JPS6357664A - Formable composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel vitreous carbon composition comprising a phenol-furfuraldehyde novolak added to a phenol-aldehyde resol resin.

Specifically, the present invention provides carbonization of large-sized shaped vitreous carbon, especially properly compressed and shaped products, and then graphitization into good vitreous carbon with low breakage rate or low change rejection rate. related to the manufacture of large thin plates made of More specifically, the present invention relates to a method of making such a vitreous carbon product.

BACKGROUND OF THE INVENTION Glassy carbon is extremely inert (non-reactive) and has no pores, making it an important and useful material for structures used in many fields and various industrial fields. In research and development, such materials are used in the manufacture of beakers, deep dishes, boats, reaction tubes, etc., and common applications include semiconductor processing, fluoride laser materials, zone refining of metals, zone refining of chemicals, etc. Used in purification, biomedical supplies, fuel cell electrodes, etc.

However, industrial use of vitreous carbon has only begun in recent years. Glassy carbon does not have wettability with a wide range of metals, including zinc, silver, copper, tin, lead, aluminum, gold, platinum, etc., so it is difficult to process these metals and their alloys, such as processing molten aluminum with chlorine gas. It was used for dehydrogenation treatment. The production of pipes immersed in corrosive liquids from this type of material is also a useful application.

The development of industrial applications for this material has been extremely difficult due to the inability to produce properly cured molded or extruded parts of the desired shape with comparable efficiency and cost using conventional molds or dies. was limited to. Furthermore, it has been difficult to manufacture thick sheets suitable for use in fuel cells.

A resol resin is a resinous reaction product between a phenol and an aldehyde that has been condensed (reacted) to the point that it still melts when heated and is still insoluble in acetone; It has a high reactivity,
Even without the addition of a curing agent, it can be cured by heating and reach an insoluble and non-molten state. Resol resins are also known as A-stage phenolic resins or single-stage resins because they can be cured without the addition of crosslinkers.

Resol resins are prepared using aldehydes and phenols in molar ratios of 1/1 or greater. There is no need to add a curing agent such as hexamethylenetetramine (hereinafter referred to as rhexaJ) to effect the final cure since there is already sufficient aldehyde to effect the cure to an insoluble, non-molten state. However, in the preparation of resol resins, it is preferred to add a small amount of hexa to obtain a harder and more easily crushed resol. For this purpose, for example hexaO,005
It is advantageous to use between 0.03 and 0.03 mol, preferably 0.01 mol. In any case, the amount of hexa used in the preparation of the resol is not counted in the amount added to accelerate the curing of the novolak-resol mixture.

In contrast, novolak resins are prepared in an aldehyde-depleted state and therefore will not cure unless a curing agent such as hexa is added.

Novolacs, in any application, are therefore defined as resinous reaction products of phenol-aldehydes that do not harden or change to an insoluble, non-molten state upon heating, but remain soluble and meltable.

When using resin granules, it is particularly important that the novolak is a phenol-furfuraldehyde resin. If the novolak uses furfuraldehyde, compression methods are suitable for molding the resin mixture into the desired shape, but this method is not suitable for novolaks prepared using other aldehydes. do not have.

In patent applications No. 182,755, No. 358,893 and No. 502.181, numerous documents are cited regarding the reaction of novolacs and resol resins. These include U.S. Patent No. 3,998,906;
No. 7,140, No. 3,879,338, No. 3,410
, 718, JP-A-53-75294 and British Patent No. 1,098,029. Although these documents concern curable vitreous mixtures of resins,
Both methods involve removing water from a vitreous mixture and thereby producing a moldable composition, particularly a composition that is mixed with a carbonaceous filler such as graphite so as to be transformed into a vitreous carbon product. It's not about.

SUMMARY OF THE INVENTION According to the present invention, phenol-aldehyde resol resin is added to a 20-80 wt.
By adding 20-80% by weight of purfuraldehyde novolac resins together with appropriate amounts of amines (e.g. hexamethylenetetramine), resin compositions with excellent moldability are obtained (% expressed relative to the total weight of the two resins). value).

Note that 1lexa and novolak are added separately or simultaneously before the completion of dehydration or water removal of the resol resin. The hexa is added all at once or in two or more portions until 90% of the water is removed, preferably before 75% of the water is removed. The novolak is added after the resol components have been reacted at about 90° C. for about 30 minutes, advantageously before substantially all of the water has been removed. During the preparation of the novolak to be added to the resol, at least 25% of the water present is removed, and in the addition of the novolak to the resol, advantageously at least 35%, preferably at least 50% or 75% of the water is removed. , more advantageously,
Substantially all of the water is removed. The preferred ratio of parts by weight of novolak/parts by weight of resol before reaction is 3G/7.
It ranges from 0 to 50/5G.

Regarding the removal of water in the resin and during the production of the resin, this "water" includes water present in the ingredients, such as water contained in formaldehyde aqueous solution or caustic alkali aqueous solution, etc. Added water and water produced by resin condensation reaction are included. The amount of water is easily determined by first conducting a reaction that completely removes the water, followed by a reaction that removes only a portion of the water.

Various other amines can be used in place of hexaO, as described in more detail below. Hexa or other amines serve two functions. First, it functions to harden the resole component and prevent premature gelation, and functions to avoid premature gelation from occurring when novolak is added. Avoidance of premature gelation is important in completely removing water from the mixed reaction product to produce a millable product that is subsequently hardened in a moldable composition.

Advantageously, the specified amount of hexa is added to the resole component, preferably after refluxing of the resole component to the point where substantially all of the formaldehyde has been reacted, or before or after the addition of the novolac. and is added until 90% of the water initially present has been removed, preferably after 75% of the water has been removed.

The amount of amine is advantageously 1-15% by weight, preferably 2-10% by weight, based on the total weight of the phenolic components. Based on the total weight of the resin product, the amount of amine is advantageously 0.5-6% by weight, preferably 1-5% by weight.

After the addition of hexa and novolak is complete, dehydration or water removal is carried out until a grindable resin is obtained upon cooling the reaction mass. The resulting resin product is
Formable compositions filled with carbonaceous material (e.g. graphite), particularly suitable for graphitization to produce glassy carbon that is stress-free and free of pits and pores.
It has molding plasticity that is particularly suitable for imparting excellent fluidity to.

During the curing of novolac resins, certain amounts of curing agents (e.g. he
xa) is used. Such curing agents that may be added include aldehydes such as formaldehyde, or alkylene releasing compounds such as hexamethylenetetramine which release methylene groups for curing. However, when such a specific amount of curing agent is used in the preparation of a cured novolak resin with the ultimate purpose of producing glassy carbon, a large amount of gas is generally produced as a by-product and the resin processing In the later stage, the stress within the molded product (molded-in 5t
ress) occurs. In either case, the product may not have the desired properties.

According to the compositions and methods of the present invention, at least a majority or substantially all of the crosslinking between phenolic groups is carried out through the methylol groups present in the resole resin, producing a resin with excellent moldability. Due to the fact that resins can be prepared to ultimately produce vitreous carbon with very good properties. In this way, the need to add crosslinking agents to the final product to provide crosslinking groups for the novolac molecules is avoided or reduced. The carbonizable phenolic resin produced from the composition according to the invention can be used in phenol-furfural novolac resins and resol resins.
It is a reaction product of exa. Some of this reaction takes place during dehydration of the resol.

This reaction resin product is used as a mixture with a finely divided carbonaceous filler such as graphite, and has sufficient molding plasticity to provide molded products with low stress and distortion. , this molded product has excellent properties during graphitization, has no depressions and pores, and also has no cracks and microcracks, thus determining its suitability as a separator in fuel cells. The present invention provides a vitreous carbon product that reduces and substantially avoids rejection due to breakage or failure in permeability tests.

The phenol-furfural novolak has a plasticizing effect on the reacted resole resin, so that the resulting viscous mass flows uniformly and easily under low pressure and completely clears the mold before a high degree of gelation and crosslinking occurs. filled with. In contrast, single-stage resins (resols) have a fast initial curing rate and produce large amounts of gelled or cross-linked polymeric molecules, thereby creating locally stressed areas within the molded part. . It is believed that this plasticizing effect allows for the production of molded articles that are substantially free of intra-molded stresses. Furthermore, when the molded article is carbonized to vitreous carbon, this stress-free state is carried over to the final product, in which superior properties are developed.

A mixture of preformed micronized phenol-furfuraldehyde novolak (PFUN) and preformed micronized phenol-aldehyde resol (PFR) is disclosed in the aforementioned Prior Patent Application No. 50 of the present applicant. ,33
Although it has been disclosed that method No. 1 can be effectively used in the production of vitreous carbon molded products, which is difficult to produce with other methods, the inventors have newly discovered that the product is not completely dehydrated. It has been found that by adding a preformed phenol-furfuraldehyde novolac resin to a solution of a phenolic aldehyde resol resin that has been polymerized to an uncontained stage, a composition more effective for this purpose is obtained; This led to the present invention. Novolac resin is
Prior to such addition, it may be completely dehydrated or may be preformed in an undehydrated state.

Especially for molded products that are difficult to effectively mold, carbonize, and graphitize, the final molded thickness is 0.10 to 0.13 cm.
m (0.04-0.05 inch), preferably 0.1
It is a 14cx (0,045 inch) plate. The above thickness and other suitable dimensions, e.g. about 51-64 cm
(20-25 inches) x 64-76CI (25-3
0 inch), or 127 x 127 if larger
Glassy carbon plates with ci (50×50 inches) are effectively utilized in fuel cells if they are gas and liquid impermeable.

The method described in the above-mentioned patent application improves the impermeability of such plates. However, if cracks occur throughout the entire plate, the plate becomes transparent and is naturally rejected.

An improved method of mixing the resins before dewatering and allowing the resins to react during dewatering produces a product that exhibits excellent impermeability even at thicknesses of 0.045 inches. Such improvements can substantially avoid the frequency of rejections, thereby reducing the cost of the plate.

Gel permeation chromatography and CI3 nuclear magnetic nuclear resonance”N
In the MR) spectrum, the molecular weight of the high molecular weight portion of PFUN slightly decreased during the mixing performed before dehydration;
It was shown that grafting of low molecular weight substances to PFUN was observed. This low molecular weight material appears to be low molecular weight hydroxymethylphenol and bis(hydroxymethyl)phenol.

The accompanying drawing shows two gel permeation chromatogram curves superimposed on each other. Curve A shows the gel permeation chromatogram of a mixture with PFUN and PPR previously prepared according to the method of patent application no. 50.531. The dashed curve B shows the same PFUN as used in curve A before dehydration carried out in a manner similar to that described in Example 5 below.
Figure 2 shows a gel permeation chromatogram of a mixture obtained by adding PFUN to a similar PFR, except that 35 parts of PFUN were added to 65 parts of PPR. The proportions and other conditions were kept as similar as possible. Curve B shows a hump to the left of the high molecular weight peak. This seems to indicate that the substance was grafted as described above.

C'' NMR spectrum shows a decrease in free hydroxymethyl group resonance at 5g-60ppm and 152-15
The grafting phenomenon is indicated by the change in the substitution pattern of the phenolic groups as represented by the 7 ppm resonance.

Novolak and resole resins include Carleton E
The Chemistry of Synthetic Resins
f5yntheticResins)J(Rei
nhold Publishing Co., New York) Vol 1, p 315 (1935
) are prepared by condensation between various phenols and aldehydes. This author is No. 13-1
Chapter 8 discloses a number of phenol-aldehyde resins, Chapter 19 discloses modified phenol-aldehyde resins, and Chapter 20 discloses modified phenol-formaldehyde resins.

Typical examples of phenols used include phenol itself and its various analogues (e.g. mono-cresol); various xylenols, hydroquinone, pyrogallol; resorcinol;
Halogenated derivatives of phenol that retain the above components (e.g. p-chlorophenol, p-bromophenol, p-bromophenol, p-chlorophenol, p-bromophenol,
-fluorophenol, etc.): various naphthols, various hydroxy-benzoic acid esters; p,p'-dihydroxydiphenylmethane;p,p'-dihydroxydiphenyl-2,2'-diphenylpropane, etc.

〇- and p-cresols can also be used when mixed with other phenols that have three reactive sites available for crosslinking, such as the ortho and para positions (e.g. -phenol). For economic reasons and ease of availability,
Preference is given to using phenol itself.

Similarly, in preparing the resol resins used in the present invention,
A wide range of aldehydes can be used. Typically, formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, glyoxal, acrolein, benzaldehyde, terephthalaldehyde, etc. are used.

In this case, too, formaldehyde is preferred from the viewpoints of cost, availability, and ease of handling. Here, "aldehyde" refers to the above-mentioned aldehyde, i.e. -
This does not refer only to compounds containing C10 groups, but also to compounds that can generate aldehydes under reaction conditions.
It also includes compounds capable of releasing crosslinking alkylene groups of the same type as those produced by aldehydes.

For example, hexamethylenetetramine releases methylene bridging groups, and acetylene under appropriate conditions reacts with phenol to produce resins similar to those produced from phenol and acetaldehyde.

The optimum molar ratio of aldehyde/phenol in preparing novolacs and in preparing resoles depends, respectively, on the nature of the aldehyde and the nature of the phenol and the conditions under which they are reacted.

If furfuraldehyde (furfural) is used as the condensing aldehyde for the novolak, its amount is advantageously about 0.8-0.9 mol, preferably about 0.7-0.75 mol per mole of phenol. Furfural is added in its entirety at one time or in two or more parts.

An important point regarding novolaks is that the requirements for acceptance as novolaks (i.e., the phenol-aldehyde resin must only cure when heated and not be thermally transformed into an insoluble, non-molten product for any purpose) ).

A further requirement for the novolak is that it must be capable of being converted into an insoluble, non-molten product by thermal reaction with an added aldehyde, such as formaldehyde or a reactive aldehyde compound such as hexa. (see Ellis, supra, I) 327). Thus, novolak is tested by adding 10% by weight hexa and heating. True novolaks are cured to become insoluble, non-melting resins. If the material does not cure during testing, further hex
Add a and repeat the test. If it still does not cure, the material is considered not to be a novolak. In carrying out the present invention, it is necessary that the material be cured by the resol to become insoluble and non-molten, so it must satisfy this curing test.

Thus, in the practice of the present invention, most of the novolak crosslinks are formed by the resol. Hexamethylenetetramine added with novolac replenishes the crosslinks formed by the resol. however,
The amount of hexa, while achieving the desired effect, must be low enough to avoid the drawbacks mentioned above.

As mentioned above, this amount is advantageously from 0.12 to 12 parts by weight, preferably from 2 to 8 parts by weight per 100 parts by weight of novolac resin.

As mentioned above, various amines that perform similar functions can be used in place of hexa.

These amines include ammonia and various amines with free hydrogen bonded to the nitrogen atom, such as mono- and dialkylamines (methylamine, dimethylamine, ethylamine, diethylamine, butylamine, dibutylamine, decylamine, etc.), mono- and diarylamines, etc. These include amines (aniline, diphenylamine, benzidine, methylene dianiline, etc.), and monoaryl-monoalkylamines (N-methylaniline, N-ethylaniline, N-propyltrilylamine, etc.). Advantageously, the hydrocarbon radical has 1 to 21 carbon atoms. Preferably it is from 1 to 1O.

Resoles are prepared using phenol and aldehyde in a wide range of molar ratios depending on the specificity of the phenol and aldehyde used. In this case as well, it is common to use phenol as the phenol component and formaldehyde as the aldehyde component. Phenol-formaldehyde resols are usually prepared under alkaline or basic conditions to produce resinous condensation products having a large number of unreacted methylol groups, along with methylene groups, both derived from aldehydes.

For the preparation of resols, the formaldehyde/phenol ratio is preferably 1. Q5/1 to 1°5/1. In some formulations, some of the crosslinking groups are hexa
replenished by.

Effective groups in the resol are likewise active functional groups,
It reacts with the novolac to form a thermoset resin that is used in subsequent carbonization to produce vitreous carbon.

In the preparation of furfural-phenol novolaks, it is preferred to use alkaline catalysts to effect a controlled condensation. The use of acid catalysts should be avoided since acids tend to cause extra polymerization reactions through the ethylenically unsaturated bonds of the furan ring with the cyclic diene-ether structure.

In contrast, when preparing novolaks using furfural under active conditions (e.g., with sodium carbonate), the furfural/phenol molar ratio is 0.
60/l to 0.90/l, preferably 0.70/1
to 0.75/1, a novolac is produced that does not cure with normal heating but does cure when formaldehyde or hexa is added. However, if acid is present during the initial condensation or added afterwards, the resin undergoes further reaction, but the resulting resin is judged to be resole in nature. For example, when furfural novolac is treated with a strong acid, addition reactions of the vinyl form are promoted, resulting in further polymerization reactions and crosslinking between polymer molecules.

The carbonized resin of the present invention can be used in electrochemical systems (e.g. chlorine cells), molten aluminum systems, electroplating systems, using strong electrolytic acids such as sulfuric acid and phosphoric acid with methane and air, hydrogen and oxygen or chlorine etc. as fuels. As an electrode in a DC power generation system, as a burn capture device or control rod in a nuclear reactor, as a member in an aerospace system, as a support or wall in a catalyst system, as a metallurgical crucible, as a diffusion sheet or plate in a diffusion device, Suitable for use as a zone purification unit etc.

The production of molded articles from the novolac-resol reaction compositions according to the invention is carried out by known technical means, such as compression molding, injection molding, transfer molding and impulse molding. In either case, the resin mixture is introduced into the hot mold under sufficient pressure to at least fill all parts of the mold with the mixture, and the resin composition is cured to an insoluble, non-molten state.

The temperature depends on the composition of the novolak and the resol to be reacted, the presence or absence of furfural added as an auxiliary crosslinker or reactive plasticizer, the amount and type of carbonaceous fillers and other non-expandable fillers, etc. It can change over a wide range. However, many of these compositions are 100 to 16
It is molded at a temperature of 6°C.

In certain cases, temperatures on the order of 180°C are utilized.

The preferred range is 149°-166°C.

As with temperature itself, the same factors mentioned above that affect the molding temperature used often also influence the selection of pressure in molding into the desired shape. However, to form a mixture containing 60% graphite filler, 40%, 20% or 0% graphite filler is required.
higher pressures are required than for those containing

Furthermore, the shape of the molded part also influences the selection of a suitable molding pressure. Based on the pressure required for compression molding, higher pressure is required for transfer molding,
Injection molding requires even higher pressures. Is it generally 2800 for transfer molding? / am”(20(
US) tons/inch, and compression molding is 700 to 91
There is 0x'(5) n/finch.

The general range of pressure is 35 to 3500 to 9/cm' (
0.25 to 25 tons/inch, preferred range is 35-
2800 to 97cm” (0,25-20) inches/inch3
), and 9/cx to 56-700 for compression molding.
'c0.4-5 tons/inch.

In the extractability test of the molded articles of the present invention, non-reactive additives (
If no plasticizer (e.g. plasticizer) is present, less than 2% of the material will be extracted with acetone based on the resin content of the product.
It was shown that it is generally 1% or less. In fact, shaped articles often contain only very small amounts of extractable substances, even when strong solvents (eg dimethylformamide) are used. In addition, the extractability test is AST
Performed according to MD 494-46.

The weight ratio between the novolak resin and the resol resin before the reaction is determined by the addition of auxiliary hardeners (e.g. hexa), reactive plasticizers (furfural), processing aids such as molding plasticizers (zinc stearate or stearyl alcohol) and various The use of the vitreous carbon depends on the use of the vitreous carbon, as well as the presence or absence of various additives or modifiers, such as fillers (graphite), etc. As discussed herein, the applications of the products of the present invention are extremely versatile, with applications such as chemically resistant piping and equipment, walls and electrodes for fuel cells, and the like.

For many applications, the PFUN:PFR ratio is 80:
20 to 20:80. Amines (e.g. hex
a) is h relative to the total weight of the phenolic components, as described above.
exal-15%, preferably in an amount of 2-10%, or 0.5-6%, preferably relative to the total weight of the resin! -5%
is added in an amount of As mentioned above (instead of hexa,
Similar amounts of other amines can be used. In order to increase plasticity, 5% by weight or less of furfural can be added per 100 parts by weight of resin.

A mold release agent may be blended into the resin. Suitable mold release agents include fatty acids having 14-22 carbon atoms, esters with alcohols having 1-22 carbon atoms, and metal salts (e.g. Ca, Z
n and Mg salt). Typical among these are oleic acid, stearic acid, Montan wax,
stearyl stearate, glyceryl monooleate,
Glyceryl monostearate, the wax sold under the name Acrawax, zinc stearate, calcium or magnesium, and the like. In the biomedical field, mold release agents that are not metals or metal compounds are used.

The mold release agent is used in an amount of 0.5-3% by weight of the entire resin composition.

A very effective class of fillers are carbonaceous fillers in which the vitreous carbon itself can exhibit high adhesion. Such materials include pyrolytic graphite, ordinary graphite (formed by flat, parallel membranes of carbon held together by van der Waals forces), and carbonized cellulose. For economic reasons, conventional graphite is generally used more than other fillers in vitreous carbon.

With reference to the case of ordinary graphite, the proportion of such fillers in the molding powder composition according to the invention is of the order of 5% in order to obtain a significant effect; 35 to 65% by weight, preferably about 40-60% by weight.

By adjusting the amount of novolac in the mixture along with the use of hexas mold release agents, furfural, etc.
The proportion of graphite in the molding composition is 30 to 76%
adjusted to. However, graphite compatibility is improved by using fine-grained graphite compared to coarse. In certain cases, it may be desirable to use a combination of graphite types with different grain roughness. By using graphite of various particle sizes in combination, a dense and dense mixture can be produced. For example, in suitable mixtures, the maximum particle size preferably does not exceed 300μ, some of which have a size of 60 to 160μ, and some of which have a size of 60μ or less. The same applies to other fillers.

The amount of carbonaceous filler is also expressed in parts by weight per 100 parts by weight of resin. Thus, the moldable composition of the present invention comprises 80-20 parts by weight of novolac and 2 parts by weight of resol.
0-80 parts by weight (in the proportions when reacted with each other, the total of novolak and resol is 100 parts by weight), up to 230 parts by weight of carbonaceous filler, preferably up to 150 parts by weight, and 5 parts by weight of furfuraldehyde. Below the department, hexao,
It consists of a thermosetting, compression moldable blend comprising 5 to 6 parts by weight, preferably 1 to 5 parts by weight, and 3 parts by weight or less of a mold release agent (the proportions of each additive include novolak and 3 parts by weight). (based on a total of 100 parts by weight of resol).

When special dispersion methods are used, such as careful milling to very fine particle sizes by ball milling,
The amount of graphite may slightly exceed the amounts mentioned above.

A typical graphite-containing composition is Graphite 60
%, phenol-furfural novolak (PFUN)
Phenol-formaldehyde resol (PFR) 22.1% reacted with 13.0% he++a 1.4
8%, stearyl stearate 0.6%, zinc stearate 1.25% and furfural 1.25%.

Another representative composition is 34.75% phenol-formaldehyde resol reacted with 40% graphite, 20.17% phenol-furfural novolak.
, 0.1% stearyl stearate, 1% zinc stearate and 0.6% furfural. The figures are in % by weight relative to the total composition.

Yet another representative graphite-containing composition is 49.9% graphite by weight, 29.2% PFR reacted with 16.6% PFUN, 1.9% hexa, 0.4% stearyl stearate, and 1° furfural. Contains 0%.

After transfer molding, which will be described later, for this composition,
It was ground and the content of acetone dissolved components was measured. The average of these tests indicated a dissolved material content of 0.48%, and the analysis indicated that the dissolved material consisted of a mixture of stearic plasticizer and unreacted furfural.

For special applications, the anisotropy allows glassy carbon to have special thermal and mechanical properties.
It is preferred to use finely dispersed pyrolytic graphite as filler rather than ordinary graphite. Pyrolytic graphite is pure crystalline graphite precipitated from carbon-containing gases at temperatures above 2000°C.

When pyrolytic graphite is used as a filler in the compositions of the invention, the vitreous carbon is such that it has a large amount of graphite (or diamond) crystal domains dispersed within a compact stack of graphitic layers. become. The reason for this is not clear, but it may be due to the nucleation effect. The ratio of the compact stack of graphite-like layers interspersed with graphite crystalline regions can be varied to a certain extent.

The blend of the present invention is converted into vitreous carbon through intermediate steps of molding and curing of the molded article. Correct curing (ie, selection of curing temperature and time) is critical, since the curing particles typically crack during carbonization. The degree of hardening is checked by measuring the amount of acetone extract. ASTM D 494-4
Satisfactory products are obtained when the acetone extract content is less than 2%, preferably less than 1%, relative to the weight of the resin component, measured according to No. 6.

A number of methods are used for shaping. As already mentioned, molded articles are produced by compression molding, transfer molding, extrusion molding or injection molding. High production rates are easily obtained using the blends of the present invention by transfer molding or injection molding in multi-cavity molds. In certain cases, shaped bodies are prepared by processing other shaped articles or extrudates.

In a typical method of operation, the ground molding composition is first preformed to remove entrapped air and electrically heated to 110°C.
Preheat to. Then, the line pressure was increased to 35 kg/cx” (
500psi) diameter 14.0ci (5,5
The preform is formed in a mold press using a ram (inch). The resulting compact is cured at 149 DEG C. for 4-5 minutes at a cavity pressure of about 1500 psi. As will be appreciated, various other methods can be used.

The molded article thus obtained is transformed into a molded vitreous carbon product by precisely controlled thermal carbonization in a furnace in an inert atmosphere until a maximum heat treatment temperature is reached. The vitreous carbon product is then cooled under an inert atmosphere in a closed furnace. Usually, a large number of molded products are processed in one heating operation.

In many cases, the optimum firing cycle of temperature vs. time is determined empirically for each molded article, since the geometrical factors of the molded article (particularly the wall thickness) are directly related to the speed. The time-temperature relationship also depends on the degradation characteristics of the final cured resin.

Different product wall dimensions lead to greater variations in firing cycles.

Generally, in a typical firing cycle, the temperature is raised continuously, but at different rates at each point in the cycle. During firing, volumetric shrinkage of the product occurs. For molded articles containing no carbonaceous fillers or other fillers, it is usually 15 to 25%. The degree of shrinkage also depends on the resin, molding method and conditions, and firing cycle. These shrinkages are reproducible and have a manufacturing tolerance of ±0.013 cm (0
, 005 inches).

During the firing of such filler-free molded articles,
Approximately 30-35% by weight of the molded article is lost as volatile gases. When carbonaceous fillers are incorporated into the resin mixture, shrinkage and weight loss are reduced in proportion to the filler content. To remove the bulk gases generated during glassy carbon formation, an inert purge gas stream such as nitrogen, helium, or argon is used, or alternatively, reduced pressure (10-" Torr or less) is applied. Outgassing is active in certain temperature ranges, e.g.
Up to 60-371'C (500-TOOoF), the rate of temperature rise is typically 0.6-2.8°C/hour (l
−5°F/hour). Above 371'C (700F), the temperature is 5.6 to 27.8C/hour (10
-50°F/hour) rather rapidly. In general, regarding many molded products! , 371℃ (700'
F ) or above, temperature is 5,6℃/hour (10℃
/hour) at a rate of 427-455°C (goo-850°
11.1-27.8°C/hour (2G-50°F/hour) to a maximum temperature (typically 98°F)
The temperature need not exceed 2°C (1800°F).

In certain cases, the maximum temperature is 538°C (tooooF)
There is no need to exceed. If a high degree of thermal stability is required for the shaped vitreous carbon product, heating will be at least 109
up to 3°C (2000°F), in some cases at least 1
Continue to 649°C (3000°F) and maintain this temperature for at least 24 hours. Then, the temperature was set to 5.6-
Gradually reduce the temperature at a rate of 11.1°C/hour (10-20@F/hour).

In some cases, temperatures of about 149-482°C (300-9°C
00°F) is called carbonization, and the temperature is approximately 1149°C.
(2100°F) or higher is called graphitization. Heating in either case is done gradually as described above.

If necessary, the critical temperature regime (r6gime) is determined by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The thermal regime thus measured is characteristic of the chemical and thermal history of the shaped phenolic resin article.

When the novolac-resol reaction resin of the present invention is molded for a purpose other than changing to glassy carbon, various fillers other than the above-mentioned carbonaceous fillers may be used, such as wood flour, asbestos, lime, etc.
Calcium carbonate, MgO, glass fibers, etc. are used, and various mixtures of these or other known modifiers are also used in preparing the molding compositions.

The reacted novolak-resole resin prepared as described above can also be used to prepare molding compositions for purposes other than the production of glassy carbon products, and the molded articles obtained thereby are free from the stress of the novolak and resole resins. It has various improved properties due to the mutual effect that does not cause In such cases, the proportions of fillers and additives correspond substantially to those described above for use in compositions that are converted to vitreous carbon.

Before the dehydration of the resol begins or substantially ends, the preformed novolak may be completely or partially dehydrated before it is added to the resol solution. Advantageously at least two portions of the water initially present
5%, preferably at least 50% is removed before addition to the resol.

The product obtained after the dehydration of the mixture is completed is a graft polymerization product.

The resin of the present invention is prepared by adding a preformed phenolic-furfuraldehyde novolac, preferably a phenol-furfuraldehyde novolac, to an aqueous solution or suspension of a phenolic-aldehyde, preferably a phenol-formaldehyde resol, to form a resole resin. prepared by adding it before dehydration. Upon addition to the resol, the novolak is completely or partially dehydrated. On the other hand, the resol is partially dehydrated upon addition, but preferably the addition is carried out before the dehydration begins.

As mentioned in the description with reference to the accompanying drawings, the product obtained in this manner is a graft polymerization product with improved physical properties. This fact also applies to the properties of glassy carbon produced from this. These new products are a significant improvement over those obtained according to other methods. The results of this improvement not only have a positive impact on the physical properties of the vitreous carbon plate, but also
In particular, it avoids the use of such plates being refused on the basis of transparency.

In the compositions associated with the accompanying drawings, the novolac is PFUN produced by the method of Example 1 below;
The resol was produced by the method of Example 3 -PF
R and the graft polymerization product was obtained according to Example 5. In each case, the ratio is 65 parts PFR to 35 parts PFUN, and the fillers and modifiers are used in the amounts mentioned above. According to the invention, 127X
127X 0.11cm (50X 50X O,045
It is possible to manufacture thin vitreous carbon plates with a size of about 1 inch).

The present invention will be explained by the following examples, but these examples are merely for illustrating the present invention and are not intended to limit the spirit or mode of implementation of the present invention. Unless otherwise indicated, parts and percentages are by weight.

Example I Phenol-furfuraldehyde novolak (PFUN
) In a resin container (4 g) equipped with a stirrer, distillation condenser, heating mantle and thermometer, [ISP Phenol 20009
(21,28 mol) and furfural 14809 (1
5.25 mol). The mixture was heated to 66° C. and 30.09 (0.36 mol) of sodium carbonate were added. The contents were then slowly heated to 121'C, at which temperature the heating mantle was removed.

The reaction became exothermic and the temperature continued to rise until boiling began at 135°C. The distillate was collected in a separate apparatus and the furfural phase was removed periodically and returned to the batch during the course of the reaction. Distillation at batch temperature of 133°C to 139°C
It continued for 3 hours and 40 minutes while maintaining the time between. The resin is then drained from the container and cooled to a melting point of 89°C (192°F).
) and a glass transition temperature of 330°K (134,6°C) (yield 32309). This product is
It is a non-curing novolac resin as evidenced by testing on a 165.5°C (330°F) hot plate, but when mixed with HEXA 10 pph.
A cure time of 65-69 seconds at 186°C (330°F) is shown.

Example 2 The procedure was the same as in Example 1, except that during the distillation, glyceryl monooleate 309 was added, mixed well, and the distillation was continued. The resulting resin has a melting point of 85.5°C (186°F)
, and had a glass transition temperature of 327'K.

This resin is also non-curable, with a cure time of 67-68 seconds when 10 ppm hexa is added.

Example 3 Phenol-formaldehyde resol resin (PFR)
Preparation (a) In a container similar to that used in Example 1, add U.
Filled with SP phenol 1500 g (15,96 mol), formaldehyde aqueous solution (52%) 11979 (20,75 mol), hexa 239 (0,16 mol) and sodium hydroxide (97%) 79 (0,170 mol) . The mixture was warmed to 90°C and maintained at this temperature for 1 hour. After this time, the reflux condenser was replaced with a vacuum distillation condenser and receiver. Then, the batch was depressurized to 66C.
JI (26″) Hg and batch temperature of 90°C (
Heat was applied until the temperature reached 194°F. The vacuum was then adjusted to 71 CJl (28'') Hg and distillation continued for 1 hour. Afterwards, the reaction was stopped and the product was discharged from the vessel. The amount of distilled water collected was 940 g. Weighing yielded product 18559, which was added to a gradient bar.
) method mp 79°C (175°F), glass transition temperature (measured by differential scanning calorimetry) 321″K (118,4
(°F) and a hot plate cure time of 17-18 seconds at 166°C (330°F).

(b) 30% ammonia water 3B, 39 (NH30,
The above procedure was repeated using 64 mol, 1o, gg9) but omitting hexa. The product sample is
The melting point was shown to be 79°C (175°F). This product also has the same characteristics as the resol produced in (a) above.
Can be crushed.

(c) Same as (a) above, but formaldehyde aqueous solution IQ 5g! The reaction was carried out using 11 (18.34 mol). The product was a grindable resol.

(d) Using 13359 (23.15 mol) instead of 1197 g of formaldehyde aqueous solution, the above (a)
) reaction was performed. The product was a grindable resol.

Example 4 Phenol-formaldehyde novolac resin (PPM
) Preparation of 2000 g of USP phenol (21
, 28 mol), formaldehyde aqueous solution (52%) 88
29 (15,28 mol), water 2009 and phosphoric acid (85
%) 129 (0.10 mol). The pH of the resulting mixture was 1.05.

This mixture was then heated to reflux for a total of 5 hours. The free formaldehyde content in the mixture at this point was 0.84%. Here, the reflux condenser was replaced with a distillation condenser, and distillation was carried out under atmospheric pressure for 1 hour until the batch temperature reached 160°C. After that, water 709
51% formaldehyde aqueous solution mixed with 1739 (:
(,0 mol) of the mixture was added gradually over 36 minutes. During the addition the temperature of the batch decreased to 142°C. Once all the formaldehyde aqueous solution had been added, the batch was held at 142-150°C for 15 minutes. The distillation condenser receiver was then replaced with a vacuum receiver so that the batch could be maintained under reduced pressure. Next, the degree of vacuum 71cx (2g
The resin was dehydrated by heating to a temperature of 165° C. in Ig. The vacuum was released and the resin was removed from the vessel, yielding product 20279. The product has a glass transition temperature (determined by differential scanning calorimetry) of 70°C (1
58°F). This resin was heated at 166°C (33°C).
It is a non-curing novolak as shown when tested on a hot plate at 0°F. However, hexa
166°C (330°
When heated at F), it has a curing time of 24-25 seconds.

Example 5 4 equipped with thermometer, reflux condenser, stirrer and stopper
In the neck resin flask (4e), add 1712 g of phenol (1
8,21 mol), formaldehyde 1199 g (20,
78 mol). The mixture was cooled to 39°C,
At this point 8.09 (0.2 mol) of sodium hydroxide and 8.09 (0.2 mol) of hexamethylenetetramine were added. This mixture was heated to 90°C for 30 minutes and
Maintained at 0°C for 30 minutes. Next, a vacuum distillation device was installed in place of the reflux condenser, and the batch was heated to a vacuum degree of 66 cm (26 cm).
inch) by vacuum distillation at a temperature of 6.
Allowed to rapidly cool to 3°C. Heating mantle variable resistor 5
Phenol-furfural novolak finely ground to pass through a 60 mesh sieve at
2509 (prepared in Example 1) was added. Total addition time is 2 minutes. During the addition, the temperature slowly rose to 64°C. At the end of the addition, the vessel was closed and vacuum distillation was carried out to a temperature of 92°C at a vacuum of 66 cx (26'') Hg. At this point, a continuous read wattmeter attached to the drive motor was reading 110 watts at speed setting 5. The resin was discharged into a dish and allowed to cool. After cooling, the resin had a melting point (by gradient-end bar method) = 8.
It had a curing time (stroke curing method) of 30.5 seconds at 4°C and 165°C. The yield of graft copolymer was 24,599.

The above reaction product was ground to pass through a 60 mesh sieve and milled in a differential 2-roll mixing mill (front roll was 1
(maintained at 21°C, rear roll maintained at 27°C). This resin was then melted and mixed for a total of 17 minutes without adding any additives and mixed with Gravender (Br
abender) minimum torque and duration, each 2
A product of 700 mg and 40.5 seconds was obtained. The Gravender measurements were performed using a standard Gravender viscometer equipped with a half-size head and roller blade. The measured temperature is 125° C. at 60 rpm with a connector setting of 1.5 and a sensitivity (no torque suppression) of 45 (X 5 ).

Then, line pressure 42 to 97 cm” (600 psi)
The product is molded in a standard transfer press using a standard ASTM compressive strength, tensile strength, flexural strength,
Izod impact strength and dielectric strength samples were prepared.

When these molded products were tested, the following results were shown.

Specific gravity 1.28 Compressive strength 2242.8 to 97cm” (32,0
40psi) Bending strength 1005.6&9/CI'
(14,366psi) lzod impact strength 0.01
32kg-x/cm (0,24ft-1b/1n) (with notch) Tensile strength 519.4&9/cff” (7,4
20psi) Dielectric strength 170V/Km (
272V/n1l) 18.5 to 9/cm” (264ps
Distortion temperature at i) of 186°C (367°F) After reflux, preferably the desired cooling effect, advantageously 31-39°C (55-70°I), as seen in Example 5.
It is advantageous to add the novolak after sufficient water has been removed so that . If desired, cooling can be effected by other means, with novolac addition starting after reflux and before water removal. In both cases, water removal takes place after the addition of the novolak.

Example 6 Polyhydroquine methylphenol-grafted phenol-furfural novolak (grafted sol/
Phenol-furfural novophenol 1522g (
16,19 mol), formaldehyde (52% solution) 1
066g (18,48 mol), sodium hydroxide 7.1
09 (0,178 mol), hexamethylenetetramine 7
6.1 g (0.54 mol) and the phenol of Example 1
The same procedure as in Example 5 was carried out using furfural novolac 2509. The addition time was 3 minutes and the temperature was slowly increased to 81"C. Vacuum degree 63.0C.
Vacuum distillation was carried out at a temperature of 93° C. at m (24,8 inches) Hg. The wattmeter reading at speed setting 5 was 120 watts. The recovered resin has a melting point = 183.8
C and curing time = 30.5 seconds at 165C.

The yield of graft copolymer was 24,689. Mixing was carried out for 21 minutes, yielding a product with Gravender minimum torque and duration of 2200 mg and 73.5 seconds, respectively.

The results of the molded article tests were as follows.

Specific gravity 1.28 Compressive strength 2126.6? /cm'' (30, 38
0 ps i) Bending strength 878.1 to 9/cm”
(12,544psi) Izod impact strength 0.01
3 to 9 cm (0,24 ft'lb/inch) notched) Tensile strength 469 kg/cff” (6,70
0psi) Dielectric strength 171.9 V/Km
(275V/mi+) 185kg/cm'' (264ps
Distortion temperature in i) 160° C. (320° F.) Example 7 1332 g (14,17 mol) of phenol, 9329 (16,15 mol) of formaldehyde (52% solution), 6.209 (0,156 mol) sodium hydroxide , hexamethylenetetramine 66.69 (0.48 mol) and phenol-furfural novolak 7509 of Example 1
The same operation as in Example 5 was carried out using . The addition time was 12 minutes and the temperature was slowly increased to 68°C. Vacuum distillation was carried out at a vacuum degree of 64 cz (25 inches) Hg to a temperature of 92°C. The wattmeter reading at speed setting 5 was 120 watts. The recovered resin has a melting point of 8
At 2°C and curing time = 31.5 seconds at 165°C. The yield of graft copolymer was 24,809. Mixing was carried out for 20 minutes, yielding a product with Gravender minimum torque and duration of 2000 IIl-g and 73.5 seconds, respectively.

The results of the molded product tests were as follows.

Specific gravity 1.28 Compressive strength 2059.4 to 9/cyr'' (29,4
20psi) Bending strength 681.0&2/cm'
(9,728psi)I zod impact strength O,ot
3 to 9 cm (0.24 ft-1 b/inch) (notched) Tensile strength 433.1 & 9/cm” (6,18
7psi) Dielectric strength 190V/Km (3
04V/ml) 185 to 9/cx' (264psi
Distortion temperature at 147° C. (297° F.) Example 8 Phenol 11429 (12.15 mol), formaldehyde (52% solution) 799y (13.85 mol), sodium hydroxide 5. (39 (0,133 mol), hexamethylenetetramine 57.19 (0,41 mol) and phenol-furfural novolak 1000 of Example 2
9, and the same operation as in Example 5 was performed. The addition time was 5 minutes and the temperature was slowly increased to 77°C. Vacuum distillation was carried out at a vacuum degree of 61 cR (24 inches) Hg to a temperature of 93°C. The wattmeter reading at speed setting 5 was 120 watts. The recovered resin has a melting point of 8
At 6°C and cure time = 28.5 seconds at 165°C. The yield of graft copolymer was 24,889. Mixing was carried out for 5 minutes at 19° to give a product with Gravender minimum torque and duration of 220011-g and 45 seconds, respectively. The results of the molded product tests were as follows.

Specific gravity 1.28 Compressive strength 1874. ly/cm' (26,78
0psi) bending strength 864.6 to 97c1 (12
, 351 psi) Izod Impact Strength o, ot3 to 9s/cjI (0,24 ft・lb/inch) (notched) Tensile Strength 331.5 kfl/ax” (4,7
36psi) Dielectric strength 200V/Km (
320V/ff1il) 18.5 & 9/c11” (26
Example 9 Phenol 15009 (15,96 mol), formaldehyde (52% solution) 1050 g (18,2 mol),
Sodium hydroxide 7 g (0,175 mol), hexamethylenetetramine 759 (0,54 mol) and Example 1
The same procedure as in Example 5 was carried out using phenol-furfuranyl novolak 19339. The addition time was 46 minutes and the temperature was slowly increased to 77°C.

Vacuum distillation was carried out at a vacuum degree of 48 G2 (19 inches) Hg and a temperature of 89°C.

The wattmeter reading at speed setting 5 was 90 watts. The recovered resin had a melting point = 84°C and a curing time = 16
The time was 34.5 seconds at 5°C. The yield of graft copolymer was 3904 g. Mixing was carried out for 23 minutes, and the minimum torque and duration of Gravender were 2400 m・
g and 120 seconds of product were obtained. The results of the molded article tests were as follows.

Specific gravity 1.28 Compressive strength 1810.2&9/cm' (25,8
60psi) Bending strength 766.1&9/cm''
(10,944psi) Izod impact strength 0.014
&9s 7cm (0,26rllb/inch) (with notch) Tensile strength 534.8ky/cm” (7,64
0psi) Dielectric strength 175 V/Km (2
80V/ml) 18.8 to 9/ax'' (264psi
) Distortion temperature at 108°C (228°F) Example IO Phenol 5719 (6,08 mol), Formaldehyde (52% solution) 3999 (6,93 mol), Sodium hydroxide 2.669 (0,066 mol), Hexamethylenetetramine 28.549 (0,204 mol) and the phenol-furfural novolac of Example 2 175
Using 01F, the same operation as in Example 5 was carried out. The addition time was 22 minutes and the temperature was slowly lowered to 66°C. Vacuum distillation was carried out at a vacuum degree of 61 ci (24 inches) Hg to a temperature of 90°C. The wattmeter reading at speed setting 4.5 was 100 watts. The recovered resin had a melting point of 41°C at melting point = 87°C and curing time = 165°C.
．． It was 5 seconds. The yield of graft copolymer was 2497g.
Met. Mixing was carried out for 37 minutes, Gravender minimum torque and duration were 19 (10a+-g and 105
A second product was obtained.

The results of the molded product tests were as follows.

Specific gravity l, 28 Compressive strength 1216.6&9/cm” (17,3
80psi) Bending strength 457.0kg/cm'' (
6,528psi) Izod impact strength 0.0135&
9゜x/cx (0,25ft4b/inch) (notched) Tensile strength 216.5&g/cm' (3,09
3psi) Dielectric strength 178.1 V/KI11 (
285V/n+1l) 18.5kg/cm” (264p
Distortion temperature at si) 86°C (187°F) Example 11 Phenol 380.59 (4.05 mol), formaldehyde (52% solution) 266.49 (4.62 mol),
Sodium hydroxide 1.789 (0,045 mol), hexamethylenetetramine 19.039 (0,136 mol)
and phenol-furfural novolak 2 of Example 1.
The same operation as in Example 5 was carried out using 0009. The addition time was 30 minutes and the temperature was slowly lowered to 78°C. Vacuum distillation was carried out at a vacuum degree of 48cj+ (19 inches) Hg to a temperature of 80°C. The wattmeter reading at speed setting 4 was 150 watts. The recovered resin had a melting point = 110°C and a cure time = 33.5 seconds at 165°C.

The yield of graft copolymer was 27,959. Mixing was carried out for 5.5 minutes, yielding a product with Gravender minimum torque and duration of 2500 mg and 52.5 seconds, respectively. The results of the molded product tests were as follows.

Specific gravity 1.28 Compressive strength L948.8kg/ax” (27,8
40psi) bending strength 631.1 to 97ax''
(9,024 psi) Izod Impact Strength O, O12 9 S/cm (0,24 ft・lb/inch) (notched) Tensile Strength 320.6 & 9/cm” (4,58
0psi) Dielectric strength 158.1 V/I [m
(253V/ml)lLs&g/Cm” (264ps
Example 12 Preparation of Graphite Filled Compositions The resins of Examples 1 and 3(a) were added to
Grind separately to pass through a 5-inch sieve,
It was mixed as follows.

Resin of Example 1 (PFUN) 850(9) Resin of Example 3(a) (PFR) 1500 Graphite powder 2560 Hexamethylenetetramine powder 100 Stearyl stearate
20 Furfural 50 Stearic Acid 50 After mixing in a ribbon blender for 1 hour, the resulting mixture was heated to a differential 20-lumin (front roll maintained at 93°C (200°F) and rear roll at 149°C (300°F). (°F)). The mill time after the resin is completely melted is 15 seconds. The sheet was then peeled off the roll, cooled and ground to a particle size of 6-80 mesh CU, S standard sieve). This powder was tested for plasticity and hardening properties in the Gravender viscometer as described in Example 5 and was shown to have a minimum plasticity = 500111-g and flow duration = 285 seconds at 125°C.

Next, this compound is processed by a transfer molding method.
57.2x 69.9x O, 114 (thickness) cm (2
2.5 x 27.5 x 0.045 inch) sheets. When using this formulation, the flow duration is not sufficient so that conventional transfer molding methods cannot always be performed reproducibly. However, 5.
lc (2 inch) preforms (each weighing !621F
) When using 868 g and using a large 600 ton compression press, good molding can be achieved with good reproducibility. The cavity pressure during this molding was 105 kg/cm' (1500 ps
ig), each plate at 149°C (300°F);
Molds in 3-4 minutes.

These plates were prepared by the method of Example 14 described below.
Effectively transformed into graphite-filled vitreous carbon with acceptable properties.

Example 13 The resin of Example 7 was ground to pass a 0.05 inch screen and blended with the following ingredients.

Resin of Example 7 2350 (9) Graphite powder 2560 Hexamethylenetetramine powder 100 Stearyl stearate
20 Furfural 50 Stearic Acid 50 After mixing in a ribbon blender for 1 hour, the resulting mixture was mixed in a differential 20-lumin (front roll maintained at 93°C (200°F) and rear roll at 149°C (300° F). The mill time after the resin is completely melted is 15 seconds.

The sheet was then removed from the roll, cooled and ground to particle size 6-80 mesh (U, S standard sieves).

When this powder was tested for plasticity and hardening properties using the Gravender viscometer described in Example 5, the minimum plasticity =
400111-g and a flow duration of -435 seconds at -125°C.

Conventional mixtures of single-stage and two-stage resins of the same composition and with the same type and amount of fillers have a Gravender value of 500 m-g and a flow duration of 2
It showed 85 seconds. This indicates that these resins have desirable and unexpected properties such as increased flow duration and flowability. These properties allow the mixture to thoroughly penetrate complex shaped molds before gelling, allowing curing under high pressure to yield dense, void-free parts.

It is believed that the grafted novolacs of the present invention are superior to mixtures of similar resins due to improvements in flowability and physical uniformity.

Next, this compound is processed by a transfer molding method.
57.2X 69.9X O, 114 (thickness) cR (2
2.5 x 27.5 x 0.045 inch) sheets. Alternatively, using 868 g of 5. ICI (2 inch) preforms (each weighing 629) and compression molding using a large 600 ton compression press, each sheet is placed in a similar plate. Can be molded. The cavity pressure during this molding was 105 kg/cm' (1500 psi).
g) and each plate was heated to 149°C (300°F'
), molded in 3-4 minutes. These plates are effectively transformed into graphite-filled vitreous carbon with acceptable properties by the method of Example 14 below.

Example 14 Carbonization of the Moldings of Examples 12 and 13 To evaluate the carbonization potential of these materials, the plates of Examples 12 and 13 were placed in a graphite container in a furnace with a nitrogen atmosphere. The carbonization cycle used was T
As described by Hornbury and Morgan (rsoc, Plast, Eng, P
ACTEC1975JSeptember 16-18.1975. p
47). Gradually increase the temperature of the furnace to 1.1-1.7℃ (
Temperature 3716C (700°) at a rate of 2-3°F) 7 hours
F), and at this point the temperature increase rate was increased to 42
Approximately 5.6°C up to 7-454°C (800-850°F)
(10°F) for 7 hours, then 982°C (180°C).
0°F) for 7 hours and then maintained at this temperature for about 25 hours. Then,
The temperature was gradually reduced to room temperature at a rate of about 5.6-11.1°C (10-20°F) while maintaining the temperature of the nitrogen atmosphere in the closed furnace. In both cases, impermeable vitreous carbon plates of excellent quality were obtained.

Example 15 Reactive resins of Examples 6.8 and 9 (PFR/PF
tlN ratio = 80/2G, 6G/40 and 5 (1150
) (mixed with graphite according to Example 13), the same operation as in Example 14 was carried out, and satisfactory results were obtained in each case.

Example 16 (a) In the preparation of the novolak and resol used in Example 5, the same amount of m-cresol was used instead of phenol; (b) In the preparation of the novolak used in Example 5. , using the same amount of p,p'-diphenylolmethane in place of phenol, and (C) using the same amount of β-naphthol in place of phenol in the preparation of the resol used with PFUN in Example 5. The operations of Examples 1.5.13 and 14 were carried out using the following methods, and satisfactory results were obtained in the production of vitreous carbon.

To clarify the difference between the use of phenol-formaldehyde novolacs and the use of phenol-furfuraldehyde novolacs according to the invention, phenol-formaldehyde novolacs (PFN) are added before dehydration of the resol.
to a series of phenol-formaldehyde resols (PF
A test conducted with the addition of l'l) is shown in Example 17 below. These tests are based on resol/novolak (i.e. PFR/PFN) crush ratios of 40/60 to 8.
This experiment was carried out on a series of mixtures of 0/20. Note that PPM was obtained by the method described in Example 4. In the preparation according to the invention, dehydration was carried out under reduced pressure until the power applied to the stirrer reached a wattage that correlated to the desired melting point in the resin product. As shown in Example 5, in this case 110 watts were required at stirrer motor speed setting 5.

Completion of the reaction is also indicated by the relative amount of distilled water. 11 + of water added into formaldehyde solution
It is calculated based on the amount of water released by the reaction of CH, O and phenol. The distillate is primarily water containing 5% by weight of free aldehydes and 5% by weight of free phenols. For the reaction shown in Example 17, these measurements are:
In neither case did the gelation that occurred in each case indicate that the reaction was complete. Furthermore, resols prepared by standard methods are not grindable and in order to impart grindability to the resols, Example 3(a), (b), (c
) and (d), the presence of hexa or ammonia was required. In Example 17, in which hexa was not used, the product was a rubbery gel.

In an attempt to produce a grindable resin, in operation C h
exa was used, but the results showed that the gelation was much faster than that produced in Runs A, B, and D.

Example 17 Preparation of PFR-PFN grafted resin In a resin flask (4000 m12) equipped with a stirrer (with a wattmeter to read the power supplied to the stirrer motor), a thermometer and a reflux condenser, Four types of experiments were conducted. The flask was charged with appropriate amounts of USP phenol, formaldehyde (52% aqueous solution), and NaOH as a catalyst. In each case, the mixture of phenol and aqueous formaldehyde was cooled to 40° C. and NaOH was added.

The temperature was then increased to 90°C, and at this temperature approximately 172°C
Time was maintained. After that, equipment for vacuum distillation was attached, and fine powdered phenol-formaldehyde novolac (P
FN) was added. Decompression degree approximately 68cm (26 inches)H
g, but the reaction did not reach completion as indicated by the wattage reading or the amount of distilled water collected. The proportions of reactants, conditions of reaction and results obtained are shown in Table A.

The method according to the invention is considerably simpler and gives better reproducibility than when carried out using the resin mixture described in said patent application no. 50,531.

With respect to phenol-furfural novolaks, this includes novolaks in which small amounts of furfuraldehyde are replaced with other aldehydes in the preparation of the resin. As described above, phenol-furfural novolacs include novolacs in which most of the aldehydes used for condensation with phenol are furfural. In other words, for this purpose furfural 1
00% is preferred, but as long as at least 50 mole % of the aldehyde condensed is furfural, the resulting novolacs give satisfactory results for the purposes of the present invention.

During molding, higher pressures generally need to be used if plasticity is poor. As shown in the examples above, when using the PFUN reaction (PFR) formulation mixture, the pressure
lower pressures, preferably 56 psi), give satisfactory results and often improve plasticity during forming.
-105 kg/am'' (800-1500psi)
becomes possible. 105 kg/cm” (1500ps
i) more than 140 kg/cm” (2000 psi)
Pressures above ) create stresses and strains within the molded article and the resulting vitreous carbon product. These stresses and strains often cause cracks, especially microcracks, in the product. These stresses and their associated cracks and microcracks are avoided or at least reduced through the use of lower molding pressures made possible by the improved molding plasticity of the PFUN-PPR reactants of the present invention.

As mentioned above, the reaction product between the phenol-furfuraldehyde novolak and the resol has molding plasticity such that the viscous mass flows uniformly and easily and can completely fill the mold. This is particularly evident when the resin contains fillers such as graphite. This improved plasticity allows for 127 x 127 cm (50 x 50
(inch) and thickness 0.10-0.13cm
(0.04-0.05 inches) and good permeation resistance, allowing for molding and modification into vitreous carbon PFUN-reactive PFR-graphite blended plates without cracks and pits. In contrast, PFN-PFR-graphite blend mixtures do not have satisfactory plasticity and flow properties suitable for this purpose. A suitable PFtlN/PFR ratio is between 20/80 and 50/50.

The vitreous carbon produced from the above-mentioned reaction products is greatly improved with respect to the absence of cavities and pores. The improvements in the absence of pits and pores and cracks in the vitreous carbon products of the present invention result in improved permeation resistance that allows larger sheets of vitreous carbon to be exposed during use in fuel cells. This is evident from the fact that people are less likely to be rejected when taking various tests to determine whether or not they meet the requirements.

In the parent application of this application, the examiner examined U.S. Pat.
．． No. 906 and JP-A-53-75294 were cited.

These inventions relate to the preparation of granules for producing bonding resins and molds for metal casting.

However, these do not teach the unexpected superiority of phenol-furfural novolak resins in the mixtures described here, nor do they teach the unexpected superiority of phenol-furfural novolac resins in the mixtures described here, nor do they teach the addition of an amine such as hexamethylenetetramine to the resol prior to the addition of the novolac. There is no suggestion of any advantage that may be obtained.

The examples shown below show that phenol-formaldehyde novolac (PFN
') indicates that the mixture is inferior. These examples include adding hex to the resol-novolak reaction mixture to prevent gelation and provide improved molding plasticity.
This clearly shows that the addition of a is important. In these examples, for comparison, the ratio of phenol-formaldehyde resol/PFN or PFUN was set to 60/40 (because this value is the optimal ratio).

Each of the resins produced in these examples was mixed with graphite according to the method of Example 3 at a line pressure of 140 kg/C.
x' (2000 psi) and molded for 3-4 minutes at 149°C (300°F)
A plate of size 27.5 x 0.045 inches was prepared. Each plate was carefully inspected for defects, scratches, etc., and graded according to the following criteria. That is, there are bulges (B), stitch lines (Knitlines).
) (KL), with hole in the center, (IIC), porous (P)
, with underfilled corners (SC), with slightly underfilled corners (SSC), with underfilled sides (SS) and NF without visible flaws.

Comparative Examples 1 to 7 below are PFRs in which a certain amount of hexa is added prior to the grafting operation and various amounts of water are removed from the novolak before addition to the resol.
/ Concerning the use of PPN mixtures. hexa
The amount of addition is a small amount that is necessary only for improving the resol. Comparative Examples 8 and 9 relate to the use of PFR/PPN mixtures in which large amounts of hexa are added before or during the grafting operation and various amounts of water are removed from the novolak before addition to the resol component. .

In these comparative examples, ``without rhexa'' means that nothing other than a small amount of hexa for resol is added, and ``with rhex'' means that a sufficient amount of hexa to act in the graft reaction is added. .

As you can clearly understand, in the operation of these comparative examples,
It is not possible to produce a plate that is satisfactory.

Comparative example! This example is a reproduction of the operation described in Example 3 of JP-A-53-75294.

Phenol 9409 (
10 moles), 1214 g (17 moles) of 42% formalin (formaldehyde aqueous solution), and 419 trisodium phosphate to prepare a resol precondensate.

The mixture was refluxed for 1.5 hours. The obtained dried persimmon mixture (21
96 g) had a resin content of 50% and a volatile content of 50%.

Separately, the same reactor was charged with 940 g of phenol, 571 g of 42% formalin, and 9.49 g of oxalic acid, and the mixture was refluxed for 2 hours, yielding 15189 novolak resin precondensate.

The total amount of resol precondensate (2196 g) was added to 844 g of novolac precondensate, and the resulting mixture was reacted under reduced pressure to remove water and unreacted phenol until the temperature reached 90°C. At this point the reaction mixture gelled. The reaction mixture was then taken out of the reactor and cooled, yielding 2896 g of semi-solid gel.

This resin was molded into a plate in the same manner as described above.

This plate has underfilled corners, underfilled sides, stitch lines, and central holes, making it completely unsatisfactory for subsequent processing into vitreous carbon.

Comparative Example 2 The operation described in Example 4 of JP-A-53-75294 was repeated.

Novolac resin 15 produced by the same operation as in Comparative Example 1
725 g of resol resin was added to No. 139. The mixture was processed as in Comparative Example 1, yielding 1452 g of solid resin. The gradient end bar melting point of this resin is 82℃
(180″F) and exhibited a rubbery cure in 30 seconds at 166°C (330°F).

When this resin was molded into plates as described above, the same unsatisfactory results as in Comparative Example 1 were obtained.

Comparative Example 3 The operation described in Example 1 of Rice Patent No. 3,998,906 was repeated.

In a reactor equipped with a temperature control device and a reflux device,
USPS Efur 1177 parts 95% paraformaldehyde (5% water) 395 parts water to make paraformaldehyde equivalent to aqueous formaldehyde 1759 parts
parts and 200 parts of 50% Na0Il aqueous solution were mixed. First, the first three ingredients were mixed and a small amount of NaOH aqueous solution was added to dissolve the paraformaldehyde. The temperature was raised to 50-55°C and the remainder of the Na0l+aqueous solution was added. The temperature was then raised to 90 °C and the mixture was allowed to react for 30 minutes, after which the temperature was lowered to 80-85 °C and the mixture was reacted for 6
The reaction continued for 0 minutes. The product was then cooled to room temperature.

Pre-electrocombinant B (resol) was added to U in a similar reactor.
1177 parts of SPS Efur, 925 parts of 95% paraformaldehyde, 2177 parts of water and 1 part of 50% NaOH aqueous solution
809. In the same way as above,
However, if the initial heating is performed at 80-65℃, the remaining N
After adding the aOH solution, reduce the temperature to 50-55 °C,
The operation was carried out with the reaction lasting for 120 minutes.

The reaction was then heated for 45 minutes before cooling the reaction product to room temperature.
Continued for an additional 60 minutes at -50°C.

Precharged coalescence A (938 parts) and precharged coalescence B (938 parts) were added to a similar reactor along with 33.8 parts of 50% NaO solution until the viscosity of the reaction mixture (measured at 25°C) was 2.
160-2520Kg/m-h (600-700ce
85°C for a sufficient time to reach
It was maintained at -87°C. Then, the reaction temperature was increased to 75-80°C.
90.2 parts of 50% NaOH aqueous solution was added, and the viscosity of the resulting resin (1K constant at 25°C) was 1440-
1800 K9/ m-h (400-500 centi
react at 75-110°C until reaching (poise),
At this point the resin was allowed to cool to room temperature.

Three plates were formed from this resin using the procedure described above. None of these were satisfactory. That is, three of these plates all had underfilled angles and porosity, and two had underfilled sides and stitch lines or holes.

Comparative Example 4 (a) In an apparatus as used in Example 1, USP Phenol 20009 (21,28 mol), formaldehyde aqueous solution (52%') 8229 (15,28-F-1), water 200B and phosphoric acid (85 mol) were added. %) 29 (0,10 mol)
filled with.

The mixture was then heated to reflux for a total of 5 hours. At this point, replace the reflux condenser with a distillation condenser,
The batch was distilled until the batch temperature reached 160°C.

To this mixture was added slowly over 36 minutes a 51% aqueous formaldehyde solution 1739 (3.0 mol) mixed with 70y of water. During the addition, the batch temperature decreased to 142°C. After adding the entire amount of formaldehyde aqueous solution,
The batch was held at 142-150°C for 15 minutes. The receiver on the distillation cooler was then replaced with a vacuum receiver to allow continuous removal of water. Reduce the degree of pressure reduction to 71cx (28
inch) Hg and distillation continued until 25% of the water (relative to the amount of water collected at 100% removal rate) was collected. This PFN product is then used as described below.

(b) In a four neck resin flask (4σ) equipped with a thermometer, reflux condenser, stirrer and stopper, add USP
142 g (12.15 mol) and 7999 (13.85 mol) of medium luminaldehyde aqueous solution (52%) were charged. This was cooled to 39° C. and 51.7 g of hexa and 5,339 (0,133 mol) of sodium hydroxide were added.

This mixture was heated to 90°C for 30 minutes and heated to 90°C for 30 minutes.
It was maintained for a minute. The reflux condenser was then replaced with a vacuum distillation apparatus and the batch was rapidly cooled to a temperature of 63° C. by vacuum distillation at 66 cm (26 inches) Hg. The variable resistor of the heating mantle was set to 56, and the phenol-formaldehyde novolak (P
FN) 2180? was added. During the addition, the temperature was slowly increased to 64°C. After the addition was complete, the vessel was closed and vacuum distillation was carried out to a temperature of 92°C at a vacuum degree of 66 cm (26") g. At this point, the continuous reading wattmeter attached to the drive motor read at speed setting 5. So 110
It was Watsuto.

Three plates were prepared from this resin by molding as described above. All three plates had various drawbacks. That is, all three had pores and were porous, two had underfilled sides, and one of these two also had underfilled sides.

Comparative Example 5 Similar to Comparative Example 4, except that 41% of water was added from the novolac (PFN) prior to addition to the resol in step (b).
The operation was carried out by removing 09 (50%). Five plates were prepared by molding the obtained resin in the same manner. Four out of five were unsatisfactory. 3 of these have porosity, the rest have pores and underfilled corners, 2 of the 3 have underfilled sides, and the remaining 1 has underfilled corners. It had a department.

Comparative Example 6 Similar to Comparative Example 4, except that 70% of water was added from the novolac (PPN) prior to addition to the resol in step (b).
The operation was performed to remove 59 (75%).

A plate was prepared by molding the obtained resin in the same manner, but
It was unsatisfactory as there were corners that were underfilled and sides that were underfilled.

Comparative Example 7 Similar to Comparative Example 4, except that 94% of water was added from the novolac (PFN) prior to addition to the resol in step (b).
The operation was performed with 0 g (100%) removed. The resulting resin is pulverizable, but when two plates were prepared by molding as described above, they had holes in the center, underfilled corners, and underfilled sides. , which was completely unsatisfactory due to its porous nature.

Comparative Example 8 (a) USP Phenol 15009, Water 1669, Hexa 1009, Water 18
009 and 364 g of paraformaldehyde (95%) were charged. Heat was generated when a small amount of caustic solution was added. Slowly add the remaining caustic solution and bring the mixture to 9.
It was heated to 0°C and maintained at this temperature for 30 minutes. At this point the mixture was cooled to 85°C and maintained at this temperature for 60 minutes. Distillation is then carried out under atmospheric pressure until 2649 g of water (corresponding to 25% of the amount of water collected if all water is removed) is collected, at which point the product (solids content 45.5%) was cooled and used in step (b) below.

(b) In a 4-necked resin flask (4Q) equipped with a thermometer, reflux condenser, stirrer, and stopper, add USP Phenol 1
1429 (12.15 mol) and 799 g (13.85 mol) of formaldehyde aqueous solution (52%) were charged. This was cooled to 39° C. and 51.7 g hexa and 5.33 g (0.133 mol) of flaked sodium hydroxide were added. The mixture was heated to 90°C for 30 minutes and maintained at 90°C for 30 minutes. Then, the reflux condenser was replaced with a vacuum distillation apparatus, and the batch was heated to a vacuum degree of 66 cx (26
The mixture was rapidly cooled to a temperature of 63° C. by vacuum distillation with Hg. Phenol-pormaldehyde novolac (PFN) prepared in step (a) above is added to this mixture.
20459 was added. After the addition was complete, the vessel was closed and vacuum distillation was carried out to a temperature of 70°C at a vacuum degree of 61 cx (24″) Hg. At this point, the continuous read wattmeter reading on the drive motor was at speed setting 5. 110 watts.The resin was removed to a dish and cooled.

The obtained grafted resin was blended and molded according to the method described above to prepare four plates, but none of them were satisfactory. Both have holes, and two
The pieces had stitch lines, central holes, and slightly underfilled corners.

Comparative Example 9 The operation was carried out as in Comparative Example 8, except that 50% of the water was removed from the novolac before it was added to the resole component in step (b). Three plates were prepared by blending and molding the obtained grafted resin according to the method described above, but none of them were satisfactory. All three had underfilled corners and holes, and one also had underfilled sides.

Comparative Examples IO to 13 below differ in the amount of water removed from the novolac before addition to the resol component, and an amount of hexa is added that affects the resol but not the grafting. PFR/P
It concerns the use of FUN. In none of these examples does a satisfactory plate be produced.

Comparative Example 10 (a) In a resin container (412) equipped with a stirrer, distillation condenser, heating mantle and thermometer, USP Phenol 20
009 (21,28 mol) and furfural 1480 g
(15.25 mol) was charged. The mixture was heated to 65° C. and sodium carbonate 3Q, Q9 (0.36 mol) was added. The charge was then slowly heated to 120°C, at which temperature the heating mantle was removed. The reaction was exothermic and the temperature continued to rise until boiling began at 135°C. Until 64.79 of water (25% of water) has been collected.
The distillate was collected in a fractionator with the furfural being returned to the reaction mixture. Reduce temperature, emery oil 20
9 was added and stirred for 5 minutes. The resulting resin was discharged from the container and stored until use in step (b) below.

(b) Phenol 114 was added to a four neck resin flask (412) equipped with a thermometer, reflux condenser, stirrer and stopper.
29 (12,15 mol) and formaldehyde (52%
) 7999 (13,1115 mol) was charged. The mixture was heated to 90°C for 80 minutes and held at 90°C for 30 minutes. Then, the reflux condenser was replaced with a vacuum distillation apparatus, and the patch was rapidly cooled to a temperature of 63 °C by vacuum distillation with 66 cz (26") Ig. The variable resistor of the heating mantle was set to 56. Phenol-furfural novolak (PPUN) from step (a) 1
667g was added. During the addition, slowly increase the temperature to 6
The temperature was increased to 4°C. After the addition is complete, close the container and
Vacuum distillation was carried out at a reduced pressure of 66 ci (26") Hg to a temperature of 92°C. At this point the continuous reading wattmeter attached to the drive motor was reading 11 O watts at speed setting 5. It was taken out and allowed to cool.

The resulting resin was molded as described above to prepare five plates. These five plates were incomplete, with t) misalignment, underfilled corners, underfilled sides, and stitch streaks.

Comparative Example 11 The operation was carried out similarly to Comparative Example IO, except that 50% of the water was removed from the novolac (PFUN) prior to addition to the resol in step (b).

The resulting resin was similarly molded as described above to prepare five plates, four of which had underfilled corners, underfilled sides, and stitch lines; 3
All of them were unsatisfactory, with some having swelling.

Comparative Example 12 Similar to Comparative Example 10, except that 7 ml of water was added from the novolac (PFUN) prior to addition to the resol in step (b).
The operation was carried out by removing 5%. The resulting resin was molded in the same manner as described above to prepare four plates. All four plates have corners that are insufficiently filled,
All of them were unsatisfactory, with underfilled sides and stitch lines, three of which also had bulges, and one of these three also had holes.

Comparative Example 13 The procedure was as in Comparative Example 10, except that all (100%) of the water was removed from the novolak (PFUN) prior to addition to the resol in step (b). The resulting resin was molded in the same manner as described above to prepare four plates. All four plates had underfilled corners and stitch lines, and three of them also had bulges, so all were unsatisfactory.

Examples 18 to 21 below describe he
This invention relates to the use of PFR/PFUN supplemented with xa. Various amounts of water are removed from the novolak (PFUN) prior to addition to the resole component.

Plates obtained from these resins are quite satisfactory.

Example 18 (a) Phenol-
Furfuraldehyde novolac (PFUN) was prepared.

(b) Phenol 11
42 g (12,15 mol) and formaldehyde (52
%") 7999CL 3.85 mol) was charged.

The mixture was cooled to 39°C and flaked NaOH5,33
9 was added. The mixture was heated to 90°C for 30 minutes and maintained at 90°C for an additional 30 minutes. Then, the reflux condenser was replaced with a vacuum distillation device, and the degree of vacuum was 86cz (26″).
The batch was rapidly cooled to a temperature of 63°C by vacuum distillation with Hg. The heating mantle variable resistor was set to 56 and 1667 g of phenol-furfural novolak (PFUN) from step (a) was added. During the addition,
The temperature was slowly increased to 64°C. After the addition was complete, the vessel was closed and vacuum distilled to a temperature of 90° C. at a vacuum of 66 cx (26″) Hg. At this point the continuous read wattmeter attached to the drive motor read: At speed setting 5: 120 watts.The resin was taken out into a dish and cooled.

The resulting resin was molded as described above to prepare five plates. Two plates had no defects and 1
One had very few bubbles and no pitting defects, and the other two had underfilled corners.

Example 19 (a) Phenol-furfuraldehyde novolak (PFUN) was prepared according to step (a) of Comparative Example 10, but with 50% of the water removed in the water removal step.

, (b) in a separate reactor, step (b) of Example 18.
The procedure was carried out according to the same procedure, except that instead of the novolak used in Example 18, the novolak prepared in step (a) above was used. Three plates were prepared from the resin thus obtained by molding according to the method described above.

None of these three plates had any defects.

Example 20 (a) Phenol-furfuraldehyde novolac (PFUN) was prepared according to step (a) of Comparative Example 10, but with 75% of the water removed in the water removal step.

(b) In a separate reactor, the operation was carried out according to step (b) of Example 18, but using the novolak prepared in step (a) above instead of the novolak used in Example 18. From the resin obtained in this way,
Three plates were prepared by molding according to the method described above.

Two of the plates had no defects and the remaining one had only very slight underfilled corners.

Example 21 A grafted PFR/PFUN was prepared according to the method of Example 8 with substantially complete removal of water from the novolac. Eight plates were prepared from this resin. None of these eight plates had any defects.

Table B shows the results for the plate moldings obtained in Comparative Examples 1 to 13 and Examples 18 to 21.

As shown in the comparative examples and examples, in each case the resol/novolac ratio is 60/40. On each side, the resol is a phenol-formaldehyde resol (PFR). The symbols in the table are as described above.

(flame dyed ζ decay door (ζ body: mi (moxibustion concentration: 0 (u'kf'J
Ln COh
CD ■k Moxibustion door dyeing condensation adjoining door ζ
Dye (+i 1)
Wipe-j Sissy Go Ko Go Go 啄c'eao■ Low cry QP! r u ull
1 i l i and 44--wh connection + appetizer (welfare construction construction dyeing) As is clear from examining the results reported in Table B above, in PFR/PPM mixtures (those with and without hexa added) None of them can produce a graft copolymer that can be molded as described above to produce a defect-free plate, in other words, a plate that is satisfactory for carbonization into a vitreous carbon plate in the next step (Plate No. 12). except for).

In short, only 1 out of 23 plates produced is satisfactory.

Similarly, the resin combination is PFR/PFUN and h
If exa is not added, the generated plate 1
None of the seven were defect-free, and no plate was prepared that was satisfactory for carbonization into a glassy carbon plate in the next step.

When hexa was added during grafting of PFR/l'FUN, out of 19 plates produced, only 3 were unsatisfactory with 1 defect, and 1 was borderline. The other 15 have no defects and are satisfactory for carbonization into glassy carbon plates.

In other words, 95.8% of PFR/PFN plates (with and without hexa doping) are unsatisfactory and have defects that make them unsuitable for subsequent carbonization into glassy carbon plates. have. Similarly, PFR/
If hexa is not added during grafting of PFUN resin, all 17 out of 17 plates (100%) prepared are unsuitable for subsequent carbonization into glassy carbon plates. have.

In contrast, with the PPR/PFUN mixture of the present invention in which at least 25% of water has been removed from the novolak and sufficient hexa has been added for grafting, only 3 or 4 of the 19 molded plates (15,8
% or 21%) with defects, the remaining 84.2%
Or 79% have no defects. The water removed from the novolak before use in the grafting reaction is 50-75
% (which is a more preferable range), only 1 out of 6 plates (17%) has defects, and the remaining 83% have no defects, and the vitreous carbon It is satisfactory in terms of carbonization. Additionally, as noted above, substantially 100% of the water is removed from the PFUN prior to addition.
is removed, the plate is 100% defect-free and suitable for subsequent carbonization into a glassy carbon plate.

In view of the above, at least 25%, advantageously at least 35%, of the water present during the novolak preparation before addition of the resol components to the mixture or at the initial stage of resol production;
The use of a graft reaction product of phenol-furfuraldehyde and formaldehyde-phenol resol, preferably with at least 50% or 75% removed, is considered optimal. Similarly, substantially all of the water is removed prior to such addition.

As mentioned above, amines can also be used in place of hexa. Such amines must have one or more nitrogen atoms to which at least one hydrogen is attached. It is clear that in the reactions described here only one reaction occurs per nitrogen atom to which a hydrogen is attached. he
In the case of xa, even if there is no bonding hydrogen,
There are 4 nitrogen atoms available for reaction. Therefore, he
One equivalent of xa has a molecular weight of 174, or 140/4 (
35). For other amines, one equivalent corresponds to the molecular weight of the amine divided by the number of nitrogen atoms to which at least one hydrogen is attached. For example, 1 equivalent of ethylamine is 45
/1, that is, 45. 60 for ethylenediamine
/2, that is, 30.

Example 22 Examples 1.8, 13 and 16 were carried out using the following amine in place of 57.1 g (0.41 mol) of hexamethylenetetramine from Example 8.

(a) Ethylamine 7:(,49(b) Dimethylamine 73.49(C) Aniline
152.59(d) Ethylenediamine 49.
29(e) Phenylenediamine 88.69(f) N
, N'-dimethyl-phenylenediamine 111.59 (g) N-methylaniline 175.49 (h)
lf, N'-dimethyl-ethylenediamine 72.29 (i) Propylene diamine 65.69 (D Piperylene 139.49 (k) Piperazine 7
7.19 In either case, a graft copolymer was obtained in the same manner as in Example 8 and molded in the same manner.
Defect-free plates were produced, which were successfully carbonized into vitreous carbon plates by operating similarly to Example 14.

Although the features of the invention have been described in detail with respect to various embodiments, it will be obvious that other modifications may be made within the spirit and scope of the invention, and the invention is of course not limited thereto.

[Brief explanation of drawings]

The figure is a gel permeation chromatogram illustrating the properties of the novolac-phenol reaction mixture of the present invention. (Measure)

Claims (1)

Claims: 1. In a moldable composition having improved mold flow properties, an aqueous solution or suspension of a phenol-aldehyde resol resin contains a compound removable from the aqueous solution or suspension of the resol resin. Before 90% of the water is removed, add phenol-aldehyde novolac resins in which at least 50 mole % of the aldehydes are composed of furfuraldehyde, provided that the amount of these resins is 20-80 parts by weight of said novolak resin and said 20-80 parts by weight of resol resin, 100 parts by weight in total, and then the resin,
hexamethylenetetramine and at least 1 nitrogen atom
Hexamethylenetetramine 1-
15% by weight and is prepared by removing water from the resulting reaction mass while maintaining the resin in a moldable state, said novolak resin being removable during novolak preparation. A moldable composition, characterized in that it has been prepared by removing at least 25% by weight of water. 2. The composition according to claim 1, wherein the amount of the amine is 1-10% based on the total weight of the phenol component.
% by weight of the moldable composition. 3. The composition according to claim 1 or 2, wherein the amine is hexamethylenetetramine.
Moldable composition. 4. The moldable composition of claim 1, wherein the amine is hexamethylenetetramine and the phenolic component of the novolac is phenol. 5. The moldable composition according to claim 4, wherein the phenolic component of the resol is phenol and the aldehyde component of the resol is formaldehyde. 6. A moldable composition according to claim 5, wherein the furfuraldehyde content in the novolac is at least 75 mole % of the aldehyde component. 7. The moldable composition of claim 5, wherein the furfuraldehyde in the novolac is approximately 100 mole percent of the aldehyde component. 8 Claims 1, 2, 4 to 7
A moldable composition according to any one of the preceding paragraphs, wherein the addition of the novolak is carried out after sufficient refluxing to substantially complete the reaction of the resole aldehyde. 9. A moldable composition according to claim 7, wherein the novolac is added before the initiation of water removal from the aqueous solution or suspension of resole resin. 10. The moldable composition of claim 7, wherein the novolac is added before 25% of the water is removed from the aqueous solution or suspension of resole resin. 11. The moldable composition of claim 7, wherein the novolac is substantially completely water-free prior to addition. 12. The composition of claim 7, wherein at least 50% by weight of the water present in the novolac preparation is removed before addition. 13. The composition of claim 7, wherein at least 75% by weight of the water present in the novolac preparation is removed before addition. 14. A moldable composition according to claim 4, comprising 40-316 parts of finely divided carbonaceous filler per 100 parts of resin. 15 Claims 4, 8, 12, 1
In the composition according to any one of paragraphs 4 and 15, 40-150 parts of finely divided graphite per 100 parts of resin.
A moldable composition comprising: 16. In the composition according to any one of claims 1, 2, or 4 to 15, the weight ratio of the resol resin/the novolak resin is 70/3.
A moldable composition ranging from 0 to 50/50. 17. A moldable composition according to any one of claims 1, 2, or 4 to 15, wherein the amine is added before or simultaneously with the addition of the novolac. 18. A moldable composition according to any one of claims 4 to 15, in which hexamethylenetetramine is used in a proportion of 1 to 5% by weight relative to the weight of the resin product. Composition. 19 Claims 1 to 18 of a method for manufacturing a molded product that is substantially free of depressions and holes and hardly cracks or breaks during manufacturing and use. The composition according to any one of the above is heated at a temperature of 10
0 to 180℃ and pressure 35kg/cm^2 (500
lb/inch^2) or 2800kg/cm^2(
Characterized by molding at 20 tons/inch^2),
Manufacturing method for molded products. 20 In the manufacturing method described in claim 19, the molded product has a thickness of 0.10 to 0.13 cm (0.04-0.
．． 05 inch) plate, a method for manufacturing a molded product. 21. A method for manufacturing a molded article according to claim 19, wherein the molding is performed at a pressure of 56 to 105 kg/cm^2 (800 to 1500 pounds/cm^2). 22 Claims 19 to 21 provide a method for producing vitreous carbon that is substantially free of depressions and pores and hardly cracks or breaks during production and use. The molded article obtained by the method described in any one of the paragraphs is gradually heated to a final temperature of at least 1800°C, and the molded article obtained by the method according to any one of paragraphs 1 and 2 is heated gradually to a final temperature of at least 1800°C,
A method for producing vitreous carbon, which is characterized by its ability to be maintained over time. 23 In the method according to claim 22, the vitreous carbon product has a thickness of 0.10 to 0.13 cm and other dimensions of at least 50.8 x 63.5 cm (20 x 2
5 inches). 24. The method of claim 23, wherein the other dimensions are about 50 x 50 inches.