JPH0762104B2 - Curing accelerator for phenolic resole resin - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to methods and compositions for promoting the cure of phenolic resole resin binder compositions which are cured with magnesium oxide or magnesium hydroxide alone or in combination with an ester functional curing agent. . Such curing can occur at about room temperature.

[0002]

BACKGROUND OF THE INVENTION Accelerating the cure of phenolic resole resins by using a lightly calcined magnesium oxide or magnesium hydroxide hardener alone or in combination with an ester functional hardener, ie the time required for its hardening. Shortening is often desirable, especially as long as such acceleration does not significantly affect the hardness, tensile strength and other desirable properties of the cured resin, especially in cold climates and low temperature conditions. There is.

In the present invention, magnesium oxide or magnesium hydroxide with or without ester functional hardener is used as the hardener. Applicants have shown that the curing of phenolic resole resin compositions mixed with a curing amount of lightly calcined magnesium oxide or magnesium hydroxide, alone or in combination with an ester functional curing agent, can be accomplished from a curing agent mixed with certain amines or resins. It has been found that it can be promoted by using a compound that improves the solubility of magnesium ions. Accelerators, for example,
It is a compound which gives various kinds of amino compounds such as chloride ion, sulfate ion and sulfamate ion and 2,4,6-tris (dimethylaminomethyl) phenol.

Lightly calcined magnesium oxide and magnesium hydroxide are well known room temperature curing agents for phenolic resole resins. Furthermore, magnesium oxide and magnesium hydroxide are also used as condensation catalysts when producing phenol formaldehyde resole resin from phenol and formaldehyde. Furthermore, relatively inert magnesia, such as periclene or refractory grade magnesia, is a common refractory that is often bonded to various shapes with phenolic resole resins, but this periclase is relatively inert. It is not used as a curing agent. References disclosing the use of magnesium oxide or magnesium hydroxide to cure the phenolic resole resin in each type of composition include, for example, US Pat. No. 2,869 of RH Cooper. , 1
No. 94 (January 20, 1959); Cooper No. 2,
869,196 (January 20, 1959); Cooper's No. 2,913,787 (November 24, 1959).
Sun); T. Murata et al., No. 3,66
No. 6,703 (May 30, 1972): J.S. Michell's No. 2,712,533.
No. (July 5, 1955); Adams (WH, Ada
ms, Jr.), No. 2,424,787 (1947).
No. 4,794,051 of M. K. Gupta (December 27, 1988);
Can be mentioned.

Gupta US Pat. No. 4,794,051 also points out the use of certain ester functional hardeners or lactones with magnesium hardeners, although admixtures with calcium hardeners are preferred. There is. Cooper's U.S. Pat. No. 2,869,194 discloses that magnesium oxychloride and magnesium oxysulfate prepared by mixing magnesium oxide powder with magnesium chloride or its equivalent or an aqueous solution of magnesium sulfate or its equivalent is magnesium oxide alone. It also points out that the curing time is often shortened compared to. Cooper's U.S. Pat. No. 2,913,787 discloses the inclusion of "novolac-type" phenolic resins in its composition as an optional component, as well as hexamethylenetetramine or ethylenediamine, diethyleneamine and similar It is also pointed out to include an equivalent phenolic resin hardener or accelerator containing low molecular weight polyamines and para-formaldehyde.

US Patent Application No. 450,989 entitled "Phenolic Resin Composition" (Application December 1, 1989)
5th, Inventor Lemon (PHRB Lemon),
King (J. King), Leoni (H. Leoni),
G. Murray and Jarber (A.H.
Gerber); GB882984.7 (Application 88: 1)
(February 22)) prepares a phenol resin by using an alkali metal compound or an alkaline earth metal compound as a basic catalyst, and then an esterified phenol resin as an ester functional curing agent and oxides of magnesium and calcium. And using various bases including hydroxides to cure the resin at room temperature. European Patent Application Publication No. 0094165 (published November 16, 1983, inventor Lemon (PHRRBL)
(emon) et al.) are listed extensively, and various alkaline materials including magnesium oxide (magnesia) for condensing phenol and formaldehyde to form a phenol-formaldehyde resin and further for increasing the alkalinity of such resin. The use is pointed out and an ester functional agent is used to cure the phenolic resin. European Patent Application Publication No. 0243,172 (1987)
(October 28, 2010, Inventor Lemon, et al.), As well as European Patent Application Publication No. 0094165, cited above.

US Pat. No. 4,939,188 (199)
Announced on July 3, 0, Inventor Jarber (AH Ger
ber) discloses the use of an alkalizing agent that generates lithium ions in the resole resin binder composition, which when cured with an ester functional curing agent generates sodium or potassium ions. Exhibits a tensile strength superior to that of the composition using the alkalizing agent.

Higgenbotto
m) U.S. Pat. No. 4,011,186 (March 1977).
May 8th) and Dahms, No. 4,21
No. 6,298 (August 5, 1980) relates to a phenol resole resin neutralized with oxalic acid or an acid salt thereof using an alkaline earth metal hydroxide as a catalyst. Is dispersed in the resole as a stable, insoluble oxalate salt, further increasing the viscosity of the resole resin.

US Pat. No. 3,624,247 to Gladney et al. Relates to the removal of residual calcium catalyst used in the production of phenolic resins. Residual calcium catalyst is removed by treatment with an alkaline solution of ammonium salt and adjusting the pH to form an insoluble salt containing calcium. U.S. Pat. No. 3,624,247
As the soluble ammonium compound used in the publication No. 3, sulfates, phosphates and carbonates are indicated.

US Reissue Patent No. 32,720 to Lemon et al.
No. 32 (July 26, 1988) and No. 32,812 (December 27, 1988) are further literature examples,
Disclosed is room temperature curing of a highly alkaline phenol formaldehyde resin with an ester curing agent. JP 60-90251 (May 21, 1985, Kyushu refractories) discloses cold curing of thermosetting resol resins by using ethylene carbonate and magnesium oxide.

US patent application Ser. No. 07 / 562,206, the parent of the present application, discloses materials such as various anions for retarding the cure of phenolic resole resins with a magnesium hardener.

[0012]

Room temperature curing of phenolic resole resin compositions in which a curing amount of a lightly calcined magnesium oxide or magnesium hydroxide, alone or in combination with an ester functional curing agent, has been determined. It has been found that this can be facilitated by materials that improve the solubility of magnesium in the reaction mixture. Further, when lightly calcined magnesium oxide having a relatively small surface area is mixed with magnesium oxide having a large surface area, there is almost no accelerating effect exceeding the curing rate of the phenol resin composition based on the large surface area material, but the composition during thermosetting Lithium carbonate has both the function of an accelerator and a strength improver of a phenolic resin composition; and the use of a sulfamate accelerator in a low molecular weight phenolic resin having a high free phenol content It was also found that the strength is improved. The phenolic resole resin used in the present invention is
It generally has a pH of about 4.5 to 9.5.

One aspect of the present invention is a binder composition having reduced curing time by mixing a phenolic resole resin with a magnesium curing agent and / or accelerator with or without an ester functional curing agent and a binder composition thereof. It is to provide a preparation method. Another aspect of the invention is to patch or repaint various rigid substrates such as concrete and asphalt structures using the compositions and methods described above with aggregates.

Another aspect of the present invention is to provide a shaped article, wherein the shaped article is a combination of aggregates bonded together with a resin binder, where the binder is accompanied by an ester functional hardener. A phenol formaldehyde resin cured in the presence of a magnesium hardener and an accelerator without it.

[0015]

As an example of the accelerator, a material which gives a chlorine ion, a sulfate ion, a sulfamate ion, or a phosphite ion corresponding to a basic nitrogen compound and an acid addition salt of a compound represented by the following formula: Can be mentioned. In the above formula, X is a lower aliphatic hydrocarbon group, and R ¹ and R
² is an alkyl group or, together with the nitrogen to which they are attached, forms a heterocyclic group, R ³ and R ⁴ are hydrogen or an alkyl group, or when combined with the nitrogen to which they are attached, a heterocyclic group. Form a ring group.

The methods and compositions of the present invention use a small amount of amine or various compounds that enhance the solubility of magnesium in a resin composition to accelerate the curing of the resin, thereby curing the phenolic resole resin with a magnesium curing agent. Speed up to about 15.6-48.9 ° C (60-120 °
It provides a means to facilitate over a wide temperature range such as F). One of the variables that affects the curing rate of phenolic resin is temperature. If the temperature is low, the curing speed will decrease. The accelerators of the present invention can be used to accelerate the cure rate over a wide temperature range, such as room temperature and ambient temperature, especially in cold climates and cold workplaces. By using the accelerator of the present invention, it is possible to accelerate the curing rate at a low temperature, and to develop an appropriate strength while maintaining a desired processing time.

The methods and compositions of the present invention allow for the selection of the magnesium surface area to be used, the selection of a particular accelerator, and optionally the amount of a particular ester and hardener and accelerator. Can influence the reaction rate of the phenol resole resin.

The preferred methods and compositions of this invention use an ester functional hardener in combination with a magnesium hardener. When the ester is used in combination with the mildly calcined magnesia or magnesium hydroxide curing agent and the accelerator,
This is because the reaction rate of the phenol resin composition is strongly influenced. Further, the phenol resole resin cured by using both the magnesium curing agent and the ester functional curing agent has a larger compressive strength or tensile strength than the phenol resol resin cured by magnesium oxide or magnesium hydroxide alone, and The resistance to organic acid aqueous solution is also large.

The methods and compositions of the present invention are described in US Reissue Patent No. Re 32,720 to Lemon et al. (July 26, 1988).
Sun) and Lemon et al., No. 32,812 (198).
It has a number of advantages over curing a phenolic resole resin with an ester alone as shown in Dec. 27, 8). The methods and compositions of the above-mentioned US Reissue Patent require an alkali metal hydroxide, and in practice the pH of the resin is 1
It is 2 or more. In contrast to this, the pH in the present invention
The values are substantially lower and do not require alkali metal hydroxides or their salts. The above-mentioned US reissue patent has pH 1
The compositions and methods of the present invention have a number of advantages over requiring a high alkalinity of 0 or 12 or more, especially high alkali metal concentrations for highly alkaline compositions. Is. For example, the phenolic resins of the present invention have better storage stability; improved color stability of the resin over time and upon exposure to the atmosphere; low viscosity even at high solids levels and therefore especially aggregates. And wettability of base materials and bond strength are increased; safer handling of materials and wastes; density when curing high solids level resins, compositions such as aggregates High and low porosity, thus improving strength and resistance to solvents and aqueous media; and improved stability of aggregates normally attacked by high pH sodium and glass fibers and polyesters It has properties such as improved stability to fibers. Excess alkali can result in strength loss. For example, according to Table 4 of US Reissue Patent No. Re32,812, such as Lemon, a KOH / phenol molar ratio of 0.68 (34.6) was obtained.
7 MPa, 5032 psi) to 1.02 (29.
When it is increased to 43 MPa and 4271 psi), the compressive strength of the resole resin steadily decreases. In contrast, excess magnesium hardener enhances the strength and insolubility of the final composition. This is because the use of sodium or potassium alkali causes chain termination, whereas divalent magnesium causes crosslinking.

Accelerators are used to reduce stripping time of molding and casting materials, or merely to improve cure rates, especially at temperatures significantly below 21.1 ° C. (70 ° F.). It is advantageous.

Magnesium oxide and magnesium hydroxide
Curing agent

The term "accelerator" as used in the present invention refers to a method and composition of the present invention such as a curable binder containing a phenolic resole resin, a magnesium hardener and an optional ester functional hardener. It refers to a material that accelerates or simply accelerates the gelling or curing of a phenolic resole resin. It appears that some of the accelerators of the present invention have the function of altering the solubility of the magnesium compound in the curable mixture to increase the amount of magnesium or magnesium compound in the solution.

The term "curing agent" as used in the present invention refers to a material which enhances the curing rate of phenolic resole resins, for example at room temperature or ambient temperature (RT). Curing is
This is achieved by gelling, which generally forms an inflexible solid with increased viscosity and firm feel. The curable binder composition of the present invention comprising a phenolic resin, a magnesium hardener and an optional ester functional hardener, but no accelerator, generally comprises 23.9 ° C (75 ° F).
It becomes hard when left for about 24 hours. This cure (hard
Ening can also be referred to as curing, but curing with a curing agent does not develop the tensile strength or compressive strength of thermal curing.

The term "room temperature cure" refers to compositions of the present invention at about 18.3 to 32.2 ° C (65 to 90 ° F), especially about 18.3 to 26.7 ° C (65 to 80 ° F). ) It means that it hardens at the temperature. However, the use of accelerators in the methods and compositions of the present invention results in 15.6-4.
Lower and higher temperatures, such as 8.9 ° C. (60 to 120 ° F.), accelerate curing of the compositions of the present invention. About 15.6
In addition to room or room temperature curing at 60 to 120 degrees Fahrenheit (60 to 120 degrees Fahrenheit), the composition of the invention may be thermally cured after curing with a curing agent, or thermally before curing with a curing agent. It can also be cured. The term thermal curing as used herein is 76.
Temperatures above 7 ° C (170 ° F), typically 100 ° C (2
It means that the composition is cured at a temperature of 12 ° F. or higher.

Magnesium hardeners are magnesium hydroxide, lightly calcined magnesium oxide or other magnesium oxides whose hardening activity for phenolic resole resins is that of lightly calcined magnesium oxide, for example 10 m ^2.
Magnesium oxide having a surface area of / g or more. Lightly calcined magnesium oxide is the preferred magnesium hardener and magnesium hydroxide gives the cured composition low strength. A small amount of calcium hydroxide, calcium oxide or calcined dolomite (doloma) can be added as a hardening agent. However, calcium oxide,
The use of calcined dolomite or calcium hydroxide alone or in large amounts in combination with a magnesium hardener brings serious defects. That is, calcium-based oxides or hydroxides containing calcined docomite are strongly basic and react excessively quickly, greatly shortening the pot life of the mixture. However, a small amount of a calcium-containing compound, such as a magnesium hardener weight of less than about 1 to 50%, mixed with a magnesium hardener can be used in place of an equal weight of magnesium hardener. This amount is approximately 1/1 of the total weight of the magnesium oxide or magnesium hydroxide hardener.
A small amount not exceeding 4 is preferred. A further disadvantage of using calcium-based oxides is the insolubilization of certain promoters.

The reactivity and surface area of magnesium oxide (magnesia) differ greatly depending on the method of making magnesia. Light firing grade magnesium oxide is about 871 to 982 ° C
Calcined at a temperature in the range (1600 to 1800 ° F). Heavy firing grade is about 1538 to 1649 ℃ (2
Calcined at a temperature in the range of 800 to 3000 ° F.
Dead burned grade or periclase grade magnesium oxide is 2204 ° C (400
Calcination at temperatures above 0 ° F. Lightly calcined grades are generally available in powder or granular form, and heavily calcined grades are available in kiln runs, grinds or sieve sizes. Periclase is generally available as a briquette and as a sieve or ground fraction. The surface areas of these various magnesiums differ significantly. That is, lightly calcined magnesia has a surface area of about 10 to 200 square meters or more per gram, and lightly calcined magnesia has a surface area of about 1 square meter per gram. On the other hand, the surface area of dead-burned magnesia is less than 1 m ² / g. Dead-burning magnesia or periclase magnesia, which are commonly used as refractory aggregates. However, neither heavy-baked magnesia nor dead-burned magnesia is an effective curing agent. An effective hardener is lightly calcined magnesia. Magnesia products with different surface areas are available from Martin Marietta Compan.
y) to MagChem Magnesium Oxide
It is available under the trade name of Products). For example, Magukemu 30 has a surface area of about ^{25 m} 2 / g, Magukemu 50 whereas with a surface area of about ^{65 m} 2 / g, the surface area of Magukemu 200D is about 170m ² /
It is g.

One of the variables for viscosity increase, gel formation and subsequent curing of the phenolic resole resin is the surface area of the light calcined magnesium oxide. Magnesium oxide is more active at higher surface areas and reduces gelling and hardening times. Therefore, the lightly calcined magnesium oxide having a surface area of less than about 25 m ² / g has a slow action, and the activity is about 48.
It is generally not used when it is desired to cure the binder composition for a relatively short time at temperatures below 9 ° C (120 ° F). On the other hand,
High surface area magnesia, such as about 62 m ² / g or more, cures the same binder composition in less time. For many applications it is preferred to use magnesia with a surface area of about 25 to 65 m ² / g. Heavy-baked magnesia reacts too slowly as a curing agent and has no practical value. Dead-burned magnesia is so inert that it is usually used only as a refractory, and when used in phenolic resin binders it has little or no effect on room temperature cure rates.

The phenolic resole resin of the present invention contains at least one volatile solvent containing water. Loss of solvent in the thermally cured composition increases porosity, increases liquid permeability and reduces strength. One means of increasing strength and reducing porosity is to use large amounts of lightly calcined magnesium oxide hardener. However,
This results in an increase in viscosity and a reduction in gelling time.
By the way, it has been found that the use of lightly calcined magnesium oxide having two or more different surface areas brings about an improving effect such as improving strength without substantially promoting an increase in viscosity. The lightly calcined magnesium oxide curing agent that achieves the above-mentioned improvement effect is about 25 to 75% by weight.
Has a surface area of 50 m ² / g or more, of which about 25 to 7
5% by weight consists of particles with two or more different surface areas having a surface area of about 10 to 25 m ² / g. The magnesium oxide hardener for providing such an improving effect is preferably one essentially consisting of particles having two or more different surface areas as shown in the preceding sentence. According to the method using different surface areas, gelation at room temperature or room temperature is
Although it occurs in about the same time as when the high surface area curing agent was used alone, despite the substantially higher amount of curing agent present, the compressive strength of the composition upon curing is substantially improved, Porosity and permeability are reduced. In addition, compositions with increased magnesia have improved flame retardancy. Compositions containing lightly calcined magnesia of different surface areas optionally have the accelerators, ester functional hardeners and fillers, modifiers, aggregates and other additives of the present invention with different surface areas. It may be contained in the same concentration as in the case of the lightly calcined magnesium oxide containing no hardener mixture.

The amount of lightly calcined magnesium oxide or magnesium hydroxide used as the curing agent in the present invention is an amount sufficient to increase the rate of gelling or curing of the phenolic resole resin. This amount can vary widely. The amount of magnesium hardener used will vary depending on whether or not an ester hardener is used in the composition, the surface area of magnesium oxide, the specific ester hardener, the amounts of magnesium and ester hardener, the temperature and the desired effect. That is, the amount of magnesium oxide or magnesium hydroxide hardener generally varies from about 5% to 40% by weight of the resin for the various compositions and methods of the present invention. However, when using lightly calcined magnesium oxide mixtures of different surface areas, the amount of magnesium oxide is less than that of the resin.
It is preferable to change within the range of 50 to 50% by weight or more. When the magnesium oxide or magnesium hydroxide curing agent is used without the ester curing agent, it is used in an amount of about 10 to 40% by weight, particularly 15 to 30% by weight based on the weight of the resin.
It is preferably used in the range of wt%. When magnesium oxide or magnesium hydroxide is used in combination with an ester functional hardener, the amount of magnesium oxide or magnesium hydroxide hardener is in the range of about 5 to 30% by weight, especially about 5 to 20% by weight of the resin. It is preferable to change.

Ester Curing Agent Ester-functional curing agents, also called ester-functional curing agents, are used in combination with magnesium curing agents to accelerate the cure of the resole resin. Further, the system in which both the magnesium curing agent and the ester curing agent are mixed and used in the resole resin provides a curing system which is extremely sensitive to a small amount of the accelerator of the present invention. Mixtures of phenolic resole resins and ester-functional curing agents that do not contain magnesia or other alkalis do not cure at 21.1 ° C (70 ° F) for more than 7 days. The ester functionality that cures the phenolic resole resin can be imparted by lactones, cyclic organic carbonates, carboxylic acid esters, or mixtures thereof.

Generally, ester functional curing agents include:
Low molecular weight lactones such as beta- or gamma-butyrolactone, gamma-valerolactone, caprolactone, beta-propioclactone, beta-butyrolactone, beta-isobutyrolactone, beta-isopentyl lactone, gamma-isopentyl lactone and delta-pentyl lactone are suitable. Examples of suitable cyclic organic carbonates include propylene carbonate: nitylene glycol carbonate; 1,2-butanediol carbonate; 1,3-butanediol carbonate;
-Pentanediol carbonate: and 1,3-pentanediol carbonate. However, it is not limited to the above.

The carboxylic acid ester usable in the present invention includes phenolic ester and aliphatic ester. Aliphatic esters are those of short to medium chain length, eg about 1 to 1
Esters of 0-carbon mono- or polyvalent saturated or unsaturated alcohols with aliphatic, saturated or unsaturated mono- or polycarboxylic acids of short to medium chain length, for example about 1 to 10 carbons, are preferred. Preferred aliphatic esters are
Esters of mono-, di- or trivalent alkyl alcohols with mono- or di-unsaturated mono-, di- or trivalent carboxylic acids. This carboxylic acid may be substituted with a hydroxyl group, a cyano group, chlorine or bromine.

The aromatic ester can be obtained by esterifying a monovalent or polyvalent aromatic phenol group to prepare its formate ester or acetate ester. In addition, the aromatic ester contains one or more phenolic hydroxyl groups and / or
Or an esterified phenolic compound containing one or more esterified phenolic hydroxyl groups, and one or more esterified compounds located at ortho and / or para to the phenolic hydroxyl group or the esterified phenolic hydroxyl group It may further contain a methylol group. Such a phenol ester and a method for producing the same are described in U.S. Patent Application No. 450,989 (filed on Dec. 15, 1989, inventor Leon, same inventor GB8829984.
No. 7 (corresponding to December 22, 1988)), and both of the US patent and the UK patent are cited. Esterified phenolic compounds are phenols with one or more nuclei having one or more esterified methylol groups, wherein one or more esterified methylol groups are phenolic hydroxyl groups or esterified It is understood to be bound to the aromatic ring carbon atom in the ortho or para position of the phenolic hydroxyl group. The acid portion of the phenolic ester can be the same as the acid portion of the aliphatic ester.

Specific carboxylic acid esters include formic acid n-
Butyl: ethylene glycol diformate; methyl lactate; hydroxyethyl acrylate; hydroxyethyl methacrylate; n-butyl acetate; ethylene glycol diacetate; triacetin (glycerol triacetate); diethyl fumarate; dimethyl maleate; glutaric Dimethyl acid; dimethyl adipate; 2-acetyloxymethylphenol; 2-methacryloxyphenol; 2
-Salicyloyloxymethylphenol; 2-acetyloxymethylphenol acetate; 2,6-diacetyloxymethyl p-cresol; 2,6-diacetyloxymethyl p-cresol acetate; 2,4,6-triacetyloxy Methylphenol; 2,4,6-Triacetyloxymethylphenol acetate; 2,6-Diacetyloxymethylphenol acetate; 2,2 ', 6,6'-
Tetraacetyloxymethylbisphenol A; and 2,
There is 2 ', 6,6'-tetraacetyloxymethylbisphenol A diacetate. However, it is not limited to the above. Acetates derived from aliphatic alcohols of 1 to 5 carbon atoms; benzyl alcohol,
Preferred are formic acid esters and acetic acid esters of alaa, alaa-dihydroxy xylenol, phenol, alkyl-substituted phenol, dihydroxybenzene, bisphenol A, bisphenol F and low molecular weight resole.
Sometimes it is advantageous to use a mixture of ester functional hardeners.

The gas esters such as formic acid C ₁ to C ₂ alkyl esters, as ester functional hardening agent of low density products, or the binder can be used in applying to the fabric or paper substrate. When using a gas ester as a curing agent, the ester is generally not mixed with a resin binder or aggregate, but is fed to the shaped article as a gas, as is well known in the art.

The ester-functional curing agent is present in an amount that enhances the tensile and crimp strength of the cured composition. Such an amount also increases the curing rate of the phenol resole resin in the presence of the magnesium curing agent. This amount will vary over a wide range such as about 5 to 40% by weight of the phenolic resole resin, preferably about 10 to 25% by weight. With respect to the aforementioned magnesium hardeners, the exact amount will depend on the particular ester hardener used, the particular magnesium hardener used and its amount, the working concentration and storage temperature of the composition and the desired result.

Phenolic Resole Resins A wide range of phenolic resole resins are used in the present invention. These resins are phenol formaldehyde resole resins or some or all of the phenols replaced by one or more phenolic compounds such as cresol, resorcinol, 3,5-xylenol, bisphenol A or other phenols. And part or all of the aldehyde part can be acetaldehyde,
It can be replaced by fulleraldehyde or benzaldehyde. The preferred phenolic resole resin is the condensation product of phenol and formaldehyde. Resole resins are thermosetting and when heated form infusible three-dimensional polymers. Resole resins are typically produced by reacting phenol with an excess molar amount of a phenol-reactive aldehyde in the presence of an alkali metal compound or an alkaline earth metal compound as a condensation catalyst.

The phenolic resole resins suitable for use in the present invention have less than about 1% by weight of water soluble sodium or potassium, preferably 0.5% by weight or less. A typical phenolic resole resin has a molar ratio of phenol to formaldehyde in the range of about 1: 1 to 1: 3 (phenol:
It is a phenol-formaldehyde resin produced by reacting with formaldehyde). The preferred molar ratio for use in the present invention is about 1 mole of phenol to about 1 mole of aldecht.
It is in the range of 1 to 2.2 mol, in particular the phenol: aldehyde molar ratio is in the range of 1: 1.2 to 2. Phenolic resole resins are commonly used in solution.

The pH of the phenolic resole resin used in the present invention generally varies from about 4.5 to 9.5,
A pH of about 5 to 9, especially about 5 to 8.5 is preferred.
Typical amount of free phenol is about 2 to 25% by weight of resin
And the preferred level is 5 to about 12%. The weight average molecular weight of this resin is about 200 to 500.
It varies in the range of 0, and 300 to 2000 is preferable.
All other things being equal, the higher the molecular weight and the lower the free phenol, the shorter the gelling or setting time and the better the strength. Weight average molecular weight

(Mw) is measured using gel permeation chromatography and phenolic compounds and polystyrene standards. The sample for measuring the molecular weight is prepared as follows. A resin sample is dissolved in tetrahydrofuran, made slightly acidic with 1N hydrochloric acid or sulfuric acid, and dried over anhydrous sodium sulfate. The resulting salt is filtered off and the supernatant is passed through a gel permeation chromatograph.

The resin solids content in the resole resin varies over a wide range of about 50 to 90% by weight of the phenol resole resin. This resin solids content is preferably about 50 to 80% of the phenolic resole resin.

The phenol resol resin, or simply resin, has a viscosity of about 100 to 4,000 c at 25 ° C.
It can vary over a wide range of ps. This viscosity is about 3,000 cps at 25 ° C, especially about 250 to 2,000 at 25 ° C.
It is preferable to change in the range of 0 cps. The viscosity measurement in the present invention is performed by Brookfield R at 25 ° C.
It is given in centipoise (cps) measured with a VF viscometer or a Gardner-Holt viscometer at 25 ° C. Gardner-Holt viscosity specific gravity to centistokes (generally 1.
Multiplying by 2) gives cps at 25 ° C.

When the aggregate is used in the raw material batch composition, the amount of the resin based on the aggregate is based on the weight of the aggregate.
It can be varied over a wide range, preferably about 3 to 20% by weight, in particular 5 to 15%.

The liquid part of the resin is water or a mixture of water and a non-reactive solvent. The resin can contain various optional modifiers or additives such as silane, hexa or urea. Solvents added to water include alcohols of 1 to 5 carbon atoms, diacetone glycol, glycols of 2 to 6 carbon atoms, glycol mono- and dimethyl ethers or butyl ethers, low molecular weight (200-60O) polyethylene glycols and their methyl ethers, 6 to 6 15-carbon phenolic compounds, phenoxetanol, aprotic solvents such as N, N-dimethylformamide,
N, N-dimethylacetamide, 2-pyrrolidinone, N
-Methyl-2-pyrrolidinone, dimethyl sulfoxide,
It can be selected from tetramethylene sulfone, hexamethylphosphoramide, tetramethylurea, methyl ethyl ketone, methyl isobutyl ketone, cyclic ethers such as tetrahydrofuran and m-dioxane, and the like.

The typical water content of the resins used in the present invention varies from about 5 to 20% by weight of the resin and can therefore be referred to as aqueous.

The use of organofunctional silane contact promoters is recommended when the composition of the present invention contains silica-based aggregates such as silica sand, crushed candles and silicates, and bone-like aggregates such as alumina.

The organofunctional silane is used in an amount sufficient to improve the contact between the resin and the aggregate. Typical usage levels of these silanes are 0.1 to 1.5% based on resin weight. Examples of useful silanes are those of general formula 1. Formula _{1: (RO)} 3 on _{-Si-CH 2 -CH 2 -CH 2} -X wherein a R = _{C 3} or _C 2 _{H 5,} Is. Other useful silanes not represented by Formula 1 are 2
-(3,4-epoxysiccohexyl) nityltrimethoxysilane, bis (trimethoxysilylpropyl) ethylenediamine, N-trimethoxysilylpropyl-N,
N, N-trimethylammonium chloride and secondary amino silane _{[(RO 3) Si-CH} 2 CH 2 CH 2] 2 N
H.

A wide variety of materials have been found for accelerators. Accelerating the curing of the phenolic resole resin shortens the time from the mixing of the composition until it is sufficiently cured to be usable. Without the use of accelerators, in many cases phenolic resole resins with or without fillers or aggregates, magnesium hardeners and optional ester functional hardeners hardened to give sheets or bars of such compositions. The time at which it becomes damaged when bent is at 23.9 ° C (75 ° F) within 24 hours.

In the case of ionizable compounds, it is an anion, for example C1 ^−, which makes the material act as a promoter. That is, cations such as Na ⁻ , H ⁻ , and Li ⁻ do not change the fact that the anion is an accelerator, although they have some influence on the degree of gelation or curing. The salts containing the following cations are particularly suitable as the accelerator of the present invention. That is, sodium; potassium; lithium; calcium; magnesium: ammonium; and lower alkyl-substituted ammonium compounds such as those having 1 to 4 carbon atoms in each alkyl group. Early cations as well as hydrogen, such as hydrogen in nitric acid, are preferred cations for the promoters of this invention. However, some compounds that do not appear to ionize may also be promoters.

The accelerators of the invention are slightly soluble in the reaction medium. Its solubility is different from that in water, especially when the reaction medium contains a significant amount of ester and contains about 15 water.
This is the case when the content is less than%. However, for general purposes, the solubility of the promoter in water is 25 ° C, except for the promoter containing reactive organic bound chlorine or bromine.
Is 0.1% by weight or more, preferably 1.0% by weight or more. Accelerators containing reactive organically bound chlorine or bromine are often substantially insoluble in water. The accelerator may be in acid form, such as hydrobromic acid, or may be in salt form, such as an acid addition salt of a basic nitrogen compound, or a phenolic resin, a magnesium hardener and optional ingredients. It may be in a form that simply gives a promoter anion when mixed with the ester. If the acid form is used in the presence of a magnesium hardener, the acid salt is formed in situ. For example, when the phenol resole resin of the present invention and a curing agent composition are added, a magnesium salt is formed, and an acid or salt gives a suitable anion.

Ionizable accelerators, such as those that impart anions such as chloride and sulphonate to the curable mixture, increase magnesium solubility, ie, increase the amount of soluble magnesium released from the magnesium curing agent in the curable mixture. It seems to let you. This accelerates the curing of the phenolic resin. As mentioned above, the accelerator must have some solubility in the curable mixture. In this regard, the cation associated with the anion of the ionizable promoter should be selected so as not to render the anion insoluble. This means that various types of calcium-containing compounds that can be used in combination with a magnesium curing agent may be used to cure the phenolic resole resin when using other materials that may insolubilize some of the accelerator anions such as acid addition salts of amines. apply. To avoid this insolubilization, either the accelerator anion is one that is insolubilized in such materials, or the curable mixture contains a large amount of accelerator anion and a sufficient amount of anion is present to solubilize the magnesium hardener. It is necessary to remain. Calcium is the cation of the accelerator compound, or, when using a calcium-containing curing agent, the accelerator anion forms a water-soluble calcium compound having a water solubility of 1% by weight or more at 25 ° C. There should be no correlation.

In the case of a compound which dissociates in water or alcohol to give an anion, the following compound giving an anion is an accelerator and is used in an aqueous solution of a magnesium hardener, a phenol resole resin and other components in the curable mixture. It seems that increasing the amount of magnesium will be effective. The above anions are chlorine ion, nitrate ion, sulfate ion, sulfite ion, bisulfite ion, hydrogen sulfate ion, phosphite ion, hypophosphite ion, cyanate ion, bromine ion, formate ion and thiosulfate ion. is there. Such accelerators increase the amount of soluble magnesium in a curable mixture consisting of a phenolic resin, a magnesium hardener and an optional ester hardener or other ingredients, without further addition of magnesium oxide or magnesium hydroxide. Let The compound that provides the anion promoter can take various forms such as an acid, a salt, an acid addition salt of an amine, or a compound in which reactive chlorine or bromine is bonded to an organic group. In the case of acid addition salts of amines, the salt is 25 ° C
It must have a water solubility of 1% by weight or more. Compounds containing reactive chlorine or bromine bound to organic groups include covalently bound chlorides or bromides, such as water, alcohols, phenolic resins or amines, especially in the presence of magnesium or calcium oxides or hydroxides. Means a material that liberates chlorine ion or bromine ion by solvolysis reaction or nucleophilic substitution reaction with another hydroxyl compound.

Examples of compounds which provide the acid form accelerator include hydrochloric acid, phosphorous acid, hydrobromic acid, formic acid, hypophosphorous acid, sulfamic acid and sulfuric acid. Examples of salts that provide anion promoters include sodium chloride, potassium chloride, sodium bromide, lithium chloride, magnesium chloride, lithium carbonate, magnesium bromide, calcium chloride, ammonium sulfate, potassium bromide, potassium sulfamate, phosphorous acid. Examples include monosodium and choline formate.

Lithium carbonate is the strength of the cured resin composition,
In particular, it is an accelerator that also improves the strength after heat curing. Lithium carbonate should be avoided when the composition contains more water soluble calcium than lithium carbonate. This is because carbonate may be decomposed by water-soluble calcium such as calcium oxide. Sulfamic acid and its salts contain about 10% or more phenol resole resin, for example 10 to 25%.
With a free phenol content of about 150
When it has a relatively low molecular weight of 500 to 500, it is an accelerator that also improves the strength of the phenol-resole resin composition cured at room temperature.

Examples of promoter compounds containing reactive chlorine or bromine bound to an organic group include cyanuric chloride (2,
4,6-trichloro-S-triazine); 2,4-dichloro-6-n-propoxy-S-triazine; 2,4-
Dichloro-6-anilino-S-triazine; 2,4-dichloro-6-o-chloroanilino-S-triazine; methanesulfonyl chloride; α, α, α-trichlorotoluene; and 2,3-dibromopropionitrile. be able to. Additional examples of compounds containing reactive chlorine or bromine attached to an organic group include epichlorohydrin, epipromohydrin, 2,4-dichloro or dibromo-6-substituted-S-triazines, such as the substituent -6 carbon alkoxy or alkylamino, 6-10 carbon aryloxy and arylamino and other heterocyclic polychlorides such as 2,4-dichloropyrimidine; dichlorodiphenylsilane, chlorides or bromides of silicon such as silicon tetrachloride, Silicon tetrabromide, phenylchlorosilanes, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane; other carbon-chlorine or bromine compounds such as allyl chloride, benzyl chloride and cinnamyl chloride, 1,4 -Dichloro-2-butene, methyl 2-chloroacetate, 1.4-dibromo-2-butene, 2,3-dic Ropuro propionaldehyde, 2,3-dichloro Purobio nitrile, alpha,. Alpha .'-
Dibromoxylene, α, α′-dichloroxylene, 2-
Chloromethyl-m-dioxolane and chlorides such as acetyl chloride, pivaloyl chloride, benzoyl chloride, isophthaloyl chloride, terephthaloyl chloride and sulfur-chlorine compounds such as sulfonyl chloride compounds of benzene and torunine, 1,3-benzenedisulfonyl chloride and methane. There is a sulfonyl chloride. Further, it is also possible to use a compound which liberates a promoter anion such as hydrogen chloride or a compound in water or alcohol, for example, dichlorophenylphosphine.

In addition, certain strongly basic tertiary amines are also promoters. Examples of such accelerators include 1,3
5-tri (lower alkyl) hexahydro-1,3,5-
Triazines in which lower alkyl has 1 to 3 carbon atoms; 1,4-diazabicyclo [2.2.2. ] Octane; 2,2′-bipyridine; 1,1,3,3-tetra-lower-alkyl (1 to 3 carbon atoms) guanidine; 2,4-
Di (lower alkylaminomethyl) phenol, 2,6-
(Lower alkylaminomethyl) phenol and 2,4
Mention may be made of 6-tris (di-lower alkylaminomethyl) phenol (each alkyl group having 1 to 3 carbon atoms) as well as compounds of the formula However, in the above formula, (i) R ¹ and R ² are each selected from the group consisting of alkyl having 1 to 3 carbon atoms,
R ¹ and R ² represent those selected from the group consisting of piperidino, piperazino, morpholino, thiomorpholino and pyrrolidino when they combine with the nitrogen to which they are attached. (Ii) X is n is 1 to _{6 (-CH 2 -) n,} -
_{CH = CH-CH 2 -,} - C And (iii) R ³ and R ⁴ are each selected from the group consisting of hydrogen, alkyl of 1 to about 3 carbon atoms, and R ³ and R ⁴ When combined with the nitrogen to which they are attached is selected from the group consisting of piperazino, morpholino, thiomorpholino, piperidino and pyrrolidino. Lithium carbonate is a useful promoter compound, as well as acid addition salts of the above basic amine promoters or other anions which are not retarders, where the acid comprises one of the above promoter anions.
Other anions which are not retarders include formate ion, trifluoroacetate ion, chloroacetate ion, benzoate ion, benzenesulfonate ion and substituted benzoic acid wherein the substituent is alkyl having 1 to 4 carbon atoms, halogen or nitro group. There are ionic and substituted benzene sulfonate ions. Still another group of accelerators are certain chelating agents, such as heptane-2,4-dione; pentane-2,4-dione, also called acetylacetone; 2,2'-bipyridine;benzoylacetone; 2-acetylcyclo. Pentanone; and 2-formylcyclopentanone.

The amount of accelerator used in the present invention will vary widely depending on the activity of the particular accelerator, the degree of promotion desired, room or ambient temperature, the surface area and amount of lightly calcined magnesium oxide and the type and amount of ester hardener. It can change. That is, the amount of accelerator sufficient to accelerate gelling and curing of the phenol resole resin can vary over a wide range, from about 0.1 to 5% by weight of the phenol resole resin. However, it is preferred that the amount of accelerator is about 0.5 to 5%, especially 1.0 to 5% by weight of the resin. Chloride is an effective accelerator even when used in as little as 0.1% by weight of the resin, but other accelerators generally require higher amounts.

Filler, Aggregate and Modifier The composition of the present invention may contain a filler, a modifier and an aggregate which are usually used for phenol resole resin. Aggregate is a granular material in the form of particles, powder or flakes. Suitable aggregates include magnesite, alumina, zirconia, silica, zircon sand, olivine sand, silicon carbide, silicon nitride, boron nitride, bauxite, quartz,
There are chromite and corundum. However, it is not limited to the above. Depending on the application, low-density bone and minerals such as vermiculite, perlite and pumice stone are suitable.
High density aggregates suitable for other applications include limestone, quartz,
There are sand, gravel, crushed rock, crushed bricks and air-cooled blast furnace slag. Sand, gravel, and crushed rock are suitable aggregates for polymer concrete. Fillers such as calcium carbonate, kaolin, mica, wollastonite and barite can be used in amounts up to about 50% of the resin blend weight. The amount of this filler can be equal to that of the resin. Glass, phenolic resin or ceramic sphere microspheres,
It can be used in amounts up to about 20% of the resin formulation. Other optional modifiers, especially those used in polymeric concrete, include steel fibers, alkali resistant glass fibers, polyester fibers, carbon fibers, silicon carbide fibers, asbestos fibers, wollastonite fibers, and DuPont. there have fibers such as aromatic polyamide fibers and polypropylene fibers such as Kevlar ^{▲ R ▼} amide fibers sold. The amount of this fiber can be varied over a wide range sufficient to improve the strength of the composition and is used in the composition, for example in an amount of about 2 to 5% by weight of the aggregate.

The raw material batch composition produced by combining the curable resin binder, aggregate, curing agent (s) and accelerator is a non-reactive solvent, silane, hexamethylenetetramine, clay, graphite, oxidation. Any of a number of optional modifiers or additives including iron, carbon pitch, silicon dioxide, metal powders such as aluminum and magnesium, silicon, surfactants, dispersants, air vents and mixtures thereof. May be included. Air vents such as defoamers, such as dimethyl polysiloxane, can be used in sufficient amounts to increase the strength of the composition. This amount can vary over a wide range from about 0.005 to 0.1%, preferably about 0.01 to 0.05%, based on the weight of the resin. As an example of a further air extracting agent, Air Products and Chemicals (Air Product
and Chemicals, Inc. ) Surfinol, for example Surfinol DF
-110L, such as Surfynol 104 and Surfynol GA Examples include dimethylpolysiloxane such as PS073 that is supplied as s) and various siloxanes such as dimethylsiloxane-alkylene oxide block copolymer. Silane adhesion promoters such as gamma-aminopropyltrinitoxysilane are suitable additives for casting applications and applications where sand binder overlays and silica sand are used as aggregates. For refractory applications, clay, metal powders (eg aluminum, magnesium or silicon) and graphite are preferred additives. When graphite or metal powders of aluminum, magnesium or silicon or mixtures thereof are used as additives, the amount of aggregate such as alumina or magnesia can be reduced to as low as about 70% of the composition weight.

Uses The methods and compositions of the present invention provide shaped articles such as bonding refractory aggregates to produce bricks and castable monoliths; coated abrasives; provide concrete with resistance to acids, oils and organic solvents. Polymeric concrete (also called resin-filled aggregate) for protective overlays or restorations; manufacture of precast shaped articles such as pipes, tiles, wall panels where hydrolysis resistance, solvent resistance, acid resistance and heat resistance are desired;
And especially useful in the preparation of impregnated papers for automotive oil and air filters. Refractory shaped products include refractory bricks and integrated refractories. Conventional refractory compositions contain a curable phenolic resole resin; a magnesium hardener: and optionally an ester functional hardener, metal powder and graphite. Aggregates commonly used as refractories are magnesium (periclase); alumina: zirconia; silica; silicon carbide; tein nitride, boron nitride: bauxide; quartz; corundum, zircon sands; olivine sands; and mixtures thereof. Suitable aggregates for refractories are refractory magnesia, also called periclase, alumina and silica. The amount of graphite generally varies from about 5 to 25% by weight of the refractory bone mass, and metal powders such as aluminum, magnesium and silicon generally vary from about 1 to 5% by weight of the refractory aggregate. . In the case of a refractory material such as brick, the refractory material composition is pressed into a desired shape and heat-cured, or the composition after pressing is left at room temperature and cured, and then heat-cured.

Some refractory applications may require preformed shapes other than brick-like shapes. These "integrated refractories" are cast by placing the liquid flowable binder-aggregate system in a mold and then filling the mold by vibration. Once the binder-aggregate system has hardened at room temperature, the mold is removed and the shape is thermally hardened for use either before or after being transferred to the place of use of the integrated refractory.

Calcium aluminate, a hydraulic refractory, is
It constitutes the current integrated refractory bonding technology. However, the melt of molten metals such as iron, steel and aluminum reacts chemically with the hardened cement to dissolve, soften or simply weaken the hydrated cement phase, which increases the permeability of hardened refractory shapes. The problem occurs. Therefore, the life of the refractory shaped article is severely limited. After room temperature curing, this monolith can be thermally cured or carbonized, preferably in the area of use, for example as part of a furnace lining. Carbonization occurs at temperatures above 800 ° C or 1000 ° C.

Polymer concrete is formed by polymerizing monomers, resins or mixtures thereof in the presence of aggregate. An early application of polymer concrete was the restoration of Portland cement concrete. Today, polymer concrete has many uses, as mentioned above. The binder composition of the present invention is particularly advantageous for these applications. The binder composition of the present invention is not highly alkaline and does not affect the aggregates due to low sodium or potassium levels and is curable within a reasonable time at room or outdoor or ambient temperatures. Is. One use of the compositions of the present invention is as a coating or topping on rigid surfaces such as concrete. That is, there is provided a room temperature curable floor composition comprising a resin binder and aggregate system prepared as described above. The aggregate for the overlay coating can be selected from low density materials, high density materials or mixtures thereof. The presence of small amounts of sodium in the preferred compositions of the invention does not adversely affect the concrete.

One preferred use of the composition of the present invention is a shaped article produced by casting, curing at room temperature or room temperature, and then thermally curing. In order that those skilled in the art may more fully understand the invention presented herein, the following methods and examples are provided. Unless otherwise stated, all parts and percentages in the examples and other cylinders and claims in the specification are by weight and temperatures are in ° C (° F).

Preparation method of polymer concrete and its pressure
Test method for crimp strength A 5.5 liter (5 quart) Hobart mixer was placed in an industrial grade sand no. 4 (Vulcan Materials Co.) Also referred to as coarse sand in the present application 990.0 g Industrial grade sand No. 4 10 (Vulcan Materials Co., Ltd.) Also referred to as medium-sized sand in the present application 360.0 g Oklahoma Mill Creek Foundry Sand (US Silica Co., Ltd.) 150.0 g also referred to as fine sand in the present application and Magchem 50 (65 m ² / g) 22.5 g Martin Marietta Magnesia Specialties (Martin Marietta Specialties)
ies) lightly fired magnesia. 1.8 g
180.0 g of Resin A containing 3-glycidoxypropyltrimethoxysilane of was added. The resin-aggregate was mixed for a total of 2 minutes (1 minute on medium setting and 1 minute on high setting), then 3.38 cm deep.
(1-1 / 2 inch) and 3.38 cm diameter (1-1 /
The mixture was transferred to a mold containing 2 (15) cylindrical cavities. Each cavity was lined with a thin polyester film to facilitate removal of the cured specimen. Next, the filled mold is used as a synchrotron vibration table (Syntron Vibrating Table).
And was set to 5.1 and vibrated for 2 minutes. The surface was slightly troweled. Next, this mold is kept at constant temperature (22, 2 ± 1,
1 (72 ± 2 ° F) -transferred to a constant temperature (51 ± 2%) chamber.
After 24 hours, the cured test specimens were removed and stored for testing or later evaluation. The compressive strength of polymer concrete is Tinius Olsen.
The tensile tester was used to measure at a low speed of 3.8 mm / min (0.15 inch / min). The number of pounds when broken is 1.77
The value divided by represents the compressive strength in psi.

Preparation of Polymer Concrete and Tensile
Strength test method 5.5 liters (5 quarts) 89 in Hobart mixer
1.0 g of industrial grade sand No. 4, 324.0 g
Industrial grade sand No. 10 (both made by Balkan Materials) 135.0 g of Oklahoma Milk Creek Foundry Sand (US Silica) and 13.5
g of Magchem 50 (Martin Marietta Specialties) was charged. To this mixture was added 1 part of Resin A containing 1.62 g of 3-glycidoxypropyltrimethoxysilane.
62.0 g was added. This resin / aggregate mixture for 2 minutes,
1 minute was mixed at medium speed and 1 minute was mixed at high speed. The mixture is then transferred to an aluminum mold (previously sprayed with release agent),
Length 76.2 mm (3 inches), thickness 25.4 mm (1
Inch) and a neck width of 25.4 mm (1 inch) dogbone shaped specimens were cast. The sprinkling mold was pre-placed on a polyester film on an aluminum tray. It was filled in a dog-bone type and vibrated for 2 minutes with 5.1 setting on a synchrotron vibration table.
The surface was slightly troweled. Next, the assembled device is kept at a constant temperature (22.2 ± 11 ° C. 11) and a constant humidity (51 ± 2).
%) Transferred to the room and allowed to cure. Samples were removed from the molds after 24 hours and stored for testing or later eye evaluation. Tensile strength was measured using a Tinius-Olsen tensile tester.
The measurement was performed at a low speed of 8 mm / min (0.15 inch / min).
The digital read value indicates reading in psi.

With / With an Ester Curing Agent
Trees with and without additives / with and without additives
Soluble macromolecule produced by reaction of fat A with magnesia hardener
Measurement of Gnesium In a glass screw cap vial (28 x 95 mm) Resin A 6.0 g Water 0.5 g γ-butyrolactone 1.5 g

(Sometimes referred to as 2-methoxyethyl ether in the examples of the present application or in the table), it was mixed lightly to make the solution uniform, and 0.75 g of lightly calcined magnesia (Martin Marietta) was added. Magchem 50) from Magnesia Specialties Inc. was added. S / P Vortex mixer (American Science Fic Products Inc. (American Scie)
The mixture was thoroughly mixed for 1 minute using the Nucleic Products)) setting at 9. 1.5
g of the uniform dispersion was added to 4.5 g of N, N. Immediately transfer to a vial containing dimethylformamide (DMF) and 0.5 g of methanol. After mixing thoroughly for 1 minute, the contents were transferred to a centrifuge tube and centrifuged for 5 minutes. The relatively clear liquid was filtered through a Teflon microfilter. A certain amount of a transparent solution was weighed and placed in a platinum dish, which was heated to 600 ° C. in a muffle furnace to be incinerated. The residue was treated with hydrochloric acid, diluted appropriately, and analyzed for magnesium by atomic absorption spectrometry. The above new mixed solution / magnesia dispersion (1.5 g / vial) was transferred to another empty vial and placed in a 25 ° C. water bath. 4.5 g of DMF was added at the appropriate time and the resin was completely dispersed by stirring for 2-3 minutes. Next, 0.5 g of methanol was added and mixed again, then centrifuged and analyzed as described above. % Magnesium in the first sample = measured magnesium% x
4.27 (Compensation for solvent dilution) Resin / Curing agent / Magnesia / Aggregate mixture flow measurement Width 7.6 cm (3 ") Depth 5.1 cm (2") dome-shaped 150 ml glass bowl release agent Was sprayed lightly, divided into three parts, and filled with a composite mixture obtained from a resole, an ester hardener, a lightly calcined magnesia hardener and an aggregate (silica sand or dead-burned magnesia refractory). Each addition of each ingredient was tapped with a pestle. The bowl and contents were transferred back to a polyester film taped to a Syntron vibrating table. The table was then oscillated at setting 8 (3/4 of maximum setting) for 20 seconds. The diameter (inch) of the obtained hemisphere was measured, and the flow% was calculated by the following formula. Gelation Assay 6.0 grams of Resin A or Resin B (shown in Table or Examples) in glass vials (28 × 95 mm) with screw stoppers; Additives (Shown in Tables or Examples); 0 Charge .5 grams of water; and 1.5 grams of gamma-butyrolactone. After thoroughly mixing this solution, the surface area is 65
adding mild calcination magnesia 0.75g of m ² / g.
S / P of American Scientific Products Co., Ltd.
Using a vortex mixer, set to 9 and mix this mixture thoroughly for 1 minute. Immediately transfer 5 grams of this mixture to a glass test tube (18 x 155 mm). A crow trowel with a magnetized head mount was introduced into the mixture and attached to a Sunshine gel time meter, which was rotated. During the exam
The test tube was immersed in a water bath at 25 ° C. The gelling time was measured with Resin C using 5.0 g of the mixture obtained by mixing 8.0 g of Resin C, 1.2 g of gamma-butyrolactone and 1.6 g of lightly calcined magnesia having a surface area of 65 m ² / g. did. Solvents were optionally used. 25 for gelation measurement
C. or 60.degree. C. (chloroform boiling point). Resin D
At 100 ° C. gelation time, a mixture obtained by mixing 8.4 g of resin D, an organic curing agent 2-methoxyethyl ether having an ester equivalent of 0.008 l and 0.16 g of lightly calcined magnesia having a surface area of 25 m ² / g. 5.0 g was used. The total weight of ester curing agent and 2-methoxyethyl ether was kept constant. The gelation time of resin E was 3.85 g of resin and 1.16 g of ethyl lactate or resin E4.0.
g and 1.0 g of triacetin were used.

Properties of Phenolic Resin Phenol resole resin E is a product of Borden Chemical Company (B
orden Chemical Company is a commercial product sold under the trade name of Alphaset. Resin E is used for comparison purposes in the present invention. This resin contains about 50% solids and 50% water.
And the viscosity at 25 ° C. is 150 cps and the pH is 13. Phenol resole resin (also simply called resin A)
Is phenol (P) and 50% formaldehyde (F)
Is a phenol-formaldehyde resol resin prepared by reacting and with an F / P molar ratio of 1.25 using sodium hydroxide as a catalyst and further mixing. Resin A is obtained by blending this resin intermediate with acetic acid, ethanol, methanol and N, N-dimethylformamide (DMF).
Resin A has a viscosity of 2,560 when heated by Gardner at 25 ° C.
Centistokes, or about 3000 cps at 25 ° C
Solid content 68%; free phenol 7%; lower alkyl alcohol 10%; water 12%; DMF 4%, pH 5.9 and weight average molecular weight 4,000.
Is.

Phenol resole resin B (also simply referred to as resin B) is a more alkaline, water-dilutable homologue of resin A, containing no acetic acid and N, N-dimethylformamide (DMF), and instead resin B. Based on the above, ethanol was added so that the ethanol content was 7.5% and the potassium hydroxide was 0.75%.
H is 8.9, the weight average molecular weight is 4,000, (BOR) solid content 67%, water 1 based on the resin weight.
It contains 8% and 7% free phenol.

Phenol resole weight C (also simply referred to as resin C) is prepared by the reaction of phenol (P) and 50% formaldehyde (F) at a F / P molar ratio of 1.25 using a sodium hydroxide catalyst. This resin has a 250 cps viscosity at 25 ° C; solids 68.6% B.S. O.
R. Free phenol 15.7% B.I. O. R. Water 11.
7% B.I. O. R. And has a pH of 8.9; and a weight average molecular weight of 290.

Phenol resole resin D (also referred to simply as resin D) is prepared by the reaction of phenol (P) and 50% formaldehyde (F) at a F / P molar ratio of 2.0 using a potassium hydroxide catalyst. The resulting intermediate resin has a weight average molecular weight of 390 and is blended with phenol and Dowanol DPnB (Dow Chemical's dipropylene glycol monoptyl ether) to form the final resin. Final resin is 78% solids;
Free phenol 16%; Water 8%; Dowanol DPnB8
%; Containing 1.3% potassium, pH 9.2; 25 ° C.
Has a viscosity of 3450 cps.

[0073]

Example 1 In this example, the effects of various additives on the curing rate of a phenol resole resin at 25 ° C. under the condition that a magnesium curing agent and an ester curing agent coexist are based on the resin weight (unless otherwise specified). B.O.R.) 2%
It was tested at the standard. The cure rate is determined by measuring the gelation rate according to the method described above under the heading "Measurement method for gelation". The resin used was resin A, the ester was γ-butyrolactone, and the magnesium curing agent was Magchem 50. The control example in Table 1 was a composition containing no additive, and its gel time was 48 minutes. Also in the case of the low molecular weight homologues of resin A indicated by the subscript [(a)] in Table 1, the composition contained no additive, and the gelation time was 67 minutes. That is, an additive having a gelation time of less than 48 minutes without the suffix [(a)] after the time indicates an accelerator, and the suffix [(a)] after the time.
Additives without gelation time exceeding 48 minutes represent retarders. The results of this example are shown in Table 1. Some of the key results shown in Table 1 are as follows.

Chloride is the most effective accelerator. About 2
Organic materials containing chlorine or bromine that react with water or alcohols to liberate chloride or bromide ions at 5 ° C and a pH of about 5 to 9 act as reactivity promoters. Fupide salts and acid fluoride salts are retarders. Phosphorus and phosphates are effective retarders. Surprisingly, phosphorus phosphide, sodium phosphite and hypophosphorous acid are promoters.

[0075]

[Table 1]

Examples 2 and 3 In these examples, tests were conducted to determine the effect of lightly calcined magnesia or magnesia hydroxide, esters and additives on the compressive strength of polymeric concrete. These examples were conducted according to the polymer concrete preparation and testing methods described above. Table 2
In the data of the polymer concrete shown in 3 and 3, unless otherwise specified, the compressive strength was measured at room temperature (R .T.) Measured on cured test pieces. The following can be seen from Tables 2 and 3. (A) Compared to the control sample, the fluoride retarder had a R.V. T. Although decreasing in strength, this relative effect becomes even more dramatic after 8 hours. Lithium carbonate and calcium formate were used for 1 day. T. Increases strength, but lithium fluoride (very low solubility) has no effect. (B) When magnesia is replaced with a chemically equivalent amount of magnesium hydroxide, the compressive strength is dramatically reduced. However, magnesium hydroxide responds to promoting effects and retarders. Chloride was used for 24 hours. T. Increases compressive strength, but reduces fluoride. (C) Replacing the γ-butyrolactone ester with an equal weight of an inert high-boiling solvent (glycol ether), 3 and 7 days. T. The strength drops dramatically. Dry for 3 days T.
When it is immersed in 10% acetic acid for 4 days after curing, the strength is 7 days dry. T. Lower than when cured. When butyrolactone is used, an increase in strength is observed after acetic acid treatment. (D) Concrete prepared using γ-butyrolactone and lightly calcined magnesia was dried for 3 days. T. Immersion in hot (90 ° C.) water for 4 days after curing gives significantly higher strength than systems using inert solvents instead of esters or magnesium hydroxide instead of magnesia. (E) Sulfamate is a good accelerator, but has a negative effect on the strength (8 or 24 hours) with resin A. However, sulfamate
There is an improvement in strength when using a resin having a low molecular weight and high free phenol content, for example 10 to 25% free phenol based on resin weight. This state can be seen from Example 10 and Table 10. It shows a 24% strength increase after 24 hours in the moderate accelerator LiCO ₃ .

[Table 2]

[Table 3]

[0076]

Example 4 In this example, a test was conducted to determine the effect of the surface area of a lightly calcined magnesia curing agent on gelation time. The test composition was resin A 6.0 g; water 0.5 g; γ
It contained 1.5 g of butyrolactone and 0.75 g of a magnesia hardener of varying surface area. The results are shown in Table 4. From Table 4, it can be seen that the gelling time is a function of the surface area and concentration of magnesia, and the larger the surface area or concentration, the shorter the gelling time.

[Table 4]

[0077]

Example 5 This example is the same as the previous room temperature (RT) at 25 ° C.
It was carried out to show the effect of additives, which were accelerators or retarders during curing, on the solubilization of magnesium in the reaction mixture. This example was performed according to the "Method for Quantifying Soluble Magnesium from Reaction of Resin A with Magnesia Hardener with / without Ester Hardener and with / without Additives" above. The results are shown in Table 5. The% B. O. R. The value of is the percentage of additive (BOR) based on resin weight. It can be seen that chloride promotes the solubilization of magnesium in the reaction mixture and fluoride reduces it. A similar effect is observed with the ester-free mixture 4-6 using 2-methoxymethyl ether as an inert solvent instead of the ester. The chelating agent pentane-2,4-dione also increases the solubilization of magnesium.

[Table 5]

[0078]

Example 6 In this example, a number of diamino and triamino compounds including acrylic and cyclic compounds were tested as accelerators, the results of this example are shown in Table 6, Mixture 8 is a mixture of TRIS and chloride. Shows an additional promoting effect.

[Table 6]

[0079]

Example 7 A test was conducted showing the effect of various additives in combination with certain esters on the gel time. This gelation time test was carried out according to the above-mentioned "gelation measuring method". The test results shown in Table 7 show the action of various additives in combination with various temperatures and various esters and resins as accelerators or retarders.

[Table 7]

[0080]

Example 8 This example was conducted to determine the effect of magnesia / lime ratio and additives on the gel time of resole and ester. The results of this example are shown in Table 8.
In Resin A, even if the MgO curing agent was replaced with CaO up to 33%, the gelling time was not substantially affected (mixture 1
-4) It turns out that a 1: 1 ratio (mixture) is problematic. In contrast, Resin C (low molecular weight and high free phenol) did not significantly affect gelation time and M
Less than 20% of gO can be replaced by CaO (Mix 10 vs. Control Mix 8). U.S. Pat. No. 4,794,051 to Gupta, cited above, at column 4, lines 45-53 and lines 34-37, shows that magnesium oxide and magnesium hydroxide are too slow curing agents, and calcium and magnesium. Although the use of a mixture with a ratio of 10: 1 to 0.1: 10 is preferred, the above results are contrary to this. Furthermore, Gupta's composition is "2 at about 20-70 ° C.
4 to 100 hours or more "but remains thermoplastic (column 60 line 23 of the Gupta patent), the mixture of the phenolic resole resin of the present invention and the curing agent without retarder cures in less than 24 hours. I have to point out what to do.

[Table 8]

[0081]

Example 9 This example was conducted to show the effect of additives on the gel time of Resin E, a highly alkaline phenolic resole resin having a pH of about 13. The composition of this example does not contain a magnesium hardener. The results of this example are shown in Table 9. Usually in resin E, ethyl lactate induces hardening of the resin, as shown by the gelation of mixture 1. However, all additives, including chloride, which are accelerators of the magnesium hardener, acted as retarders or had no effect in this case. From Table 9 it can be seen that for this resin most of the additives are retarders, especially acid fluorides. The delayed action of ammonium chloride in this mixture is in marked contrast to the magnesium hardener system of the present invention.

[Table 9]

[0082]

Example 10 This example presents a series of experiments in which a composition with certain accelerators has an increased tensile strength as compared to the same composition without the accelerators. The results of this example are shown in Table 10. The composition of Example 10 is (a) a refractory magnesia bone village consisting exclusively of granules with a sieve size of 14 to 48:
(B) Resin F, 10% by weight of aggregate; (c) Gamma-butyrolactone, 15% by weight of resin (BOR) and MA.
GOX98 Premium consists of 30% by weight of Resin F, and the above-mentioned MAGOX98 Premium is based on Premier Refractories and Chemicals (Prmier reflect
ories and Chemicals, Inc. )
Is a lightly calcined magnesium oxide curing agent with a surface area of 100 m ² / g sold by. The amount of accelerator used was at a level of 1% on a resin weight basis (BOR). The tensile strength numbers given in Table 10 of this example are average values of three samples, and the values in parentheses are intermediate values. Resin F is a phenol formaldehyde resin having the following properties.
Resin. That is, 64.1 of solid content and resin weight
2%; water content, 5.65% of resin weight; free phenol content, 25.19% of resin weight; number average molecular weight (Mn)
107: Weight average molecular weight (Mw) about 200; M1 / 4 viscosity on Gardner-Holt scale at 25 ° C., 325 centistokes, converted to about 390 centipoise. In the production of resin F, formaldehyde / phenol was charged into the reactor at a molar ratio of 0.93 and 25.2% by weight of phenol remained unreacted in the resin even after distillation to reduce water to about 6%. Therefore, the reaction is carried out under mild heating conditions such that the molar ratio of formaldehyde charged to the reactor is increased to more than 1. Tensile specimens of resin-bonded magnesia refractory were prepared and tested as follows. Resin F and magnesium hardener were intimately mixed with refractory magnesia. Accelerators, when used, were added at this stage, following this stage gamma-butyrolactone was added to the mixture and the mixture was further mixed for about 3 or 4 minutes. A 150 gram sample of this mixture was then placed in a dog bone die and a ram pressure of 15 tons was applied for 1 minute to produce a tensile strength test piece. This test piece has a length of 7
6.2 mm (3 inches), thickness 25.4 mm (1 inch), neck width 25.4 mm (1 inch), which is 22.2 ° C. ± 1.1 ° C. (72 ° F. ± 2 ° F.) 51%
24 at ± 2% (relative humidity) under constant temperature and humidity (RT)
After leaving for an hour, Tinius-Olsen (Tinius)
Olsen) It was broken by a tensile tester. Some of the dogbone test pieces are under constant temperature / constant temperature conditions (RT) 24
After being exposed for a time, it was heat-treated at 110 ° C. for 2 hours, allowed to cool to room temperature, and fractured. From Table 10 that the addition of the accelerator sulfamate increases the room temperature tensile strength as compared to the same composition without the sulfamate additive; and the addition of lithium carbonate to the same composition without it. It can be seen that both the room temperature tensile strength and the thermosetting tensile strength are increased as compared with.

[Table 10]

[0083]

Example 11 In this example, the compressive strength of a polymer concrete composition at various times was determined to be 2% by weight of the resin A (B.O.R.) accelerators N, N, N ', N. '
The same composition containing tetramethyl-1,3-propanediamine and optionally resin weight basis (BO.
R. ) In comparison with the one additionally containing 0.1% antifoam SAG10. SAG10 is an antifoaming agent that also functions as an air extracting agent, and is manufactured by Union Carbide (Union).
It is a 10% emulsion of dimethylpolysiloxane sold by Carbide Corporation. This Example 11 and the compressive strength test method for the basic composition, ie the standard mixture, are the methods described above under the heading "Preparation of Polymer Concrete and Test Method for Compressive Strength". The results of this example are shown in Table 11. From Table 11, the compressive strength of the standard mixture or control at room temperature (RT) is greater than the compressive strength of the standard mixture after including 2% accelerator on resin weight (BOR). Furthermore, this 2% accelerator-containing product is a standard mixture + 2% (B.O.
R. ) Accelerator + 0.1% (BO, R.) It is found that it is smaller than the compressive strength in the case of the air extracting agent. Table 11 also shows that the compressive strength of the standard mixture when the accelerator and air vent were included in the composition was greater than that of the standard mixture plus accelerator cured at room temperature for one day. ing.

[Table 11]

[0084]

Example 12 This example shows the gelling time of Resin A according to the above-described method and composition entitled "Gelometry" also referred to in the standard or control compositions. The results of this example are shown in Table 12. Experiment 1 in Table 12 is a standard composition described in the above method, resin A, 6 g; water 0.5; gamma-butyrolactone, 1.5 g; and a light calcined magnesium oxide cure with a surface area of 65 m ² / g. Agent (Mg
O50), 0.75 g.

Experiment 2 in Table 12 shows 2% B. O. R. 2 shows the increase in the gelation time of the standard composition by the addition of the curing agent N, N, N ′, N′-tetramethyl-1,3-propanediamine. Run 3 of Table 12 shows the extension of the required gel time of the composition of Run 2 when the ester curing agent, gamma-butyrolactone, is replaced with an inert solvent. Experiment 4 of Table 12 is a relatively low surface area, lightly calcined magnesium oxide hardener, or Magchem 2
Even if 0M is added, gamma-butyrolactone and surface area 6
It is shown that the effect of further shortening the gel formation time of the composition of Experiment 2 containing 5 m ² / g of the lightly calcined magnesium oxide curing agent was not significantly increased. Magchem 20
M has a surface area of 10 m ² / g. Experiment 5 in Table 12
Is a comparatively low surface area (10 m ² / g) lightly baked magnesium oxide curing agent (Magchem 20M) was added in Experiment 3
It shows that there is only a comparatively small effect in shortening the gelation time of the composition.

[Table 12]

[0086]

Example 13 The composition of this example is the same as the composition of Example 12 except for the presence or absence of a magnesium hardener or an ester hardener, and the composition of Example 12 and Table 12 and Table 13 below.
In addition, it is for showing the synergistic effect obtained by using both the magnesium curing agent and the ester curing agent in the presence of the accelerator. That is, in Experiment 2 of Table 12, the composition containing both the accelerator and the ester hardener and the magnesium hardener required only 48 minutes for gelation. Table 12
Experiment 3 of 6 was the same as Experiment 2 of the same table except that the ester curing agent was not included, but the gelation was performed for 115 minutes. From Table 13 it can be seen that the same composition as the Experiment 2 composition of Table 12 did not gel after 14 days except that it did not contain a magnesium hardener or an ester hardener. Table 1
No. 3, the accelerator containing no magnesium curing agent or the ester curing agent had almost no effect of increasing the viscosity of the resin A, as compared with the case where the accelerator was used together with the ester curing agent and the magnesium curing agent. It also shows that.

[Table 13]

[0087]

Example 14 This example was conducted to demonstrate the effect of using a mixture of lightly calcined magnesium oxide hardeners of various surface areas. 65 m ² / g in a solution of 0.8 g of Resin A, 0.67 g of water and 2.0 g of gamma-butyrolactone
1.0 g of lightly calcined magnesium having a surface area of 1.0 was added. This mixture was stirred vigorously for 1 minute and then the mixture 5.
2 small cylindrical plastic vials (width 22m)
m) and cover each with a cap of 22.2 ° C. ± 1.
It was left for 4 days at 1 ° C (72 ° F ± 2 ° F). The cured mass was removed from the vial and weighed. Cylinder No. 1 and No. 2. Then, these are heated at 105 ° C. for 2 hours, and after weighing, 13
The sample was heated at 5 ° C. for another 2 hours and re-weighed. Cylinder No.
1. Lightly burned magnesia having a surface area of 10 m ² / g in the same amount of various components as those used for the adjustment of No. 1 and No. 2.
The above method was followed except that 0 g was added and the total amount of magnesia was 2.0 g relative to 8 g of Resin A. Cylinder No. 3 and No. Called 4. Compressive failure was measured with a Tinius-Olsen tensile tester.
The results are shown in Table 14. From Table 14, it can be seen that the sample containing additional magnesia has less weight loss and higher crush strength than the sample containing 50% less magnesia. The gelation time of the magnesia mixture was No. 1 and No. No. 2 is 67 minutes, while No. 2 is 67 minutes. 3 and No. 4 was 62 minutes, and as can be seen from Table 1, Mixture 1, there was little effect on gelation time. Following the same procedure as in this example, various promoters such as ammonium sulfamate, sodium chloride, pentane-2,4-dione, and 2,2'-villepyridine are added to the surface area-mixed magnesia-containing composition. The strength can be further increased while reducing the time required for gelling or curing of the binder, crude batch and other compositions of the present invention.

Table 14 Light firing with different surface areas of binder composition
Effect of mixed magnesium oxideThe embodiment of the present invention is as follows. 1. A person who promotes curing of a phenol resin binder composition
A. A. Curable phenol with a pH of about 4.5 to 9.5
Resol resin; B. Magnesium hydroxide and surface area about 10m^Two/ G or less
Selected from the group consisting of above lightly calcined magnesium oxide
Magnesium curing agent, provided that the amount of the curing agent is the resin
Sufficient to increase the cure rate of C .; (1) Solubility of 1% by weight or more in water at 25 ° C
Having, cyanate anion, formate anion, hypophosphite
Anion, nitrate anion, phosphite anion and sulf
An anion selected from the group consisting of
Compounds given to the mixture; (2) having 1 to 3 carbon atoms in each alkyl group
2,4 = di (dialkylaminomethyl) phenol,
2,6-di (dialkylaminomethyl) phenol and
2,4,6-Tris (dialkylaminomethyl) pheno
(3) each lower alkyl group has from 1 to 3 carbon atoms.
1,3,5-tri (lower alkyl) hexahydro-
1,3,5-triazine; (4) lithium carbonate; (5) 1,4-diazabicyclo [2.2.2. ] Ok
(6) pentane-2,4-dione, heptane-2,4
-Dione, 2,2'-bipyridine and benzoylaceto
A chelating agent selected from the group consisting of A compound of the formula (a) R¹And R^TwoAre each 1 to 3 carbon atoms
Selected from the group consisting of alkyl having
And R¹And R^TwoTogether with the nitrogen they bind to
When combined, piperidino, piperazino, morpholino,
Selected from the group consisting of thiomorpholino and pyrrolidino
(B) X is (-CH_Two−)_n(N is an integer from 1 to 6
Number), -CH = CH-CH_Two, -CH_Two-CH = CH-
CH_Two-,Is selected from the group consisting of: (c) R^ThreeAnd R^FourIs hydrogen, 1 to 3 charcoal, respectively
Selected from the group consisting of alkyl having elementary atoms
And R^ThreeAnd R^FourAnd the nitrogen they bind to
When combined together, piperazino, morpholino, thiomol
Selected from the group consisting of holino, piperidino and pyrrolidino
A promoter selected from the group consisting of, wherein the amount of the promoter is
A sufficient amount to accelerate the hardening of the mixture; 2. The resin has a ph of about 5 to 9 and a curing agent
Is magnesium oxide. 3. The resin is a condensation of phenol and formaldehyde
The method according to the above 1, which is a product. 4. The hardener contains particles of two or more different surface areas,
About 25 to 75% by weight of 50m^Two/ G or more surface area
Having about 25 to 75% by weight of about 10 to 25 m
^TwoThe method of 2 above having a surface area of / g. 5. The accelerator is cyanate anion, formate anion,
Phosphite anion, nitrate anion, phosphite anion and
And a sulfamate anion.
3. The method according to the above 2, which is a compound that gives ionic to the mixture. 6. The above 2 in which the accelerating agent is pentane-2,4-dione
the method of. 7. Clicks that combine with anions to form the above compounds
The method of claim 2 wherein the on is a sodium cation. 8. The above 5 in which the anion is a sulfamate anion
the method of. 9. The resin has a weight average molecular weight of about 150 to 500.
And having about 10 to 25% by weight of free phenol
8. The method according to 8 above, which comprises: 10. Combines with the anion to form the compound
The cations are hydrogen, sodium, potassium, lithium,
Calcium, magnesium, ammonium and alky
An alkyl-substituted anion in which the alkyl group has 1 to 4 carbon atoms
The above is a cation selected from the group consisting of monium
Method 5 11. The promoter has 1 to 3 carbon atoms in each alkyl group.
2,4-di (dialkylaminomethyl) phen having a child
Nole, 2,6-di (dialkylaminomethyl) pheno
And 2,4,6-tris (dialkylaminomethyl)
2) The above 2 selected from the group consisting of phenol
Law. 12. The accelerator is in the form of an acid addition salt of an amine,
The acid addition salt thereof has a water solubility of 1% by weight or more, and
The anions of the above acids are cyanate anion, formate anion,
Phosphite anion, nitrate anion, phosphite anion and
And a sulfamate anion.
11. The method of 11 above, which is Nion. 13. Accelerating agent may be one to three in each lower alkyl group
1,3,5-tri (lower alkyl) having carbon atoms
The above 2 which is oxahydro 1,3,5-triazine
Law. 14. The method of 2 above wherein the accelerator is lithium carbonate. 15. The accelerator is 1,4-diazabicyclo [2.2.
2. ] The method of the said 2 which is octane. 16. Accelerators are pentane-2,4-dione, hepta
-2,4-dione, 2,2'-bipyridine and benzo
A chelating agent selected from the group consisting of ylacetone
Method 2 above. 17. Accelerator has chemical formulaAnd a compound of the formula: R¹And R^TwoRespectively has 1 to 3 carbon atoms
Selected from the group consisting of alkyl having
R¹And R^TwoCoalesces with the nitrogen to which they are attached
When it comes to piperidino, piperazino, morpholino, thiomo
Selected from the group consisting of luforino and pyrrolidino
B. X is (-CH_Two−)_n(N is an integer of 1 to 6),
-CH = CH-CC. R^ThreeAnd R^FourIs hydrogen, 1 to 3 carbons, respectively
Selected from the group consisting of alkyl having atoms
Yes, R^ThreeAnd R^FourTogether with the nitrogen they are attached to
When merging, piperazino, morpholino, thiomorpholi
Selected from the group No., piperidino and pyrrolidino.
The method according to the above 2 characterized by: 18. The accelerator is an acid addition salt of amine,
The salted salt has a water solubility of 1% by weight or more at 25 ° C, and
The anion of the acid is a phenolic compound due to the magnesium hardener.
Is an anion that does not delay the curing of the sol resin.
Has 1 to 3 carbon atoms in each alkyl group
2,4-di (dialkylaminomethyl) phenol,
2,6-di (dialkylaminomethyl) phenol; each
1,3 having 1 to 3 carbon atoms in the alkyl group
5-tri (lower alkyl) hexahydro-1,3,5-
Triazine; 2,2'-bipyridine; 1,4-diazabi
Cyclo [2.2.2. ] Octane and chemical formulaAnd a compound of the formula: R¹And R^TwoRespectively has 1 to 3 carbon atoms
Selected from the group consisting of alkyl having
R¹And R^TwoWhen they coalesce with the nitrogen they bind to
Includes piperidino, piperazino, morpholino, thiomorpho
Lists selected from the group consisting of Rhino and Pyrrolidino
B. X is (-CH_Two−)_n(N is an integer of 1 to 6),
-CH = CH-CC. R^ThreeAnd R^FourIs hydrogen, 1 to 3 carbons, respectively
Selected from the group consisting of alkyl having atoms
Yes, R^ThreeAnd R^FourCoalesces with the nitrogen to which they bind
When you do piperazino, morpholino, thiomorpholino,
Selected from the group consisting of piperidino and pyrrolidino
The method of 2 above, which is selected from the group consisting of: 19. The above wherein the acid addition salt is a sulfamic acid addition salt.
18 ways. 20. 17. The above 17, wherein the acid addition salt is a nitric acid addition salt
Law. 21. The composition of 2 above which is cured in a greenhouse. 22. The above-mentioned 2 in which the increase in viscosity is allowed and the material is thermally cured
The composition as described. 23. Accelerates curing of phenolic resole resin composition
A method of: pH is about 5 to 9 and solids content is about
50 to 90% by weight and a viscosity of about 10 at 25 ° C
Curable phenolic resin with 0 to 4,000 cps
B. sol resin; B. Hydroxyl hydroxide, which accounts for about 5 to 50% by weight of the resin.
Gnesium and about 10m^TwoLight with a surface area of / g or more
Mag selected from the group consisting of calcined magnesium oxide
Nesium curing agent; C.I. Ester official account for about 5 to 40% by weight of the resin
A functional curing agent; and D. Occupy about 0.5 to 5% by weight of the resin, and (1) has a water solubility of 1% by weight or more at 25 ° C,
, Cyanate anion, formate anion, hypophosphite ani
On, nitrate anion, phosphite anion and sulfami
An anion selected from the group consisting of acid anions.
A compound to give a compound; (2) having 1 to 3 carbon atoms in each alkyl group
2,4-di (dialkylaminomethyl) phenol,
2,6-di (dialkylaminomethyl) phenol and
2,4,6-Tris (dialkylaminomethyl) pheno
(3) Each lower alkyl group has 1 to 3 carbon atoms.
1,3,5-tri (lower alkyl) hexahydro-
1.3,5-triazine; (4) lithium carbonate; (5) 1,4-diazabicyclo [2.2.2. ] Ok
Tan (6) Pentane-2,4, dione, heptane-2,4
-Dione, 2,2'-bipyridine and benzoylaceto
A chelating agent selected from the group consisting ofA compound of the formula (a) R¹And R^TwoIs 1 to 3 carbon atoms, respectively
By itself selected from the group consisting of alkyl having
Yes, R¹And R^TwoCoalesces with the nitrogen to which they bind
When you do piperidino, piperazino, morpholino, thio
Selected from the group consisting of morpholino and pyrrolidino
(B) X is (-CH_Two−)_n(N is an integer from 1 to 6
Number), -CH = CH-CH_Two-, -CH_Two-CH = CH-CH
_Two,Is selected from the group consisting of; and (c) R^ThreeAnd R^FourIs hydrogen, 1 to 3 charcoal, respectively
Selected from the group consisting of alkyl having elementary atoms
And R^ThreeAnd R^FourTogether with the nitrogen to which they bind
When you wear it, piperazino, morpholino, thiomorpholi
No, selected from the group consisting of piperidino and pyrrolidino
A promoter selected from the group consisting of: 24. Resin is about 200-3,000sp at 25 ° C
has a viscosity of s and the curing agent is magnesium oxide
23. The method according to 23 above. 25. If the resin is formaldehyde 1.1 to 2.2
Phenol and phenol in a molar ratio of 1 mol of phenol to
23. The method according to 23 above, which is a condensation product with lumaldehyde. 26. The above wherein the accelerator is pentane-2,4-dione
23 ways. 27. Magnesium oxide having two or more different surface areas
25 to 75% by weight of which is 50%
m^TwoHaving a surface area of / g or more and having a surface area of 25 to 75
Weight% is 10 to 25 m^Two2 with a surface area of / g
Method 4 28. The accelerator is 2,4,6-tris (dialkyl acrylate)
The method according to the above 24, which is minomethyl) phenol. 29. The accelerator comprises a sulfamate anion in the mixture.
25. The method according to the above 25, which is a compound given to. 30. 25. The method of 25 above, wherein the accelerator is lithium carbonate. 31. Said accelerator compound in combination with said anion
The cations that form are hydrogen, sodium, potassium,
Lithium, calcium, magnesium, ammonium and
And lower having 1 to 4 carbon atoms in each alkyl group
A selected from the group consisting of alkyl-substituted ammonium
The method according to the above 25, which is thione 32. Nister functional curing agents are lactones, cyclic organic
Carbonic acid esters, carboxylic acid esters and mixtures thereof
24. The method according to 24 above, which is selected from the group consisting of: 33. 32. The method according to 32 above, wherein the ester is a lactone. 34. The lactone is gamma-butyrolactone
33 method. 35. Wherein the ester is an ester of a carboxylic acid
32 ways. 36. A. It has a pH of about 5 to 9 and a solid content of
About 50 to 90% by weight of fat and at 25 ° C
Curable with a viscosity of about 100 to 4,000 cps
Phenol resole resin; B. Hydroxide mag, which accounts for about 5 to 50% by weight of the resin
Nesium and about 10m^TwoMild with a surface area of / g or more
Magne selected from the group consisting of calcined magnesium oxide
C. hardener; C.I. The calcium-containing compound is a magnesium hardener 50
Less than wt%, corresponding to the calcium-containing compound
Oxidation catalyst that replaces heavy magnesium hardener
Made from lucium, calcium hydroxide and calcined dolomite
A calcium-containing compound selected from the group; and D. Approximately 0.5 to 5% by weight of the resin, (1) having a solubility in water of 1% by weight or more at 25 ° C.
Increase the amount of water soluble magnesium in the mixture
A compound that gives an anion to the mixture, provided that the anion is
Is cyanate anion, formate anion, hypophosphite anio
Ion, nitrate anion, phosphite anion and sulfamine
Selected from the group consisting of acid anions; (2) having 1 to 3 carbon atoms in each alkyl group
2,4-di (dialkylaminomethyl) phenol,
Di (dialkylaminomethyl) phenol and 2,4
From 6-tris (dialkylaminomethyl) phenol
(3) each lower alkyl has 1 to 3 carbon atoms
1,3,5-tri (lower alkyl) hexahydro-
1,3,5-triazine; (4) 1,4-diazabicyclo [2.2.2. ] Ok
Tan (5) Pentane-2,4-dione, Heptane-2,4
-Dione, 2,2'-bipyridine and benzoylaceto
A chelating agent selected from the group consisting ofA compound of the formula (a) R¹And R^TwoIs 1 to 3 carbon atoms, respectively
Selected from the group consisting of alkyl having
R¹And R^TwoCoalesces with the nitrogen to which they bind
When it comes to piperidino, piperazino, morpholino, thiomo
Selected from the group consisting of luforino and pyrrolidino
(B) X is (-CH_Two−)_n(N is an integer from 1 to 6
Number), -CH = CH-CH_Two, -CH-CH = CH-CH
_Two-,And (c) R is selected from the group consisting of:^ThreeAnd R^FourIs hydrogen, 1 to 3 charcoal, respectively
Selected from the group consisting of alkyl having elementary atoms
And R^ThreeAnd R^FourTogether with the nitrogen to which they bind
When you wear it, piperazino, morpholino, thiomorpholino,
Selected from the group consisting of piperidino and pyrrolidino
A composition prepared by curing a mixture consisting of 37. Hardener is magnesium oxide, calcium
The amount of the compound is about 1 to 25% by weight of the magnesium hardener.
And the mixture is about 5 to 40% by weight of the resin
36. The composition of 36 above, which comprises the ester functional curing agent of. 38. The resin is condensed with phenol and formaldehyde.
The composition of 36 above which is a combined product. 39. The above wherein the accelerator is pentane-2,4-dione
37 compositions. 40. The anion provided by the compound is sulf
38. The composition according to the above 38, which is an amine acid anion. 41. A. It has a pH of about 5 to 9 and a solid content of
About 50 to 90% by weight of fat and at 25 ° C
Curable with a viscosity of about 100 to 4,000 cps
Phenol resole resin; B. Hydroxide mag, which accounts for about 5 to 50% by weight of the resin
Nesium and about 10m^TwoMild with a surface area of / g or more
Magne selected from the group consisting of calcined magnesium oxide
C. hardener; C.I. Ester functionality accounting for about 5-40% by weight of the resin
Hardener; and D. It accounts for about 0.5 to 5% by weight of the resin, and has a water solubility of 1% by weight or more at 25 ° C.
The cyanate anion, formate anion and hypophosphite
Nion, nitrate anion, phosphite anion and sulfa
The anion selected from the group consisting of
Compounds given to the mixture; (2) having 1 to 3 carbon atoms in each alkyl group
2,4-di (dialkylaminomethyl) phenol,
2,6-di (dialkylaminomethyl) phenol and
2,4,6-Tris (dialkylaminomethyl) pheno
(3) each lower alkyl group also has 1 to 3 carbon atoms
1,3,5-tri (lower alkyl) hexahydro-
1,3,5-triazine; (4) lithium carbonate; (5) 1,4-diazabicyclo [2.2.2. ] Ok
(6) pentane-2,4-dione, heptane-2,4
-Dione, 2,2'-bipyridine and benzoylaceto
A chelating agent selected from the group consisting ofA compound of the formula (a) R¹And R^TwoIs 1 to 3 carbon atoms, respectively
Selected from the group consisting of alkyl having
R¹And R^TwoCoalesces with the nitrogen to which they bind
When it comes to piperidino, piperazino, morpholino, thio
Selected from the group consisting of morpholino and pyrrolidino
(B) X is (-CH_Two−)_n(N is an integer from 1 to 6
number), Selected from the group consisting of: (c) R^ThreeAnd R^FourAre 1 to 3 carbons of hydrogen, respectively
Selected from the group consisting of alkyl having atoms
Yes, R^ThreeAnd R^FourCoalesces with the nitrogen to which they bind
When you do Piberazino, Morpholino, Thiomorpholino, Pi
Selected from the group consisting of peridino and pyrrolidino
Representing a composition prepared by curing a mixture of
object. 42. The viscosity of the resin at 25 ° C. is 200 to
3,000 cps and the curing agent is magnesia
41. The composition of 41 above which is um. 43. The resin is formaldehyde each 1.1 to 2.
Phenol in a molar ratio of about 1 mole of phenol to 2 moles
41, which is a condensation product of styrene and formaldehyde.
Composition. 44. The amount of magnesium oxide hardener is based on resin weight
Varies in the range of about 10-40%; ester functional cure
Agents are lactones, cyclic organic carbonates, carboxylic acid esters
Selected from the group consisting of tellurium and mixtures thereof.
And the accelerator is about 1.0 to 5 on a resin weight basis.
42. The composition of 42 above, which varies in the range of%. 45. The accelerator is cyanate anion, formate anion,
Hypophosphite anion, nitrate anion, phosphite anion
And selected from the group consisting of sulfamate anions
The set of 44 above, which is a compound that provides an anion to the mixture
A product. 46. A click that combines with an anion to form the compound
On is hydrogen, sodium, potassium, lithium, cal
Cium, magnesium, ammonium and each alkyl group
Alkyl-substituted ammo having 1 to 4 carbon atoms in
The above-mentioned 4 which is a cation selected from the group consisting of
The composition of 5. 47. The promoter is 1 to 3 carbons in each alkyl group
2,4-di (dialkylaminomethyl) phenyl having atoms
Enol, 2,6-di (dialkylaminomethyl) phen
And 2,4,6-tris (dialkylaminomethy)
Le) is selected from the group consisting of phenols
44. The composition of item 44. 48. The promoter is 1 to 3 carbons in each alkyl group
1,3,5-tri (lower alkyl) hexa having atoms
The composition of 44, which is hydro-1,3,5-triazine.
object. 49. The above wherein the accelerator is pentane-2,4-dione
44 compositions. 50. The accelerator is (1,4-diazabicyclo [2.2.
2. ] The composition of 44 above which is octane. 51. Accelerators are pentane-2,4-dione, hepta
-2,4-dione, 2,2'-pypyridine and benzo
A chelating agent selected from the group consisting of ylacetone
44. The composition according to 44 above. 52. Accelerator has a chemical formulaWhich is a compound of the formula: R¹And R^TwoEach have 1 to 3 carbon atoms
R is selected from the group consisting of alkyl¹Over
And R^TwoWhen they coalesce with the nitrogen they bind to
Is pibelidino, piperazino, morpholino, thiomorpho
Lists selected from the group consisting of Rhino and Pyrrolidino
Eagle B. X is (-CH_Two−)_n(N is an integer of 1 to 6),-
CH = CH-CHas well as T, CR^ThreeAnd R^FourIs hydrogen, 1 to 3 carbon atoms, respectively
Selected from the group consisting of alkyl having a child
R^ThreeAnd R^FourCoalesces with the nitrogen to which they bind
When doing, piperazino, morpholino, thiomorpholi
No, selected from the group consisting of piperidino and pyrrolidino
44. The composition of the above 44, wherein: 53. 44. The composition of the above 44, wherein the accelerator is lithium carbonate
object. 54. The accelerator is an acid addition salt of an amine, and the salt is
It has a water solubility of 1% or more at 25 ° C and has an acid content of
On is cyanate anion, hypophosphite anion, nitrate
Nion, phosphite anion and sulfamate anion
Is selected from the group consisting of
Has 2, 3-4 carbon atoms in each alkyl group
Di (dialkylaminomethyl) phenol, 2,6-di
(Dialkylaminomethyl) phenol and 2,4,6
-From tris (dialkylaminomethyl) phenol
Selected from the group: 1 to 3 in each alkyl group
1,3,5-tri (lower alkyl) having 4 carbon atoms
Hexahydro-1,3,5-triazine; 2,2'-bi
Pyridine 1,4-diazabicyclo [2.2.2. ] Ok
Tan; and chemical formulaHowever, in the above formula, A. R¹And R^TwoEach have 1 to 3 carbon atoms.
Selected from the group consisting of
¹And R^TwoWhen they coalesce with the nitrogen they bind to
Include piperidino, piperazino, morpholino, thiomol
Selected from the group consisting of holino and pyrrolidino
Representation; B. X is (-CH_Two−)_n(N is an integer of 1 to 6),-
CH = CH-CHC. R^ThreeAnd R^FourIs hydrogen, 1 to 3 carbon atoms, respectively
Selected from the group consisting of alkyl having a child
R^ThreeAnd R^FourCoalesces with the nitrogen to which they bind
When doing, piperazino, morpholino, thiomorpholi
No, selected from the group consisting of piperidino and pyrrolidino
Representing the composition of the above 44, which is selected from the group consisting of
object. 55. 54. wherein the acid addition salt is a sulfamate
Composition. 56. Table with two or more different magnesium oxide hardeners
Approximately 25 to 75% by weight of which is 50 m^Two
25 to 75 weight with a surface area of / g or more
% Is about 10 to 25 m^Two44 having a surface area of / g
Composition. 57. The resin is condensed with phenol and formaldehyde.
The composition of 44, which is a combined product. 58. The above 4 in which the ester functional curing agent is a lactone
The composition of 4. 59. The composition of 44, which is cured at room temperature. 60. 59. The composition of 59 above, which is thermally cured. 61. A. Aggregate B. The pH is about 5 to 9 and the resin solid content is the above-mentioned tree.
About 50-60% by weight of fat and viscosity at 25 ° C
Curable pheno that is about 100 to 4,000 cps
Resole resin C.I. Magnehydroxide in an amount of about 5 to 40% by weight of the resin.
Sium and 10m^TwoCalcination with a surface area of / g or more
Magnesium selected from the group consisting of magnesium oxide
Hardening agent; D. A sufficient amount of acceleration to accelerate curing of the mixture
Agents, provided that the accelerator is (1) cyanate anion, quinate anion, phosphite
Anion, nitrate anion, phosphite anion and sulphate
An anion selected from the group consisting of amine acid anions
A compound to give to the mixture; (2) having 1 to 3 carbon atoms in each alkyl group
2,4,6-tris (dialkylaminomethyl) fe
(3) Each alkyl group has 1 to 3 carbon atoms
1,3,5-tri (lower alkyl) hexahydro-1,
3,5-triazine; (4) lithium carbonate; (5) 1,4-diazabicyclo [2.2.2. ] Ok
(6) pentane-2,4-dione, heptane-2,4
-Dione, 2,2'-bipyridine and benzoylaceto
A chelating agent selected from the group consisting ofA compound of the formula (a) R¹And R^TwoIs 1 to 3 carbon atoms, respectively
Selected from the group consisting of alkyl having
R¹And R^TwoCoalesces with the nitrogen to which they bind
When it comes to piperidino, piperazino, morpholino, thiomo
Selected from the group consisting of luforino and pyrrolidino
(B) X is (-CH_Two−)_n(N is an integer from 1 to 6
Number), -CH = CH-CH_Two, -CH_Two-CH = CH-CH_Two
-,Is selected from the group consisting of; and (c) R^ThreeAnd R^FourIs hydrogen, 1 to 3 charcoal, respectively
Selected from the group consisting of alkyl having elementary atoms
And R^ThreeAnd R^FourTogether with the nitrogen to which they bind
When merging, piberazino, morpholino, thiomorpho
From the group consisting of Rhino, Piperidino and Pyrrolidino
A crude batch composition comprising a mixture of: 62. The pH of the resin is about 5 to 8.5; the amount of resin
Is about 3 to 20% by weight based on aggregate; and the mixture
Is a sufficient amount of ester to increase its cure rate
61. The composition of 61 above, comprising a functional curing agent. 63. The composition of 62, cured at ambient temperature. 64. Magnesium hardener is about 10 ~ 200m^Two/
magnesium oxide having a surface area of g, and
The mixture is sufficient to improve the flexural strength of the composition upon curing.
62. The composition of 62 above, comprising an amount of fiber. 65. The aggregate is sand and the composition is based on resin weight
About 0.1 to 1.5% silane adhesion promoter and about 0.
6 above, containing 005 to 0.1% air vent
The composition of 4. 66. The composition of claim 62, which is thermally cured. 67. Refractory grade magnesia and aluminum
Na, zirconia, silica, silicon carbide, silicon nitride, nitrogen
Boron bromide, bauxite, quartz, corundum, zircon
Group consisting of sand, olivine sand and mixtures thereof
62. The composition of 62 above, which is selected from: 68. Phenol resole resin is phenol and form
It is a condensation product of aldecht and the composition is
62. The composition of 62 above, which comprises: 69. About 5 to 25% graphite and bone based on the weight of the aggregate
About 1 to 5% of the weight of aluminum, magnesium and magnesium
And a metal powder selected from the group consisting of
67. The composition according to 67 above. 70. The composition of 69 above, cured at ambient temperature. 71. 69. The thermally cured article of item 69 above. 72. A. pH is about 5 to 9 and resin solids content is
About 50 to 90% by weight of the resin and at 25 ° C
Curing with a viscosity of about 100 to 4,000 cps
Possible phenolic resole resins; B. Magnesium hydroxide and about 10m^Two/ G or more surface
Selected from the group consisting of lightly calcined magnesium oxide having a product
Magnesium hardener selected, provided that the amount of hardener is
An amount sufficient to increase the cure rate of the resin; Ester functionality accounting for about 5 to about 40% of resin weight
Hardening agent; D. The mixture, which accounts for about 0.1 to 5% of the resin weight.
The anion that increases water-soluble magnesium in the mixture
An accelerator for the compound, provided that the anion is bisulfite
Nion, hydrogen sulfate anion, bromide anion, chloride
Nion, sulfate anion, sulfite anion and thiosulfate anion
73. A crude batch composition comprising a mixture of: The resin is about 200 to 3,000c at 25 ° C
It has a viscosity of ps and the magnesium hardener is magnesium oxide.
Um and the composition consists of aggregate and filler
72. The composition of 72 above, including that selected from the group. 74. The mixture is calcium oxide, calcium hydroxide
Calci selected from the group consisting of mud and calcined dolomite
Amount of Calcium-Containing Compound Containing Umium-Containing Compound
Varies in the range of about 1 to 25% by weight of the magnesium hardener.
And the calcium-containing compound is based on weight
Replace the equivalent amount of magnesium hardener with
Composition. 75. The anion is provided by an acid addition salt of an amine.
The anion of the acid is hydrogen sulfite anion, hydrogen sulfate
Anions, bromide anions, chloride anions, sulfate anions
Group consisting of on, sulfite anion and thiosulfate anion
73. The composition of 73 above, which is selected from: 76. 73. The composition of 73 above, wherein the ester is a lactone. 77. The above 7 in which the nister is an ester of a carboxylic acid.
The composition of 3. 78. The anion contains reactive organochlorine or bromine.
73. The composition of 73 above, which is provided by a compound. 79. The set of 73 above, wherein the anion is a chloride anion
A product. 80. The anion is sulfate anion, hydrogen sulfate anion or
The composition of 73 above, wherein is a bisulfite anion. 81. 73. The composition of 73 above, which is cured at room temperature. 82. Increase in viscosity at room temperature is allowed, followed by heat
73. The composition of claim 73, which is cured. 83. A. Curable pheno having a pH of about 5-9
Resole resin; B. Sufficient light baking to increase the cure rate of the resin
Magnesium oxide hardener, provided that the hardener has two or more phases.
Approximately 25-75% by weight contains grains of different surface areas
50m^Two25 to 75 having a surface area of not less than / g
Weight% is about 10 to 25 m^TwoHaving a surface area of / g; 84. A sufficient amount to increase the cure rate of the mixture
83. The composition of 83 above, which comprises an ester functional curing agent. 85. The amount of magnesium oxide is 5 to 50 times that of the resin.
% By weight, the amount of ester being about 5 to 40% by weight of the resin
%, And there are two or more different magnesium hardeners.
Of about 25 to 75 weight
Quantity% is 50m^TwoWith a surface area of / g or more and its 25
Up to 75% by weight is about 10 to 25 m^TwoHas a surface area of / g
83. The composition according to 83 above. 86. Phenol resole resin is phenol and form
84. The composition according to 84 above, which is a condensation product with an aldehyde. 87. 83. The composition as set forth above in 83, which was cured at room temperature. 88. Viscosity increase is allowed at room temperature, and
83. The composition as described above, which is cured.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08K 3/26 5/04 5/10 5/13 5/16 5/3492

Claims (7)

[Claims] 1. A method of accelerating the cure of a phenolic resin binder composition, the method comprising: C. Curable phenolic resole resin having a pH of about 4.5 to 9.5; B. A magnesium hardener selected from the group consisting of magnesium hydroxide and a lightly calcined magnesium oxide having a surface area of about 10 m ² / g or more, provided that the amount of the hardener is sufficient to increase the cure rate of the resin; And C.I. (1) It has a solubility of 1% by weight or more in water at 25 ° C. and is selected from the group consisting of cyanate anion, formate anion, hypophosphite anion, nitrate anion, phosphite anion and sulfamate anion. A compound giving an anion to the mixture; (2) 2,4-di (dialkylaminomethyl) phenol having 1 to 3 carbon atoms in each alkyl group,
Those selected from the group consisting of 2,6-di (dialkylaminomethyl) phenol and 2,4,6-tris (dialkylaminomethyl) phenol; (3) each lower alkyl group contains 1 to 3 carbon atoms. Having 1,3,5-tri (lower alkyl) hexahydro-
1,3,5-triazine; (4) lithium carbonate; (5) 1,4-diazabicyclo [2.2.2. ] Octane; (6) Pentane-2,4-dione, Heptane-2,4
A chelating agent selected from the group consisting of: dione, 2,2'-bipyridine and benzoylacetone; and Wherein R ¹ and R ² are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R ¹ and R ² are When coalescing with the bonding nitrogen, piperidino, piperazino, morpholino,
Represents those selected from the group consisting thiomorpholino and pyrrolidino; (b) X is (-CH ₂ -) _{n (n} is an integer of 1 to 6), -CH = CH-CH 2, -CH 2 -CH = CH-CH ₂
-, (C) R ³ and R ⁴ are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and R ³ And R ⁴ represents one selected from the group consisting of piperazino, morpholino, thiomorpholino, piperidino and pyrrolidino when they combine with the nitrogen to which they are attached; an accelerator selected from the group consisting of, but the amount of said accelerator Is in an amount sufficient to accelerate the curing of the mixture; 2. A method for accelerating the curing of a phenol resole resin composition, which comprises: The pH is about 5 to 9, the solid content is about 50 to 90% by weight of the resin, and the viscosity is about 10 at 25 ° C.
A curable phenolic resole resin that is 0 to 4,000 cps; B. A magnesium hardener selected from the group consisting of magnesium hydroxide in an amount of about 5 to 50% by weight with respect to the resin and lightly calcined magnesium oxide having a surface area of about 10 m ² / g or more; C.I. An ester functional curing agent in an amount of about 5 to 40% by weight of the resin; and D. An amount of about 0.5 to 5% by weight of the resin; A compound giving an anion selected from the group consisting of a phosphite anion and a sulfamate anion to the mixture; (2) 2,4-di (dialkylaminomethyl) having 1 to 3 carbon atoms in each alkyl group ) Phenol,
2,6-di (dialkylaminomethyl) phenol and 2,4,6-tris (dialkylaminomethyl) phenol; (3) 1,3,5-tri with each lower alkyl group having 1 to 3 carbon atoms (Lower alkyl) hexahydro-
1,3,5-triazine; (4) lithium carbonate; (5) 1,4-diazabicyclo [2.2.2. ] Octane; (6) Pentane-2,4-dione, Heptane-2,4
A chelating agent selected from the group consisting of: dione, 2,2'-bipyridine and benzoylacetone; and Wherein R ¹ and R ² in the above formula are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R ¹ and R ² are bound to them. When combined with nitrogen, it represents one selected from the group consisting of piperidino, piperazino, morpholino, thiomorpholino and pyrrolidino; (b) X is (-CH _2- ) _n (n is an integer of 1 to 6), -CH _{= CH-CH 2 -, -} CH 2 -CH = CH-CH
₂ , And (c) R ³ and R ⁴ are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and R ³ And R ⁴ represents a compound selected from the group consisting of piperazino, morpholino, thiomorpholino, piperidino and pyrrolidino when they combine with the nitrogen to which they are attached; a promoter selected from the group consisting of; And how to. 3. A. pH of about 5-9, solids content of about 50-90% by weight of the resin and 25 ° C.
A curable phenolic resole resin having a viscosity in the range of about 100 to 4,000 cps; B. A magnesium hardener selected from the group consisting of magnesium hydroxide in an amount of about 5 to 50% by weight of the resin and a lightly calcined magnesium oxide having a surface area of about 10 m ² / g or more; C. Calcium-containing compound is a magnesium hardener 5
Less than 0% by weight, the calcium-containing compound being selected from the group consisting of calcium oxide, calcium hydroxide and calcined dolomite, wherein the calcium-containing compound replaces the equivalent weight magnesium hardener; and D. An amount of about 0.5 to 5% by weight of the resin of (1) an anion having a solubility in water at 25 ° C. of not less than 1% by weight to increase the amount of water soluble magnesium of the mixture to the mixture. A compound that provides, provided that the anion is selected from the group consisting of cyanate anion, formate anion, hypophosphite anion, nitrate anion, phosphite anion and sulfamate anion; (2) 1 to 3 in each alkyl group 2,4-di (dialkylaminomethyl) phenols having 4 carbon atoms,
Di (dialkylaminomethyl) phenol and 2,4
Selected from the group consisting of 6-tris (dialkylaminomethyl) phenol; (3) 1,3,5-tri (lower alkyl) hexahydro-, each lower alkyl having 1 to 3 carbon atoms.
1,3,5-triazine; (4) 1,4-diazabicyclo [2.2.2. ] Octane; (5) Pentane-2,4-dione, Heptane-2,4
A chelating agent selected from the group consisting of: dione, 2,2'-bipyridine and benzoylacetone; and Wherein R ¹ and R ² are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R ¹ and R ² are When coalescing with the bonding nitrogen, piperidino, piperazino, morpholino,
Represents those selected from the group consisting thiomorpholino and pyrrolidino; (b) X is (-CH ₂ -) _{n (n} is an integer of 1 to 6), -CH = CH-CH 2, -CH-CH = CH-CH ₂
-, And (c) R ³ and R ⁴ are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and R ³ And R ⁴ when combined with the nitrogen to which they are attached piperazino, morpholino, thiomorpholino,
A composition prepared by curing a mixture consisting of a group selected from the group consisting of piperidino and pyrrolidino. 4. A. pH of about 5-9, solids content of about 50-90% by weight of the resin and 25 ° C.
A curable phenol resone resin having a viscosity in the range of about 100 to 4,000 cps; B. A magnesium hardener selected from the group consisting of magnesium hydroxide in an amount of about 5 to 50% by weight of the resin and a lightly calcined magnesium oxide having a surface area of about 10 m ² / g or more; C. An ester functional curing agent in an amount of about 5 to 40% by weight of the resin; and D. Approximately 0.5 to 5% by weight of the resin, (1) having a water solubility of 1% by weight or more at 25 ° C., and having a cyanate anion, a formate anion, a hypophosphite anion, a nitrate anion, A compound that gives the mixture an anion selected from the group consisting of a phosphate anion and a sulfamate anion; (2) 2,4-di (dialkylaminomethyl) phenol having 1 to 3 carbon atoms in each alkyl group. ,
Those selected from the group consisting of 2,6-di (dialkylaminomethyl) phenol and 2,4,6-tris (dialkylaminomethyl) phenol; (3) each lower alkyl group contains 1 to 3 carbon atoms. Having 1,3,5-tri (lower alkyl) hexahydro-
1,3,5-triazine; (4) lithium carbonate; (5) 1,4-diazabicyclo [2.2.2. ] Octane; (6) Pentane-2,4-dione, Heptane-2,4
A chelating agent selected from the group consisting of: dione, 2,2'-bipyridine and benzoylacetone; and Wherein R ¹ and R ² are each selected from the group consisting of alkyl having 1 to 3 carbon atoms and R ¹ and R ² are bound to them. when combined with nitrogen, piperidino, piperazino, morpholino, represents those selected from the group consisting thiomorpholino and pyrrolidino; (b) X is (-CH ₂ -) _{n (n} is an integer of 1 to 6), - _{CH = CH-CH 2, -CH} 2 -CH = CH-CH 2
-, (C) R ³ and R ⁴ are each selected from the group consisting of alkyl having 1 to 3 hydrogen atoms, and R ³ and R ⁴ Represents a group selected from the group consisting of piperazino, morpholino, thiomorpholino, piperidino and pyrrolidino when they combine with the nitrogen to which they are attached; a composition prepared by curing a mixture of. 5. A. Aggregate B. The pH is about 5 to 9, the resin solid content is about 50 to 60% by weight of the resin, and the viscosity is 25 ° C.
Curable Phenolic Resole Resin C.I. A magnesium hardener selected from the group consisting of magnesium hydroxide in an amount of about 5 to 40% by weight of the resin and a lightly calcined magnesium oxide having a surface area of about 10 m ² / g or more; D. An amount of an accelerator sufficient to accelerate the curing of the mixture, provided that the accelerator comprises (1) cyanate anion, formate anion, hypophosphite anion, nitrate anion, phosphite anion and sulfamate anion. A compound that gives an anion selected from the group to the mixture; (2) 2,4,6-tris (dialkylaminomethyl) phenol having 1 to 3 carbon atoms in each alkyl group; (3) each alkyl group 1,3,5-tri (lower alkyl) hexahydro-1, having 1 to 3 carbon atoms,
3,5-triazine; (4) lithium carbonate; (5) 1,4-diazabicyclo [2.2.2. ] Octane; (6) Pentane-2,4-dione, Heptane-2,4
A chelating agent selected from the group consisting of: dione, 2,2'-bipyridine and benzoylacetone; and Wherein R ¹ and R ² in the above formula are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R ¹ and R ² are bound to them. When combined with nitrogen, it represents one selected from the group consisting of piperidino, piperazino, morpholino, thiomorpholino and pyrrolidino; (b) X is (-CH _2- ) _n (n is an integer of 1 to 6), -CH _{= CH-CH 2, -CH 2} -CH = CH-CH 2
-, And (c) R ³ and R ⁴ are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and R ³ And R ⁴ when combined with the nitrogen to which they are attached represent a group selected from the group consisting of piperazino, morpholino, thiomorpholino, piperidino and pyrrolidino; a crude batch containing a mixture of Composition. 6. A. has a pH of about 5-9, a resin solids content of about 50-90% by weight of the resin, and 2
C. A curable phenolic resole resin having a viscosity at 5 ° C. of about 100 to 4,000 cps; B. A magnesium hardener selected from the group consisting of magnesium hydroxide and lightly calcined magnesium oxide having a surface area of about 10 m ² / g or more, provided that the amount of said hardener is sufficient to increase the hardening rate of said resin. Yes; C. An ester functional curing agent comprising about 5 to about 40% of the resin weight; D. An accelerator that provides the mixture with an anion that increases the water-soluble magnesium in the mixture in an amount of about 0.1 to 5% by weight of the resin, where the anion is bisulfite anion, hydrogensulfate anion, bromide anion, chloride. Selected from the group consisting of anions, sulfate anions, sulfite anions and thiosulfate anions; 7. A. A curable phenolic resole resin having a pH of about 5-9; B. A sufficient amount of a lightly calcined magnesium oxide hardener to increase the cure rate of the resin, provided that the hardener comprises two or more grains of different surface areas, about 25-75% by weight thereof.
Has a surface area of 50 m ² / g or more and its 25 to 7
5% by weight has a surface area of about 10 to 25 m ² / g.