a desired degree of reaction between the silanol groups of the silicone intermediate and the hydroxyl groups of the phenolic ingredient. As discussed below, the condensation reactions between the silanol groups and the hydroxyl groups of the phenolic ingredient are desired because this introduces Si-0 groups into the phenolic polymer, thereby providing improved properties of impact resistance and stiffness in the cured composition. After the aldehyde is added, the silanol groups react with the phenolic and / or methylol-hydroxyl groups of the newly formed novolak or phenolic resole, for example, the novolac resin or low molecular weight phenolic resole, introducing further groups Si-0 within the phenolic resin to provide the improved properties described above. After the ingredients are combined, the temperature of the combined mixture is elevated to reduce the reaction times associated with the formation of the phenolic siloxane composition. For example, a first embodiment of the phenolic novolac siloxane composition can be prepared by a batch process, using a lined, stainless steel reaction vessel equipped with a turbine blade or anchor type stirrer, a steam condenser , and a temperature controller. Typically, a molten phenol is charged to the reaction vessel, the agitator is stripped and the silicone intermediate is added. An acid catalyst can be added after the silicone intermediate to facilitate the formation of the phenolic novolac polymer. Then formalin (37-40 percent aqueous formaldehyde) is charged to the reaction vessel, either before raising the temperature, or by controlled addition at elevated temperature. Then comes the vigorous condensation reaction, which is highly exothermic. The condensation step is continued until the desired molecular weight distribution has been reached. During this time the mixture can become two phases with the separation of the resinous component. The effective reaction time will vary depending on the desired molecular distribution, the use of one or more catalysts, the pH, and the molar proportions of the aldehyde to the phenol to the silicone intermediate. The ingredients are mixed together, during which time the phenol and silicone intermediates react as described above, the phenol and the aldehyde react to form a phenolic novolac or resole and the silicone intermediate undergo polycondensation, which polycondensation may optionally be accelerated by the action of a catalyst, as described below. During this time, any silicone intermediates with alkoxy functional group are hydrolyzed to form silicone intermediates with silanol functional group, both of which undergo both homopolymerization to form a siloxane polymer and copolymerize with the phenol and the phenolic hydroxyls of the resin prepolymer. Newly formed phenolic novolak, to introduce the Si-0 groups within its spinal column. Accordingly, the resulting composition comprising a phenolic novolac polymer IPN and the siloxane polymer, and a continuous phase formed from the phenolic polymer having one or more siloxane groups in its backbone. The hydrolysis of the silicone intermediates with alkoxy functional group can be optionally accelerated by the action of a catalyst, as described below. Alternatively, silicone intermediates with a silanol functional group can be used in the process, which can be copolymerized directly with the phenol and the newly formed phenolic novolak resin prepolymer without hydrolysis. At the end of the condensation period, water, residual moisture, unreacted phenol and low molecular weight species can be removed by atmospheric, vacuum or steam distillation. It is important to note that the distillation step is carried out after the occurrence of the condensation reactions between the silanol groups of the silicone intermediate and the phenolic hydroxyl groups, and the hydroxyl groups of the phenolic resin and not before, as it is desired the presence of substantial amounts of the silanol groups in conjunction with the phenol and the newly formed phenolic resin. The point at which the distillation is stopped is usually determined by taking a sample of the resin and measuring its melt viscosity. After the resin has cooled, this can be treated in several ways. This can be sold as lumps or flakes, compounded to form molding powders, or it can be crushed and mixed with hexamine and other fillers. As yet another example, a first embodiment of the phenolic resole siloxane composition can be prepared by a batch process using the same equipment previously described for the preparation of a first embodiment of the phenolic novolac siloxane composition. Typically, the molten phenol is charged to the reaction vessel, the agitator is started and added to the silicone intermediate. Alkaline catalysts can be added after the addition of the silicone intermediate, to facilitate the formation of the phenolic resole polymer. Formalin is added and the batch is heated. The initial reaction is exothermic. The condensation is usually carried out at atmospheric pressure and at temperatures in the range of 60 to 100 ° C or at reflux. Because the phenolic resole siloxane compositions are themselves thermosetting, the dehydration is carried out rapidly and at low temperatures, to prevent overreaction or gelation. The final point is found by manually determining a specific gelling time in hot plate, which decreases as the resinification progresses. The phenolic resole siloxane compositions can be chilled to prolong their storage stability. The second and third embodiments of a phenolic novolak resin and a phenolic resole siloxane composition are prepared by the use of a phenolic novolak resin and a phenolic resole resin, respectively, as starting materials. Any type of phenolic resin can be used to prepare the phenolic siloxane compositions of this invention, and ultimately it is selected based on the intended end use application. Suitable phenolic resins may include those based on phenol, substituted phenols such as para-pot, xylene, bisphenol A, paraphenylphenol, para-tert-butylphenol, para-t-octylphenol and resorcinol. The phenolic resin can be prepared by combining an appropriate phenol with an aldehyde, such as those previously described in the first embodiment. The fundamental synthesis reaction of the phenolic resins can proceed in one of two ways, depending on the proportions of the two primary reactants, for example, phenol and aldehyde, depending on the pH or the mixture. As discussed above, phenolic resins prepared by the combination of a phenol and aldehyde are generally classified into one of two classes, phenolic novolak resin or phenolic resole resins. Phenolic novolac resins are thermoplastic materials and are made by heating phenol with a deficiency- to formaldehyde (usually a formalin) in the presence of an acid catalyst (often oxalic acid or sulfuric acid). It is desired that the molar ratio of formaldehyde / phenol (F / P) is less than one, otherwise crosslinking and gelation will occur during manufacture. The reaction is strongly exothermic. The reaction that forms the phenolic novolac resin can be represented as shown below.

H + H20 Resin Novolaca The reaction proceeds firstly by the formation of the phenolic alcohols and secondly the condensation of the phenolic alcohols, which occurs rapidly with excess phenol to form relatively short chain phenolic polymers, for example, comprising from two to ten phenolic rings , in which the phenolic rings are linked together by methylene groups. Phenolic novolacs are thermoplastic resins, comprise few methylol functional groups, have molecular weights in the range of about 125 to 5000, and show glass transition temperatures in the range of 45 ° C to 100 ° C. The phenolic novolacs do not further condense by themselves, unless additional formaldehyde or other reactive materials are added, for example, formaldehyde donors such as hexamethylenetetramine. Although most of the crosslinks in the phenolic novolac are methylene bridges, benzylamine structures have also been identified. Phenolic resole resins are thermosetting resins, often referred to as single-stage resins. These are prepared by heating phenol with formaldehyde (usually as formalin) using an alkaline catalyst (usually caustic soda for water-soluble resins and ammonia or an amine for electric-grade lamination resins). The molar ratio of formaldehyde to phenol (F / P) is greater than one. The phenolic resole formation reaction is depicted as shown below.

During the reaction, the methylolation of the phenol occurs, with little condensation. The resulting phenol alcohols can be condensed together under these conditions, to give polymers with ether bridges as well as with ethylene bridges between the phenolic rings. More importantly, the reaction produces phenolic polymers that also possess many outstanding methylol groups. Depending on the type of phenolic raw material, and the degree to which the reactions are allowed to proceed, the roles can cover a broad spectrum of possible structures, and can be solid or liquid, soluble or insoluble in water, alkaline or neutral, healing slow or highly reactive. Typical phenolic resoles have molecular weights in the range of about 150 to 2000.

The phenolic resols will condense by themselves with heat, to form a reticuized phenolic polymer, without the addition of any other curing agent. If desired, however, an acid catalyst can be used to reduce the cure time. Suitable optional catalysts include inorganic acids such as phosphoric, sulfuric and hydrochloric acids, and organic acids, such as paratoluensulfuric and phenylsulphonic acids. Suitable organic and inorganic acids that release the active acid functional group, after heating, can also be used. If desired, the phenolic resoles can also be cured using an optional alkaline catalyst, such as suitable magnesium oxides and the like. Any phenolic resin, eg, novolak or phenolic resole, can be used to prepare the second and third embodiments, respectively, of the "phenolic siloxane compositions according to the principles of this invention." The particular novolak or phenolic resole that is selected , are based largely on the application of the final use, on the desired physical and chemical properties of the final product, and on the methods of application or processing techniques that will be used.

For example, in the preparation of a compound such as a glass reinforced structure using a filament winding or winding process, a low viscosity phenolic resole prepared from phenol and formaldehyde could be used, for optimum wetting of the glass and the high final content of the glass. Intermediate viscosity resoles could be used to make compositions by a molding process. The manufacture of a glass-reinforced composite by extrusion by stretching, requires the use of phenolic resole with a high level of sulfonic acid catalyst for very fast healing speeds. For example, in the design of a heat-cured coating, used to line the inside of a chemical storage tank, or to line the inside of cans and drums, a phenolic resole and resole substituted, reactive to heat could be used. Such resole can be used, often in combination with an epoxy resin, for optimum resistance to chemicals and corrosion. For example, metal curative heaters can be prepared at room temperature from a phenolic resole and an inorganic (eg, phosphoric, sulfuric or hydrochloric) or organic (paratoluenesulfonic or phenylsulfonic) combined immediately before application. For example, the phenolic resins which are used to make the molding compounds are mainly novolaks which are combined with 5 to 15% hexamethylene stearate as a curing agent. These materials are glass fiber composites, mineral extenders, rubber modifiers, etc., in a pulverized form or in microspheres, which are used to manufacture various articles through compression, transfer, centrifugal molding and injection processes. The solid phenolic novolacs found most useful in this invention are prepared from any of the phenols and aldehydes previously described, and have molecular weights in the range of about 400 to 5000, with vitreous transition temperatures in the range of about 40 ° C. at 90 ° C. The phenol resins found most useful in this invention have molecular weights in the range of about 300 to 3000, solid contents of 50 to 90% by weight, and may contain from 2 to 20% by weight of free phenol or substituted phenol, and from 1 to 10% by weight of water.

Manufacturers of the appropriate phenolic resins include: B.P. Chemical Division of British Petroleum of Barry United Kingdom; the Packaging and Industrial Products Division of Borden, Inc., of Columbus, Ohio; the Durez Division of Occidental Pretoleum of Dallas, Texas; Georgia-Pacific Corporation of Atlanta, Georgia; Neste Resins Corporation of Eugene, Oregon, as well as a number of other small producers. Some preferred phenolic resins include Cellobond J2018L and J2027L, from B.P. Chemical, the SL-898 phenolic resole from Borden, and the Georgia-Pacific's GP5018 phenolic resole. A second embodiment of the phenolic siloxane composition, prepared according to the principles of this invention, comprises more about 50 percent, of the phenolic novolak resin, and preferably comprises in the range of about 50 to 95 percent by weight of the resin phenolic novolac A third embodiment of the phenolic siloxane composition comprises more than about 65 percent by weight of the phenolic resole resin, and preferably in the range of from about 65 to 99.5 percent by weight. A phenolic siloxane composition comprising at least about 50 percent by weight of the phenolic novolak resin, or less than about 65 percent by weight of phenolic resole resin, can form a composition having reduced heat resistance properties, the flame and the chemical products, when compared with a composition that comprises the preferred percentage range of the particular phenolic resin. A composition comprising more than about 95 percent by weight of the phenolic novolak resin, or more than about 99.5 percent by weight of the phenolic resole resin, will form a composition having a resistance to heat, flame and chemicals , but having reduced flexibility, and increased brittleness when compared to a phenolic siloxane composition comprising the preferred percentage range of the particular phenolic resin. With respect to the silicone intermediate, those silicone intermediates previously described for the preparation of the first embodiments of the phenolic siloxane composition are also used to prepare the second and third embodiments of the phenolic siloxane compositions. The second and third embodiments of a phenolic siloxane composition may each comprise in the range of 0.5 to 35 weight percent of the silicone intermediate with alkoxy functional group or silanol functional group. In the second embodiment, a phenolic novolac siloxane composition is prepared by combining a phenolic novolak resin with a formaldehyde donor and a silicone intermediate. Formaldehyde donors include solutions of aqueous formaldehyde, paraform, trioxane, hexamethylenetetramine and the like, a preferred material is hexamethylenetetramine. A second embodiment of the phenolic novolac siloxane composition may comprise in the range of about 3 to 15 weight percent of the formaldehyde donor. A phenolic novolac siloxane composition, containing at least about 3 percent by weight of the formaldehyde donor can form a composition having a low degree of crosslinking, and having a slow cure time when compared to a composition comprising in the range of 3 to 15 percent of the formaldehyde donor and, therefore, can show physical properties of reduced resistance to heat, flame and chemicals. A phenolic novolac siloxane composition comprising more than about 15 percent by weight of the formaldehyde donor, can formulate a composition having a high degree of crosslinking and having a faster cure time, when compared to a composition comprising in the range of about 3 to 15 weight percent of the formaldehyde donor, thus making the work of making and applying the composition difficult to form structures and / or coatings. In the third embodiment, a phenolic resole siloxane composition is prepared by combining a phenolic resole resin with a silicone intermediate. If desired, an acid or alkaline catalyst can optionally be used to reduce the reaction time associated with the final cure of the resin. Suitable inorganic acid catalysts which may be optionally used in the third embodiment include phosphoric, hydrochloric- and * sulfuric acids. Suitable organic acids which may be optionally used in the third embodiment include paratoluenesulfonic and phenylsulfonic acids. Suitable alkaline catalysts for curing the phenolic resins include various forms of barium and magnesium oxide, and the like. Suitable commercially available acid type catalysts are also useful in this invention, are available from British Petroleum Chemicals under the tradename Phencat 381 and Phencat 382. Other suitable catalysts include Borden RC-901, a phosphoric acid diphenyl ester supplying Dover Corp ., which has the product name Doverphos 231L, and GP3839 and GP308D50 from Georgia-Pacific. A third embodiment of the phenolic resole siloxane composition may comprise up to about 15 percent by weight of the optional acidic or basic catalyst, or the curing agent. A phenolic resole siloxane composition comprising more than about 15 percent by weight of the acidic or basic catalyst can form a composition having a high degree of crosslinking and fast curing time, when compared to a composition prepared without the catalyst or using less than 15 percent by weight of acid or basic catalyst, in this way, it becomes difficult to work and apply the composition to form structures and / or coatings. If desired, the second embodiment may optionally comprise up to about 15 percent of the optional acidic or basic catalyst to further reduce the cure time.

If desired, the first, second and third embodiments of phenolic siloxane compositions may each optionally comprise a sufficient amount of catalyst to reduce the reaction time and reduce the reaction temperatures associated with the condensation of the silicone intermediate and copolymerize it with the Phenolic polymer during the formation of the phenolic siloxane composition. It is understood that the use of such a catalyst is optional and is not required to prepare the first, second and third embodiments of the phenolic siloxane compositions according to the principles of this invention, since a reduction in reaction times may alternatively be achieved. without such a catalyst, by the use of elevated reaction temperatures. Suitable catalysts are selected from the group consisting of organometallic compounds, amine compounds and mixtures thereof. Compositions of an organometallic compound with an amine compound are preferred when desired to catalyze the hydrolysis and condensation of the silicone intermediate. Useful organometallic compounds include metal driers well known in the paint industry, such as octoate, neodecanes and zinc, manganese, cobalt, iron, lead and tin naphthenates, and the like. Organotitanates such as butyl titanate and the like are also useful in the present invention. A preferred class of organometallic compounds useful as a catalyst are organotin compounds which have the general formula R9-Sn-Rll where R ?, R ?, Rio and Ru are selected from the group consisting of the alkyl, aryl, aryloxy and alkoxy groups having up to 11 carbon atoms, and where any two of R8, R ?, Rio and Rn are additionally selected of a group that 'consists of inorganic atoms consisting of halogen, sulfur and oxygen. Organotin compounds useful as catalysts include tetramethyltin, tetrabutyltin, tetraoctyltin, tributyltin chloride, tribultyltin methacrylate, dibutyltin dichloride, dibutyltin oxide, dibutyltin sulfide, dibutyltin acetate, dibutyltin dilaurate, dibutyltin maleate polymer, dimeryl mercapto dibutyltin, tin octoate, dibutyltin bis- (isooctylthioglycolate), butyltin trichloride, butyltonic acid, dioctyltin dichloride, dioctyltin oxide, dioctyltin dilaurate, dioctyltin oxide, dioctyltin dilaurate, dioctyltin maleate polymer, bis- ( dioctyltin isooctylthioglycolate), dioctyltin sulphide, and dibutyltin 3-mercaptopropionate. The first, second and third embodiments of the phenolic siloxane composition may comprise up to about five percent by weight of the organometallic catalyst. A phenolic siloxane composition comprising more than about five percent by weight of the organometallic compound can form a composition having a high degree of flexibility when compared to a composition formed without the catalyst or comprising less than about five percent. by weight of the organometallic compound, due to the increased hydrolysis and / or condensation reactions by the silicone intermediary In addition, a phenolic siloxane composition prepared without the organometallic catalyst may require a longer time and / or a higher temperature to achieve a reaction of desired condensation than for a phenolic siloxane composition with the organometallic compound With respect to the amine compound, the preferred amine compounds for optionally catalyzing the hydrolysis and / or the condensation reactions of the silicone intermediate have the general formula Rl2 ~ N ~ Rl4 Rl3 where R? and R? each is selected from the group consisting of hydrogen, aryl, and alkyl having up to 12 carbon atoms, and wherein Ri is selected from the group consisting of alkyl, aryl and hydroxyalkyl having up to 12 carbon atoms. Suitable amine compounds, useful as catalysts, include dimethyl methanolamine, ethylaminoethanol, dimethyl ethanolamine, dimethyl propanolamine, dimethyl butanolamine, dimethyl pentanolamine, dimethyl hexanolamine, methylethyl methanolamine, methylpropyl methanolamine, methylethyl ethanolamine, methylethyl. -prcpanolamine, monoisopropanolamine, methyldiethanolamine, triethanolamine, diethanolamine, and ethanolamine. Preferred amine compounds include dimethylethanolamine and ethyl-aminoethanol. If desired, the organometallic compound and the amine compound can each be used independently to form a phenolic siloxane composition. However, it has been found that when combined, the organometallic compound and the amine compound act synergistically to catalyze the curing process, thereby reducing the curing time in addition and / or the reaction temperatures higher than those observed by the use of either the organometallic or amine catalyst alone. Accordingly, if desired under the circumstances, it is preferred that an organometallic compound be used in combination with an amine compound to catalyze the formation of hydroxide by hydrolysis of the silicone intermediate, in the case that a silicone intermediate is used with the alkoxy functional group, and polymerization with the condensation of the silicone intermediate with alkoxy and silanol functional group. An exemplary combination of the organometallic compound and the amine compound is dibutyltin diacetate and ethyl-aminoethanol. The dibutyltin diacetate, when combined with the amine, reacts synergistically to catalyze the healing process. Although it is believed that the synergistic effect of the organotin compound and the amine compound is mechanical in nature, the exact mechanism is unknown. An unexpected effect of the combination of an organometallic compound and the amine compound for preparing the phenolic siloxane compositions of this invention is an improvement in processing capacity. Compositions of the phenolic resole / latent acid catalyst siloxane type, prepared by the use of an organometallic catalyst and amine, show increased container lives and comparable or decreased cure times when compared to the non-organometallic / amino non-catalyzed compositions. The increase in the level of latent acid catalyst which, during the preparation of such compositions, has in fact resulted in fendica resin compositions with cure times comparable to the linear phenolic resole / latent acid catalyst systems, but with life in containers significantly longer. The exact mechanism for unexpected improvement in the processability of the resulting composition is unknown, but it is believed to be related to the neutralization of the latent acid catalyst by the amine compound. The first, second and third embodiments of the phenolic siloxane composition can comprise up to about five percent by weight of the amine catalyst. A phenolic siloxane composition comprising more than about five percent by weight of the amine compound can form a composition having a greater degree of flexibility when compared to a composition prepared without the use of an amine compound or using less than five percent by weight of the amine compound, due to the hydrolysis and / or increased condensation of the silicone intermediate. In addition, a phenolic siloxane composition prepared without the amine catalyst may require more time and / or higher temperature to achieve the desired condensation reaction than for a phenolic siloxane composition with the amine catalyst. A "preferred composition of the organometallic compound to the amine compound, when used together as the catalyst, it is approximately one to one. Therefore, the first, second and third phenolic siloxane compositions can comprise up to about 10 weight percent of the combined organometallic catalyst and amine. Accordingly, a combination of phenolic siloxane prepared by the combination of an organometallic amine catalyst, and an optional acidic or basic catalyst, may comprise up to about 25 weight percent catalyst. The first, second and third preferred phenolic siloxane compositions may comprise the catalyst in the range of 5 to 25 percent of the total composition. Water may be present in the form of an aqueous phenolic resole or in the form of an aqueous formaldehyde. For example, the phenolic resole may comprise in the range of 3 to 12 weight percent water, and the formaldehyde may comprise formalin, which is aqueous formaldehyde of about 37-40 percent. When a silicone intermediate, with alkoxy functional group is used to prepare the compositions, it is desired that the water promotes the hydrolysis of the alkoxy groups. This water may be present in the phenolic composition or absorbed from the air by processing. However, it is understood that phenolic siloxane compositions, prepared according to the principles of this invention, can be prepared without added water, or in the absence of any type of solvent. A non-aqueous phenolic resole or phenolic novolak, for example, a phenolic resole that does not comprise added water, can be used in the case that a silicone intermediate with a silanol functional group is used, instead of a silicone intermediate, with a group functional alkoxy, to prepare the composition, since the hydrolysis of the silicone intermediate is not required. The first, second and third embodiments of the phenolic siloxane composition can result in the formation of phenolic resins having very low or zero water contents, when the improved characteristics of fire stability and processing are provided. The silicone intermediate functions as a reactive diluent to give a stable product with generally low viscosity. The second and third embodiments of the phenolic siloxane compositions are prepared by combining in the above-mentioned proportions a phenolic novolak or resin, with a silicone intermediate with methoxy or silanol functional group, the phenolic resin and the intermediate of silicones are held together for a desired period of time, for example, one hour to ensure that a sufficient degree of condensation reactions occur between the silanol groups and the silicone intermediate and the phenolic hydroxyl groups, whereby a desired amount is introduced of the Si-0 groups, for example the substitution of siloxane, within the phenolic resin. This is done before the copolymerization of the phenolic resin. A formaldehyde donor is added in the second modality. If desired the catalyst for the phenolic resin and the catalyst for the silicone intermediate, for example, the organometallic compound and the amine compound, can optionally be added to reduce the reaction and curing time and reduce the reaction temperature. The ingredients are mixed together until they are uniform, during which time the phenolic resin undergoes polycondensation to form a phenolic polymer, which polycondensation is aided by the formaldehyde donor in the second embodiment, and whose polycondensation can be optionally accelerated by the action of the catalyst, for example, an acid or a base, in the third embodiment. During this time, the silicone intermediates with alkoxy functional group continue to undergo hydrolysis, forming silicone intermediates with silanol functional group. The silicone intermediates with silanol functional group are both polymerized to form a siloxane polymer, for example, the polymeric siloxane chain of the IPN, and condense with the phenolic polymer to introduce additional Si-0 groups into the phenolic polymer. The hydrolysis of the silicone intermediates with alkoxy functional group can be optionally accelerated by catalytic action of the organometallic compound and the amine compound. Accordingly, the resulting composition comprises a phenolic polymer IPN and siloxane polymer wherein the phenolic polymer contains siloxane groups in its backbone. A phenolic siloxane composition prepared in this way can have a shelf life in the range of 1 to 3 hours, depending on the particular ingredients selected and their proportions. Alternatively, a phenolic siloxane composition according to the principles of this invention can be prepared as a three component system (added water absent) by combining, on the appropriate properties, the silicone intermediate and any optional organometallic compound and compound of Amine in a first container, which can be stored until just before use. The phenolic resin is stored in a second container, and the formaldehyde donor in the second embodiment and any optional catalyst for the phenolic resin can each be stored in separate third containers, which are combined with the mixture of the silicone intermediate in the first container, just before use, to form the composition. For example, in the construction of a glass filament phenolic tube, the components of each container can be combined using a metering mixing machine, in which the mixing is pumped or emptied into a holding tank through which passes the glass filament. While not wishing to be bound by any particular theory or mechanism, it is believed that the phenolic siloxane compositions of this invention are produced in the following manner. In the preparation of the first embodiment of the phenolic siloxane composition by the use of a phenol, aldehyde and a siliceous intermediate as the initial ingredients, the theory is launched that a phenolic resole or phenolic novolac can be formed according to the well-established principles described by PW Kopp, Phenol i c Resins, Encycl opedi a of Polymer Sci ence and Engineering, vol. 11, 2 * ed., Pages. 45-95 (1988), which is incorporated by reference herein. In the preparation of a first modality, the theory is postulated that the silanol groups coming from the silicone intermediate react with the phenolic hydroxyl groups, when the two ingredients are combined, with which Si-0 groups are introduced into the phenol ingredient. . After the aldehyde ingredient is added to the mixture, the silanol groups continue to react with the phenolic hydroxyl groups and / or the phenolic methylol hydroxyl groups of the newly formed, for example, low molecular weight phenolic resin. Because the silanol groups are present during the homopolymerization of the phenolic resin, they continue to react with the phenolic and / or hydroxyl hydroxyl groups of methylol, thereby continuing to introduce Si-0 groups into the phenolic resin. The silanol groups of the silicone intermediate also react with the silanol group of other silicone intermediates, forming a siloxane polymer. The mechanism by which such reactions are believed to occur is similar to those mechanisms discussed later and illustrated in reactions 1-6. However, it should be understood that reaction mechanisms different from those described and illustrated specifically, may be responsible for the introduction into the phenolic polymer of the first mode. In addition, the theory is postulated that other reaction mechanisms of such type can produce phenolic siloxane structures different from those specifically described and illustrated. In the formation of a third embodiment of a phenolic resole siloxane composition, using an acidic or basic catalyst, to cure the phenolic resole, the phenolic resole undergoes polymerization with other phenolic resole to form a cured phenolic resole as illustrated below in reaction No. 1.

REACTION # i ACID OR BASE H? 0 In the formation of a second embodiment of the phenolic novolac siloxane composition, the phenolic novolacs undergo polymerization with other phenolic novolacs and formaldehyde, or a formaldehyde donor, to form a cured phenolic novolac as illustrated below in reaction No. 2. It is believed that most of the bridges between the phenol groups are methylene, but the benzylamine structures have also been identified.

REACTION # 2 The exact mechanism of the addition of formaldehyde to the phenol group of the phenolic novolak and the subsequent polymerization, however, is not yet clearly understood. If a silicone intermediate with alkoxy functional group in combination with a phenolic novolak or resole and an optional organometallic / amine catalyst is used to prepare the second and third embodiments of the composition, respectively, the hydrolysis of the silicone intermediate to form an intermediate of silicone with functional group silanol and an alcohol is believed to occur first as illustrated in reaction No. 3 below.

R2 -. { - CH3 + Amine + organometallic + H20 OCH3 The silanol groups of the silicone intermediate with alkoxy functional group, hydrolyzed, or the silicone intermediate with silanol functional group, can react with the phenolic prepolymer according to many different mechanisms. In one mechanism the silanol groups undergo condensation reactions with the phenolic hydroxyls of the cured phenolic resins, to introduce Si-0 group into the phenolic polymer, as illustrated in reaction No. 4 below.

Reaction # 4 The silanol group of the silanol functional group silicone intermediate can also react with the phenolic methylol hydroxyl groups to introduce Si-0 groups within the phenolic polymer, as illustrated in Reaction No. 5 below.

Reaction # 5 The condensation reactions of the silicone intermediate with the phenolic resin prepolymer illustrated in reactions Nos. 4 and 5, are believed to be responsible for the improved properties of impact resistance, tensile strength, and flexural modulus displaced by the phenolic siloxane composition. The silanol groups of the silicone intermediate also undergo condensation with the silanol groups of other silicone intermediates to form a siloxane prepolymer. The siloxane prepolymer may undergo condensation reactions with the phenolic prepolymer, as discussed above, or may undergo polycondensation reactions with the siloxane prepolymers to form a cross-linked polysiloxane network, as shown in reaction No. 6 below.

Reaction # 6 na + H20 - I I Yes Si- OH I o or I I I I I * 1- Yes Si- Si - 1 I I OH Accordingly, the phenolic siloxane compositions of this invention comprising an IPN consisting of siloxane polymer, phenolic polymer, wherein the phenolic polymer "has Si-0 groups in its backbone." The siloxane polymers of the composition can also In addition, the crosslinking may also take place to some degree between the phenolic polymers and / or between the phenolic polymers and the siloxane.

It is believed that the improved properties of impact resistance and flexibility of the phenolic siloxane compositions are due to: (1) the presence of siloxane as a linear polymer, forming an IPN of siloxane polymers and phenolic polymers; (2) the presence of siloxane as a copolymer in the phenolic polymer; and (3) the presence of siloxane polymer in a crosslinked form. The characteristics and advantages of the phenolic siloxane compositions prepared according to the principles of this invention are better understood with reference to the following examples. Table 3 lists the ingredients that were used to form glass reinforced tubes with 50 mm (2 inches) of internal diameter that were prepared using a conventional filament winding or coiling process from an unmodified phenolic resole resin. (Example 1), and from a third embodiment of a phenolic resole siloxane composition (Examples 2 and 3). Table 4 summarizes the proven properties for each of the tubes identified as Example 1, 2 and 3 in Table 3.

Table 3 TABLE 4 Example 1 An unmodified phenolic tube was prepared by combining BP Cellobond J2027L (phenolic resole) with Phencat 381 (latent acid catalyst). Example 2 A phenolic tube was formed from a phenolic resole siloxane composition according to a third embodiment of this invention, prepared using the same phenolic resole and the latent acid catalyst that is used in example 1, with the addition of 15 percent. by weight DC-3074 (a silicone intermediate with functional group of Dow Corning with an average molecular weight of 1400 and a methoxy content of 15-25 percent), four percent by weight of dibutyltin diacetate (organometallic silicone intermediate catalyst) , and four percent by weight of ethylamino-ethanol (intermediate silicone amine catalyst). The ingredients were combined and blended together by conventional means to form a homogeneous mixture.

Example 3 A phenolic tube was prepared in the same manner as in Example 2, with the exception that prehydrolyzed DC-3074 was used in place of the non-prehydrolyzed DC-3074. Prehydrolyzed DC-3074 was prepared by charging 3640 grams of DC-3074, 153.4 grams of deionized water, 153.4 grams of methanol, 220 grams of xylene and 16.25 grams of glacial acetic acid to a 5000 milliliter round bottom flask equipped with a heating mantle, stirrer and condenser. The mixture was heated to reflux and remained so for approximately two hours. The flask was then equipped with a distillation head and receiver, and the distillate was collected until the temperature of the vessel reached 150 ° C (300 ° F). The resulting product, prehydrolyzed DC-3074, was a viscous, slightly turbid liquid. Approximately 4000 grams of each phenolic siloxane composition was prepared and mixed in a 3,785 1 (one gallon) can and then transferred to a holding tank. The glass wick was passed through the phenolic siloxane composition and wound around a hollow steel mandrel on an alternating movement process tube machine, to the desired thickness. Each tube was then cured for approximately 30 minutes at 60-88 ° C (140-190 ° F) by passing a steam / water mixture through the hollow mandrel. The tube was then removed from the mandrel and post cured for approximately two hours at 120 ° C (250 ° F). The compositions of Examples 2 and 3, for example, the phenolic resole siloxane compositions, formed according to the modalities according to the third embodiment of this invention, each had a shelf life of approximately 2-1 / 2 hours, compared to the container life of about 1-1 / 2 hours for the unmodified phenolic resin composition of example 1. The glass reinforced tubes made from the phenolic siloxane compositions of examples 2 and 3 , also demonstrated short term burst pressure, significantly greater, circumferential tension and impact resistance than those of the glass reinforced tubes formed from the unmodified phenolic resin, of example 1. Specifically, the pipes manufactured according to Examples 2 and 3 illustrate the dramatic increase in impact resistance that can be achieved when siloxane compositions are used. of this invention, to make the tube, when compared to the conventional phenolic tube of example 1. In comparing these examples, it is observed that the impact resistance for the tubes of examples 2 and 3 was more than twice that of the tube of Example 1, demonstrating the benefits that result from the use of a sufficient amount of the silicone intermediate to form a phenolic composition according to the principles of this invention. In addition, the phenolic siloxane compositions of Examples 2 and 3 showed higher specific gravities than the composition of Example 1, indicating the formation of a composition having reduced foaming and reduced microporosity. The exact mechanism for this effect is not understood. However, it is believed that the silicone intermediate reacts with some of the water in the phenolic resole, before it volatilizes during the curing process to reduce the level of trapped water, thereby reducing the formation of microvoids. A reduced formation of microvoids results in the cured phenolic resole having an increased tensile strength and increased friction modulus, thereby contributing to increased impact resistance.

The reduced formation of microvoids also results in the production of a cured product having a reduced absorption of water. It is believed that the presence of the siloxane in the phenolic siloxane composition, in addition to providing improved impact strength and flexibility, can render the cured composition hydrophobic. A phenolic composition having reduced microvoids, and an associated reduction in water absorption, may be desirable for the manufacture of useful products in electrical insulation applications where exposure to water may occur. An example of such an application is for third rail cover compounds of electric trains, built according to Mil Spec M14G. No harmful effects on the fire resistance of the phenolic siloxane tube were observed. The three systems passed a jet flame test at 1000 ° C for five minutes, without burning. Accordingly, the phenolic siloxane compositions of this invention provide the above-modified advantages and improvements without and to the detriment of the flame, heat and chemical resistance inherent in the phenolic resin. These examples clearly indicate the advantages and improvements imparted by the phenolic siloxane compositions of the present invention. Table 5 summarizes the results of the chemical resistance tests on the castings that were formed from an unmodified phenolic resole, and from the third modalities of the phenolic resole siloxane compositions prepared according to the principles of this invention.

TABLE 5 TABLE 5 TABLE 5 Examples 4-6 In Example 4, casting has been formed from a composition comprising a conventional unmodified phenolic resole. Examples 5 and 6 are cast formed from a phenolic siloxane composition according to a third embodiment of this invention, using the same chemical ingredients as those previously described for examples 2 and 3. Each formulation was mixed in a plastic container at room temperature, and then emptied into a 30 x 2.5 cm (12 inch x 1 inch) steel mold at a height of approximately 8 mm (5/16 inch). The castings were cured at one hour at 65 ° C C (150 ° F), followed by five hours at 120 ° C (250 ° F).

Each emptying was then cured in 5 cm (two inch) lengths and allowed to cure for one month at 21 ° C (70 ° F) and at a relative humidity of 50 percent. Each length of five centimeters (two inches) of emptying was weighed on an analytical balance and immersed in the test chemical. After two weeks of immersion at the indicated temperature, the samples were removed, rinsed and dried for one hour at 120 ° C (250 ° F) before being reweighed. Surprisingly, the test results of examples 4, 5 and 6 show that the voids formed from the third embodiment of the phenolic resole siloxane composition show improved resistance to chemicals for organic and inorganic acids, alkali and alcohol , on that of the unmodified casting formed from the phenolic resole alone. The phenolic siloxane compositions prepared according to the principles of this invention show improved physical properties of flexibility, impact resistance, and flexural modulus without affecting the physical properties of resistance to heat, flame and chemicals, inherent in the phenolic resin. In addition, phenolic siloxane compositions prepared according to the principles of this invention have reduced microvoid formation and, therefore, densities closer to the theoretical density when compared to conventional phenolic resin compositions that do not contain siloxane, probably due to the reaction by the silicone intermediate with water in the phenolic resole, to reduce the amount of trapped water. The phenolic siloxane compositions prepared according to the principles of this invention, also show improved coating ability on substrates, or as an underlying substrate, when compared to phenolic resin compositions that do not contain siloxane. It is believed that the improved coating ability is due to the presence of the silanol groups in the composition, which provide an improved binding source for the composition when it is used either as a coating applied to a substrate, or as a substrate to support a coating. The phenolic siloxane compositions of this invention can be used in the same manner as conventional phenolic resins to form structures, for example, castings, coatings for example, coatings on glass reinforced pipe *, and the like.

Example 7 A first embodiment of the phenolic resole siloxane composition was prepared by charging about 385 grams of molten phenol to a 1000 ml three-necked round bottom flask equipped with a heating mantle. The flask was heated to approximately 52 ° C (125 ° F), and about 60.4 grams of SY-231 (silicone intermediate) and 7.7 grams of 50 percent sodium hydroxide were added with stirring. The combined ingredients were maintained at a temperature in the range of about 49 ° C to 54 ° C (120 ° F to 130 ° F) for approximately 60 minutes. Approximately 370 grams of 50 percent formaldehyde were added to the mixture, and the temperature was increased over a period of about 20 minutes from about 52 ° C to 87 ° C (126 ° F to 190 ° F) in about 20 minutes. The temperature was then adjusted and maintained at a temperature in the range of about 85 ° C to 90 ° C (185 ° F to 195 ° F) for a period of about 90 minutes. A vacuum of approximately 15 mmHg was applied to the mixture, at a temperature in the range of about 60 ° C to 93 ° C (140 ° F to 200 ° F), and the distillate was removed and collected over a period of 40 hours. minutes The phenolic resole siloxane composition formed in this manner had a Brookfield viscosity of about 28,000 centipoise at 25 ° C (77 ° F), a water content of between two and three percent by weight, a weight average molecular weight by gel permeation chromatography (GPC) of less than about 580.

Example A first embodiment of the phenolic novolac siloxane composition was prepared by charging approximately 517 grams of molten phenol to a 1000 ml three-necked round bottom flask equipped with a heating mantle. Approximately 61 grams of SY-231 (silicone intermediate) was added to the molten phenol and stirred for one hour at a temperature of about 65 ° C (150 ° F). Approximately 15 grams of oxalic acid was added to the mixture and stirred for five minutes. Molten formaldehyde (50 percent solution) was added to the mixture and the flask was heated to a temperature of about 96 ° C (205 ° F) in a period of 20 minutes.

The mixture was maintained at a temperature of about 96 ° C (205 ° F) for a period of five hours. A vacuum of approximately 10 mmHg was applied to the mixture. The distillate was removed and collected for a period of about two hours, causing the temperature to rise to approximately 176 ° C (350 ° F). The flask was cooled to a temperature of approximately 110 ° C (230 ° F), at which time the vacuum was released and the product discharged into an appropriate container. The phenolic novolac siloxane composition formed in this manner had a melt viscosity ICI at 130 ° C (266 ° F) (rotation 4105 to 12,000 sec "1) at about 3 Poises, a weight average molecular weight by GPC of about 3102, and number average molecular weight of about 1543. Phenolic siloxane compositions prepared according to the principles of this invention, can be used in the same manner as conventional phenolic resins to provide, in addition to the inherent fire resistance, heat resistance, resistance to chemicals, resistance to abrasion, and wear, improved properties of impact resistance, rigidity, flexural modulus, elasticity.

For example, the phenolic siloxane compositions of this invention can be used in the construction of composite materials. Compound materials are understood to refer to a multi-phase system or structure comprising a binder material and a reinforcing material, which combine to produce some structural and functional functions not present in any of the individual components. The phenolic siloxane composition can be used in part or totally as the binder in such a composite material, while the reinforcing materials may be in the forms of fibers, particles, metal strips, wood and the like which are attached to, or joined together by, the binder. The phenolic siloxane compositions of this invention can be used in the construction of composite materials such as fiber reinforced plastics, in the form of moldings, sections and the like used in the automotive, mass transit, building and construction industries, aerospace and defense, and mining and tunneling, to provide improved properties of flexibility, impact resistance and rigidity. Specific examples of such composite tubes 10 have reinforcing fibers or filaments, as illustrated in Figure 1. Such tubes can be formed from windings or winding of the filament formed from glass, Kevlar (aromatic polyamide), carbon, graphite or the like, or combinations thereof, as described in Examples 1-3, which are linked with a phenolic siloxane composition of this invention. As described above in Examples 1-3, the use of a phenolic siloxane composition of this invention, to form wound or wound tubes with filaments, provides improved circumferential tension and improved impact resistance on the tube formed from a resin. phenolic unmodified. The phenolic siloxane composition can also be used in the construction of steel tube 12 reinforced with filaments, such as that illustrated in Figure 2, which is formed from a combination of steel windings and filament windings attached with a composition of phenolic siloxane of this invention. As yet another example, the phenolic siloxane compositions of this invention can be used as a binder in construction board applications, such as the construction of the wood composite board 14, such as the particle board and wafer board plywood. / oriented fiberboard, as illustrated in Figure 3, to provide improved flexibility and improved resistance against moisture. As yet another example, the phenolic siloxane compositions of this invention can be used in the production of foam 16, as illustrated in Figure 4, to improve the elasticity and water resistance. Such foam can be made from the following four components: (1) the phenolic siloxane composition; (2) a blowing agent; (3) an agent / surfactant for the control of the cells; and (4) an acid hardener / catalyst. The surfactant is often incorporated into the resin, thereby reducing the number of ingredients to be mixed when all three are foamed. Chemically, the foaming process depends on an exothermic reaction between the phenolic siloxane composition and the acid hardener. The evolved heat boils off the volatile blowing agent (e.g., Freon or pentane) which has been supplied in the form of fine droplets within the phenolic siloxane composition. The phenolic siloxane composition is thus blown into a foam, which, upon termination of its completion, is cured in a rigid thermoset material. Such foams are used for insulation where fire retardation is also required, for example, in bulk transit cars, commercial aircraft, and the like. The foam made from a phenolic siloxane composition shows improved elasticity and flexibility, thereby facilitating the installation of the foam without breaking. As yet another example, the phenolic siloxane compositions of this invention can be used as a binder in the construction of compounds for friction materials, such as linings or brake lining 18, for brake shoes and supports and dampers for automobiles and similar, as illustrated in Figure 5a, and liners 20 for clutch, for the clutch discs used in automobiles and the like, as illustrated in Figure 5b. In such applications, the use of the phenolic siloxane compositions provide improved stiffness and improved impact strength. As yet another example, the phenolic siloxane compositions of this invention can be used with natural rubber and a wide range of synthetic rubber, to act as a rubber reinforcing agent in applications such as cement, adhesives, conveyor belts, hoses and footwear. The use of a phenolic siloxane composition improves flexibility and rigidity, and reduces the moisture content of such materials. As yet another example, the phenolic siloxane compositions of this invention can be used singly or mixed together with other materials to form precursors for paints, industrial coatings, paints and / or varnishes, which have properties of coating ability, flexibility, strength at reduced impact, rigidity and moisture content, improved when compared to phenolic resins that do not contain conventional siloxane. As yet another example, the phenolic siloxane compositions of this invention can be used as a binder in the production of felt insulation, such as cushioning for upholstery, mattress components, cushioning materials for packing or packaging material, and cushioning automotive, and thermal insulation, such as glass fibers and minerals. The use of a phenolic siloxane composition in such applications provides improved flexibility properties, thereby facilitating the installation of such insulation, without fear of breakage or significant change in fire retardancy.

As yet another example, the phenolic siloxane compositions of this invention can be used as binders in the manufacture of bonded abrasives, such as emery wheels 22, cutting wheels and the like, as used in Figure 6, and coated abrasives, such as abrasive papers, fabrics and discs. The use of a phenolic siloxane composition in such applications provides improved properties such as impact strength and stiffness. As yet another example, the phenolic siloxane compositions of this invention can be used as binders for high quality silica sands, in the manufacture of cores and molds to empty a number of metals. The use of a phenolic siloxane composition in such an application provides cores and molds having improved properties of stiffness, flexibility, impact resistance and reduced moisture content. For example, the phenolic siloxane compositions of this invention can be used in the manufacture of electrical laminates,. mechanical and decorative, comprising layers of substrates coated with the phenolic siloxane composition bound together by means of heat and pressure. The use of a phenolic siloxane composition in such an application provides physical properties of improved impact strength, improved flexibility and stiffness, and reduced moisture content. Although limited embodiments of the phenolic siloxane compositions have been described in the present, many modifications and variations will be apparent to those skilled in the art. Accordingly, it is understood that, within the scope of the appended claims, the phenolic siloxane compositions according to the principles of this invention may be prepared in a different manner as specifically described herein.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims (47)

1. A phenolic siloxane composition, characterized in that it comprises a phenolic polymer having Si-0 groups in the spinal column.

2. The phenolic siloxane composition according to claim 1, characterized in that the composition is free of solid particles containing silicon.

3. A phenolic siloxane composition, characterized in that it is prepared by the combination of: a phenolic compound selected from the group consisting of phenol, substituted phenol and mixtures thereof; with a silicone intermediate; an aldehyde; an acid or base; wherein the silicone intermediate is combined with at least one of the phenolic compounds and the aldehyde, and the other phenolic compound and the aldehyde is added thereafter to form a phenolic polymer having Si-0 groups in its backbone.

4. The phenolic siloxane composition according to claim 3, characterized in that it comprises in the range of 1 to 3 moles of aldehyde, and in the range of 0.01 to 0.7 moles of silicone intermediate per 1 mole of phenol.

5. The phenolic siloxane composition according to claim 3, characterized in that it comprises a sufficient amount of catalyst to facilitate the processing and curing of the composition at a temperature below about 100 ° C.

6. The phenolic siloxane composition according to claim 5, characterized in that the catalyst is selected from the group consisting of organometallic compounds, amine compounds, acids, bases, and mixtures thereof.

7. A composite material having a resin component, characterized in that it comprises a phenolic siloxane composition, prepared according to claim 3.

8. A phenolic siloxane composition, characterized in that it is prepared by combining: phenol with a silicone intermediate to form a mixture, and adding to the mixture: an aldehyde; an acid or base; a silicone intermediate; and a catalyst selected from the group consisting of organometallic compounds, amine compound, acids, bases and mixtures thereof; wherein the composition comprises a polymer network of interpenetration of the siloxane polymer and the phenolic polymer, and wherein the phenolic polymer has Si-0 groups in its backbone.

9. The composition according to claim 8, characterized in that the catalyst is a mixture of an organometallic compound, and an amine compound, and wherein the organometallic compound is an organotin compound having the formula Ri. where R ", R3, Rio and Rp are each selected from the group consisting of the alkyl, aryl, aryloxy, and alkoxy groups, having up to 11 carbon atoms, and wherein any two of R8, Rg, Rio and Ru are additionally selected from a group consisting of inorganic atoms consisting of halogen, sulfur and oxygen.

10. The composition according to claim 9, characterized in that the amine compound has the formula R12 ~ N-Ri4 113 where R 2 and 3 are each selected from the group consisting of hydrogen, aryl and alkyl groups having up to two carbon atoms, and where Ri 4 are selected from the group consisting of alkyl, aryl and hydroxyalkyl having up to 12 atoms of carbon.

11. A compound having a resin component, characterized in that it comprises the composition prepared according to claim 8.

12. A phenolic siloxane composition, characterized in that it is prepared by the combination of: a phenolic resole resin; a silicone intermediate; and a catalyst to facilitate the formation of a polymer network of interpenetration of the phenolic polymer and the siloxane polymer, wherein the phenolic polymer includes Si-0 groups in its backbone.

13. The composition according to claim 12, characterized in that it comprises more than 65 weight percent phenolic resole resin based on the total composition.

14. The composition according to claim 12, characterized in that it comprises silicone intermediate in the range of 0.5 to 35 percent by weight of the total composition.

15. The composition according to claim 12, characterized in that the catalyst is selected from the group consisting of organometallic compounds, amine compounds, acids, bases, and mixtures thereof.

16. The composition according to claim 15, characterized in that the catalyst is a mixture of an organometallic compound and an amine compound.

17. The composition according to claim 16, characterized in that the organometallic compound is an organotin compound having the formula R -N-R 10 III wherein R6, R ?, Rio and Rn are each selected from the group consisting of the alkyl, aryl, aryloxy, and alkoxy groups, having up to 11 carbon atoms, and where any two of Rs , R9, R10 and Ru are additionally selected from a group consisting of inorganic atoms consisting of -halogen, sulfur and oxygen.

18. The composition according to claim 16, characterized in that the amine compound has the formula R12-N-R14 Ris where R 2 and Ri 3 are each selected from the group consisting of hydrogen, the aryl and alkyl groups having up to twelve carbon atoms, and wherein R 4 is selected from the group consisting of the alkyl, aryl and hydroxyalkyl groups which they have up to 12 carbon atoms.

19. The composition according to claim 12, characterized in that it comprises the catalyst in the range of 5 to 25 percent by weight of the total composition.

20. A composite material having a resin component, characterized in that it comprises the composition prepared according to claim 12.

21. A phenolic siloxane composition, characterized in that it is prepared by the combination of: a phenolic resole resin; a silicone intermediate; and a catalyst to facilitate processing and curing at temperatures below 100 ° C, wherein the phenolic resole resin and the silicone intermediate react to form an interpenetration network of the siloxane polymer and the phenolic polymer, wherein the The phenolic polymer includes Si-0 groups in its backbone, and wherein the composition comprises more than about 65 percent of the phenolic resole resin, based on the total composition.

22. The composition according to claim 21, characterized in that the composition is free of solid particles containing silicon.

23. The composition according to claim 21, characterized in that the silicone intermediate is in the range of 0.5 to 35 weight percent of the total composition.

24. The composition according to claim 21, characterized in that the catalyst is selected from the group consisting of organometallic compounds, amine compounds, acids, bases and mixtures thereof.

25. The composition according to claim 24, characterized in that the catalyst is a mixture of an organometallic compound and an amine compound, and wherein the composition comprises catalyst up to 10 weight percent of the total composition.

26. A compound having a resin component, characterized in that it comprises the composition prepared according to claim 21.

27. A phenolic siloxane composition, characterized in that it is prepared by the combination of: a phenolic novolac resin; a formaldehyde donor; a silicone intermediate; and a catalyst for facilitating the formation of a thermosetting polymer interpenetration network, comprising a siloxane polymer and a phenolic polymer, wherein the phenolic polymer has Si-0 groups in its backbone.

28. The composition according to claim 27, characterized in that the composition is free of solid particles containing silicon.

29. The composition according to claim 27, characterized in that the silicone intermediate is in the range of 0.5 to 35 percent by weight of the total composition.

30. The composition according to claim 27, characterized in that the catalyst is selected from the group consisting of organometallic compounds, amine compounds, acids, bases and mixtures thereof.

31. The composition according to claim 30, characterized in that the catalyst is a mixture of an organometallic compound and an amine compound.

32. The composition according to claim 31, characterized in that the organometallic compound is an organotin compound having the formula R8 R9-Sn-R 10 tu where R3, R9, Rio and Ru are each selected from the group consisting of the alkyl, aryl, aryloxy, and alkoxy groups, having up to 11 carbon atoms, and wherein any two of R8, Rg, Rio and Rn are additionally selected from a group consisting of inorganic atoms consisting of halogen, sulfur and oxygen.

33. The composition according to claim 31, characterized in that the amine compound has the formula R12-N-R14 R13 where Ri2 and R3 are each selected from the group consisting of hydrogen, aryl and alkyl groups having up to twelve carbon atoms, and wherein R14 is selected from the group consisting of the alkyl, aryl and hydroxyalkyl groups having up to 12 carbon atoms.

34. The composition according to claim 27, characterized in that it comprises catalyst in the range of 5 to 25 percent by weight of the total composition.

35. A composite material having a resin component, characterized in that it comprises the composition prepared according to claim 27.

36. A thermosettable composition of phenolic siloxane, characterized in that it is prepared by the combination of: a phenolic novolac resin; a formaldehyde donor; a silicone intermediate; and a sufficient amount of catalyst to facilitate the curing of the composition at a temperature below 100 ° C, wherein the phenolic novolak resin, the formaldehyde donor, and the silicone intermediate react to form an interpenetrating polymer network, wherein the phenolic resin includes Si-0 groups and its backbone, and wherein the composition comprises more than about 50 weight percent of the phenolic novolak resin, based on the total composition.

37. The composition according to claim 36, characterized in that it comprises silicone intermediate in the range of 0.5 to 35 percent by weight of the total composition.

38. The composition according to claim 36, characterized in that the catalyst is selected from the group consisting of organometallic compounds, amine compounds, acids, bases and mixtures thereof.

39. The composition according to claim 38, characterized in that the catalyst is a mixture of an organometallic compound and an amine compound, and wherein the composition comprises catalyst in an amount up to 10 percent of the total composition.

40. A compound having a resin component, characterized in that it comprises the composition prepared according to claim 36.

41. A composite tube having a resin component, characterized in that it comprises a phenolic siloxane composition prepared by the combination of: a phenolic resole resin; a silicone intermediate; and a sufficient amount of catalyst to effect cure, wherein the phenolic resole resin and the silicone intermediate react to form an interpenetrating polymer network of the siloxane polymers and the phenolic polymers.

42. A foam from a blowing agent, a surfactant, and a phenolic siloxane composition, characterized in that it is prepared by the combination of: a phenolic resole resin; a silicone intermediate; and a sufficient amount of catalyst to facilitate cure, wherein the phenolic resole resin and the siloxane intermediate react to form an interpenetrating polymer network of the siloxane polymers and the phenolic polymers.

43. A method for forming a phenolic siloxane composition, characterized in that the method comprises the steps of: combining a phenol ingredient with a silicone intermediate to form a mixture, wherein the silanol groups are present in the mixture and react with the hydroxyl groups of the phenol ingredient, and wherein the silanol groups react with other silanol groups to form a siloxane polymer; and the addition of an aldehyde ingredient to the mixture, to form a phenolic polymer, wherein the composition comprises an interpenetrating polymer network comprised of phenolic polymer and siloxane polymer.

44. A method for the formation of a phenolic siloxane composition, characterized in that the method comprises the steps of: combining a phenolic resole resin with a silicone intermediate, to form a mixture, including mixing silanol groups, phenolic hydroxyl groups and phenolic methylol hydroxyl groups; the reaction of the silanol groups with at least one of the phenolic hydroxyl groups, and the phenolic methylol hydroxyl groups; and the addition of a sufficient amount of catalyst to the mixture to facilitate the cure.

45. The method according to claim 44, characterized in that it comprises the formation of a polymer network of interpenetration of the phenoic polymer and the siloxane polymer from the mixture.

46. A method for the formation of a phenolic siloxane composition, characterized in that it comprises the steps of: the combination of a phenolic novolak resin, with a formaldehyde donor and a silicone intermediate, to form a mixture, including the mixture of silanol groups and phenolic hydroxyl groups; the reaction of the silanol groups with the phenolic hydroxyl groups; and the addition of a sufficient amount of catalyst to the mixture to facilitate the cure.

47. The method according to claim 46, characterized in that it comprises the formation of a polymer network of interpenetration of the phenolic polymer and the siloxane polymer, from the mixture.