JPH04300948A - Cure accelerator for resol phenolic resin - Google Patents

Abstract

PURPOSE: To provide an accelerator that can shorten the curing time of a phenolic resole resin binding composition containing, as a curing agent, for example, magnesium hydroxide or magnesium oxide at room temperature and particularly in a cold climate or under low-temperature conditions.

CONSTITUTION: This curing accelerator is selected from (A) a compound that has a solubility of 1 wt.% or more in water at 25°C and gives anions, such as cyanate anions, formate anions, and hypophosphite anions, to a mixture, (B) a 2,4- or 2,6-di(dialkylacynomethylphenol) having 1-3C alkyl or the like, (C) 1,3,5-tri(1-3C alkyl)hexahydro-1,3,5-triazone, (D) lithium carbonate, (E) 1,4- diazabicyclo[2,2,2]octane, (F) a chelating agent such as pentan-2,4-dione and heptan-2,4-dione, and (G) a compound of formula I [R¹ and R² each represent 1-3C alkyl, X represents formula II (n is an integer of 1 to 6), formula III, etc., and R³ and R⁴ each represent H, 1-3C alkyl, etc.].

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD This invention relates to a method and composition for accelerating the curing of phenolic resole resin binder compositions cured with magnesium oxide or magnesium hydroxide alone or in combination with ester-functional curing agents. . Such curing can occur at about room temperature.

0002

BACKGROUND OF THE INVENTION The use of lightly calcined magnesium oxide or magnesium hydroxide hardeners, alone or in combination with ester-functional hardeners, to accelerate the curing of phenolic resole resins, i.e. the time required for their curing. Shortening is often desirable, especially when such acceleration does not significantly affect the hardness, tensile strength, and other desirable properties of the cured resin, especially in cold climates or low temperature conditions. There is.

[0003] In the present invention, magnesium oxide or magnesium hydroxide with or without an ester-functional hardener is used as the hardener. Applicant has discovered 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, is possible from certain amines or curing agents mixed with the resin. They discovered that this can be promoted by using a compound that improves the solubility of magnesium ions. The accelerator may be, for example,
It is a compound that provides chloride ions, sulfate ions, sulfamate ions, and various amino compounds such as 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 in the production of phenol-formaldehyde resol resins from phenol and formaldehyde. Additionally, relatively inert magnesia, such as periclene or refractory grade magnesia, is a common refractory that is often bonded into various shapes using phenolic resol resins; Not used as a hardener. Literature disclosing the use of magnesium oxide or magnesium hydroxide for curing phenolic resole resins in each type of composition includes, for example, Cooper (
R. H. Cooper) U.S. Patent No. 2,869,19
No. 4 (January 20, 1959); Cooper's No. 2 and 8
No. 69,196 (January 20, 1959); Cooper No. 2,913,787 (November 24, 1959)
; T. Murata et al., No. 3,666,7
No. 03 (May 30, 1972): Mitchell (J.S.
．． No. 2,712,533 (19
July 5, 1955); Adams (W.H., Adams, J.
No. 2,424,787 (July 2, 1947)
9th); and M.K.Gupta's 4th,
No. 794,051 (December 27, 1988).

[0005]Gupta US Pat. No. 4,794,051 also points to the use of certain ester-functional hardeners, or lactones, with magnesium hardeners, although mixtures with calcium hardeners are preferred. There is. Cooper U.S. Pat. No. 2,869,194 discloses that magnesium oxychloride and magnesium oxysulfate, which can be prepared by mixing magnesium oxide powder with an aqueous solution of magnesium chloride or its equivalent or magnesium sulfate or its equivalent, are magnesium oxide alone. It is also noted that curing times are frequently reduced compared to Cooper, U.S. Pat. No. 2,913,787, discloses the inclusion of a "novolak type" phenolic resin as an optional component in its composition, and the optional inclusion of hexamethylenetetramine or ethylene diamine, diethylene amine and similar compounds. The inclusion of equivalent phenolic hardeners or accelerators, including low molecular weight polyamines and para-formaldehyde, is also indicated.

No. 450,989 entitled "Phenolic Resin Compositions" (filed December 1, 1989).
5th, inventor Lemon (P.H.R.B. Lemon),
King (J. King), Leoni (H. Leoni),
Murray (G. Murray) and Gerber (A.H.
Gerber); GB882984.7 (filed in 1988
(February 22)) prepares phenolic resins using alkali metal compounds or alkaline earth metal compounds as base catalysts, and then esterifies phenolic resins and oxides of magnesium and calcium as ester-functional curing agents. It discloses curing the resin at room temperature using various bases including and hydroxides. European Patent Application Publication No. 0094165 (January 1983)
Announced on January 16th, inventor Lemon (P.H.R.B.Le
(mon) etc.) have extensively enumerated the use of various alkaline materials, including magnesium oxide (magnesia), for condensing phenol and formaldehyde to form phenol-formaldehyde resins and further increasing the alkalinity of such resins. The use of ester-functional agents in the curing of phenolic resins is indicated. European Patent Application Publication No. 0243,172 (published October 28, 1987, inventor Lemmon et al.) is listed similarly to the aforementioned European Patent Application Publication No. 0094165.

US Pat. No. 4,939,188 (199
Announced on July 3, 2007, inventor A.H. Gerber
ber) discloses the use of a lithium ion generating alkalizing agent in a resole resin binder composition, which composition when cured with an ester functional curing agent generates sodium or potassium ions. It exhibits better tensile strength than compositions using alkalizing agents.

[0008] Higgenbottom
), U.S. Pat. No. 4,011,186 (March 8, 1977) and Dahms, U.S. Pat.
No. 298 (August 5, 1980) relates to a phenol resol resin that uses an alkaline earth metal hydroxide as a catalyst and is neutralized with oxalic acid or its acid salt, and oxalic acid or its acid salt is stable. It is dispersed in the resol as an insoluble oxalate salt, further increasing the viscosity of the resol resin.

US Pat. No. 3,624,247 to Gladney et al. is directed 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 salts and adjusting the pH to form an insoluble salt containing calcium. U.S. Patent No. 3,624,247
The soluble ammonium compounds used in this issue include sulfates, phosphates, and carbonates.

Lemon et al. US Reissue Patent No. 32,720
No. (July 26, 1988) and No. 32,812 (July 26, 1988)
(December 27, 1988) is a further example document, which discloses the room temperature curing of highly alkaline phenol formaldehyde resins with ester curing agents. Tokukai Showa 6
No. 0-90251 (May 21, 1985, Kyushu Refractories) discloses the cold curing of thermosetting resol resins through the use of ethylene carbonate and magnesium oxide.

US Patent Application Serial No. 07/562,206, the US parent patent of this application, discloses materials such as various anions for retarding the curing of phenolic resole resins with magnesium curing agents.

0012

Room temperature curing of phenolic resole resin compositions containing cured amounts of lightly calcined magnesium oxide or magnesium hydroxide, alone or in combination with ester-functional curing agents, is difficult to cure with certain amines or It has been found that this can be facilitated by materials that increase the solubility of magnesium in the reaction mixture. Furthermore, the use of relatively small surface area lightly calcined magnesium oxide in combination with large surface area magnesium oxide has little effect on accelerating the curing rate over that of phenolic resin compositions based on large surface area materials; Lithium carbonate functions as both an accelerator and a strength modifier for phenolic resin compositions; and sulfamate accelerators when used with low molecular weight phenolic resins with high free phenol content improve the strength of the composition. It was also found that strength was improved. The phenol resol resin used in the present invention is
Generally has a pH of about 4.5 to 9.5.

[0013] One aspect of the present invention is to provide binder compositions and binder compositions thereof that have reduced cure times by mixing a phenolic resole resin with a magnesium hardener and accelerator with or without an ester-functional hardener. An object of the present invention is to provide a preparation method. Another aspect of the invention is the use of the compositions and methods described above in conjunction with aggregates to patch or resurface various rigid substrates, such as concrete and asphalt structures.

Another aspect of the invention is to provide a shaped article comprising aggregates bonded together with a resin binder, the binder being accompanied by an ester-functional curing agent and/or Phenol formaldehyde resin cured in the presence of unaccompanied magnesium curing agent and accelerator.

[0015]

[Means for Solving the Problem] Examples of accelerators include basic nitrogen compounds and materials that provide chloride ions, sulfate ions, sulfamate ions, and phosphite ions corresponding to acid addition salts of compounds of the following formula. can be mentioned. In the above formula, X is a lower aliphatic hydrocarbon group, and R1 and R
2 is an alkyl group or forms a heterocyclic group when combined with the nitrogen to which they are bonded, and R3 and R4 are hydrogen or an alkyl group, or a heterocyclic group when combined with the nitrogen to which they are bonded. form.

The methods and compositions of the present invention improve the curing of phenolic resole resins with magnesium curing agents by using small amounts of amines or various compounds that increase the solubility of magnesium in the resin composition and accelerate curing of the resin. Reduce the speed to approximately 15.6 to 48.9°C (60 to 120°F).
) provides a means of promoting over a wide temperature range. One of the variables that affects the rate of curing of phenolic resins is temperature. Lower temperatures will reduce the curing rate. The accelerators of the present invention can be used to accelerate the rate of curing over a wide temperature range, including room and ambient temperatures, particularly in cold regions and low-temperature workplaces. The use of the accelerators of the present invention accelerates the curing rate at low temperatures and provides adequate strength while maintaining desirable processing times.

The methods and compositions of the present invention can be modified by selecting the magnesium surface area used, by selecting the particular accelerator, and in some cases by selecting the particular ester and amount of curing agent and accelerator. can influence the reaction rate of the phenolic resole resin.

[0018] Preferred methods and compositions of the present invention use an ester functional curing agent in combination with a magnesium curing agent. When an ester is used in combination with a lightly calcined magnesia or magnesium hydroxide curing agent and an accelerator,
This is because the reaction rate of the phenol resin composition is strongly affected. Additionally, phenolic resole resins cured with both a magnesium curing agent and an ester-functional curing agent have higher compressive and tensile strengths than phenolic resole resins cured with magnesium oxide or magnesium hydroxide alone. , resistance to organic acid aqueous solutions is also increased.

The methods and compositions of the present invention are disclosed in U.S. Patent Reissue No. Re 32,720 to Lemon et al.
No. 32,812 (198
It has a number of advantages over the curing of phenolic resole resins with esters alone, as shown in Dec. 27, 1998). The method and composition of the above U.S. reissued patent require an alkali metal hydroxide, and practically the pH of the resin is 1.
It is 2 or more. In contrast, in the present invention the pH
The values are substantially lower and do not require alkali metal hydroxides or their salts. The above U.S. reissued patent
The compositions and methods of the present invention have a number of advantages over requiring high alkalinities of 10 or 12 or more, and especially over requiring high alkali metal concentrations to produce highly alkaline compositions. It is. For example, the phenolic resin of the present invention has better storage stability;
Improved color stability of the resin over time and exposure to atmosphere; low viscosity even at high solids levels, thereby improving wetting of aggregates and substrates in particular and increasing bond strength;
Safer handling of materials and waste; resins with high solids levels, compositions such as those containing aggregates, are denser and less porous when cured, thus improving strength and making them easier to use with solvents. It has properties such as increased resistance to aqueous media; and improved stability of aggregates that are normally attacked by high pH sodium and improved stability to glass and polyester fibers. Excess alkali can result in strength loss. For example, according to Table 4 of U.S. Reissue Patent Re 32,812 by Lemon et al., the KOH/phenol molar ratio is 0.68 (34.6
7 MPa, 5032 psi) to 1.02 (2
9.43 MPa, 4271 psi), the compressive strength of the resol resin steadily decreases. In contrast, an excess of magnesium hardener increases the strength and also insolubility of the final composition. This is because chain termination occurs when sodium or potassium alkali is used, whereas crosslinking occurs when divalent magnesium is used.

Accelerators may be used to reduce the stripping time of molding or casting materials, or simply to increase the rate of cure, especially when temperatures are significantly below 70°F. It's advantageous.

Magnesium oxide and magnesium hydroxide curing agent

The term "accelerator" as used herein refers to the curable binder in the methods and compositions of the invention, such as a phenolic resole resin, a magnesium hardener, and an optional ester-functional hardener. It means a material that accelerates or simply promotes the gelation or hardening of phenolic resole resins. Some of the accelerators of the present invention appear to 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 solution.

[0023] The term "curing agent" as used herein refers to a material that increases the rate of curing of a phenolic resole resin, for example at room or ambient temperature (RT). The hardening is
This is achieved by gelation forming a generally inflexible solid with increased viscosity and firm feel. The curable binder compositions of the present invention, including a phenolic resin, a magnesium hardener, and an optional ester-functional hardener, but without an accelerator, are generally heated to about 24°C at 75°F (23.9°C). If you leave it for a while, it will harden. This hardening
Although curing can also be called curing, curing with a curing agent does not develop the tensile strength or compressive strength of thermal curing.

The term "room temperature cure" refers to the compositions of the present invention cured at temperatures of about 18.3 to 32.2°C (65 to 90°F), particularly about 18.3 to 26.7°C (65 to 80°F). ) means curing at a temperature of However, when using accelerators in the methods and compositions of the present invention, 15.6 to 4
Temperatures as low and as high as 60-120°F (8.9°C) accelerate curing of the compositions of the present invention. Approximately 15.6
In addition to room temperature curing or cold curing at 60 to 120° F., the compositions of the present invention can be thermally cured after curing with a curing agent, or thermally cured before curing with a curing agent. It can also be hardened. The term "curing" as used in this application refers to 76.
Temperatures above 7°C (170°F), typically 100°C (2
means curing the composition at a temperature of 12° F.) or higher.

The magnesium curing agent is magnesium hydroxide, lightly calcined magnesium oxide, or other magnesium oxide having a curing activity for phenolic resol resin that of lightly calcined magnesium oxide, such as 10m2
It is magnesium oxide with a surface area of 1.2 g or more. Lightly calcined magnesium oxide is the preferred magnesium hardener; magnesium hydroxide provides only low strength to the hardened composition. Small amounts of calcium hydroxide, calcium oxide or calcined dolomite (doloma) can also be added as hardening agents. However, the use of large amounts of calcium oxide, calcined dolomite or calcium hydroxide alone or in combination with magnesium hardeners leads to serious drawbacks. That is, calcium-based oxides or hydroxides containing calcined docomite are strongly basic and react excessively quickly, significantly shortening the pot life of the mixture. However, a small amount of a calcium-containing compound mixed with the magnesium hardener, such as less than about 1 to 50% by weight of the magnesium hardener, can be used in place of an equal weight of the magnesium hardener. This amount is approximately 1/4 of the total weight of the magnesium oxide or magnesium hydroxide curing agent.
Small amounts not exceeding 100% are preferred. A further disadvantage of using calcium-based oxides is that they insolubilize certain promoters.

[0026] The reactivity and surface area of magnesium oxide (magnesia) vary widely depending on the method of producing magnesia. Lightly fired grade magnesium oxide is approximately 871-982°C
(1600-1800°F). Heavy firing grades are approximately 1538 to 1649°C (2
Calcined at temperatures ranging from 800 to 3000 degrees Fahrenheit. Dead burnt grade or periclase grade magnesium oxide is heated at 2204°C (40
00°F) or higher. Lightly calcined grades are generally available in powder or granule form, and heavily calcined grades are available in kiln run, ground or sieve sizes. Periclese is generally available as briquettes and as a sieved or ground fraction. The surface areas of these various types of magnesium vary widely. That is, lightly calcined magnesia has a surface area of about 10 to 200 square meters or more per gram, and heavily calcined magnesia has a surface area of about 1 square meter per gram. In contrast, the surface area of dead burnt magnesia is less than 1 m2/g. Dead burnt magnesia or periclase magnesia is commonly used as a refractory aggregate. however,
Neither hard-burned magnesia nor dead-burnt magnesia are effective hardeners. An effective hardener is lightly calcined magnesia. Magnesia products with various surface areas are available from Martin Marietta Co.
Mag Chem Magnesium Oxide Products (Mag Chem Magnesium
Oxide Products). For example, Magchem 30 is approximately 25m2
Magchem 50 has a surface area of about 65 m2/g, while Magchem 200D has a surface area of about 170 m2/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 as the surface area increases, reducing gelation and curing times. Therefore, lightly calcined magnesium oxide with a surface area of less than about 25 m2/g is slow acting and has a surface area of about 48 m2/g.
It is generally not used when it is desired to cure the binder composition in a relatively short period of time at temperatures below 9°C (120°F). On the other hand,
Magnesia with a large surface area, such as about 62 m2/g or more, cures the same binder composition in a shorter time. For many applications, it is preferred to use magnesia with a surface area of about 25 to 65 m2/g. Heavy-burnt magnesia reacts too slowly as a hardening agent to have any practical value. Dead-fired magnesia is so inert that it is normally used only as a refractory, and when used in phenolic resin binders it has little or no effect on room temperature cure speed.

The phenolic resol resin of the present invention contains one or more volatile solvents including water. Loss of solvent in a thermally cured composition increases porosity, increases permeability to liquids, 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 increased viscosity and reduced gelation time. Incidentally, it has been found that use of lightly calcined magnesium oxide having two or more different surface areas brings about improvement effects such as improving strength without substantially promoting increase in viscosity. The mildly calcined magnesium oxide hardener that achieves the above-mentioned improvement effect is about 25 to 75% by weight.
has a surface area of 50 m2/g or more, and 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 m2/g. Preferably, the magnesium oxide curing agent to provide such an improvement effect consists essentially of particles having two or more different surface areas as indicated in the preamble. Following the differential surface area method, gelation at room or ambient temperature occurs in approximately the same amount of time as with the high surface area curing agent alone, despite the presence of substantially more curing agent. , the compressive strength of the composition upon curing is substantially increased and its porosity and permeability are reduced. Additionally, compositions with increased magnesia also have improved flame retardancy. Compositions containing lightly calcined magnesia of different surface areas may optionally contain accelerators, ester-functional hardeners and fillers, modifiers, aggregates and other additives of the present invention.
It may be present at the same concentration as in lightly calcined magnesium oxide without curing agent mixtures with different surface areas.

The amount of lightly calcined magnesium oxide or magnesium hydroxide used as a curing agent in this invention is an amount sufficient to increase the rate of gelation or curing of the phenolic resole resin. This amount can vary widely. The amount of magnesium hardener used will vary depending on whether an ester hardener is used in the composition, the surface area of the magnesium oxide, the particular ester hardener, the amount of magnesium and ester hardener, the temperature, and the desired effect. That is, the amount of magnesium oxide or magnesium hydroxide curing agent will generally vary from about 5% to 40% by weight of the resin in the various compositions and methods of the invention. However, when using lightly calcined magnesium oxide mixtures of different surface areas, the amount of magnesium oxide is
It is preferable to change the amount in the range of 50% by weight or more. When used as a magnesium oxide or magnesium hydroxide curing agent without an ester curing agent, about 10 to 40% by weight, especially 15 to 30% by weight, based on the weight of the resin.
It is preferable to use it within a range of % by weight. When magnesium oxide or magnesium hydroxide is used in combination with an ester-functional hardener, the amount of magnesium oxide or magnesium hydroxide hardener ranges from about 5 to 30%, particularly about 5 to 20% by weight of the resin weight. It is preferable to change.

Ester Curing Agents Ester functional curing agents, also referred to as ester functional curing agents, accelerate the curing of resole resins when used in conjunction with magnesium curing agents. Additionally, systems using a combination of both magnesium and ester hardeners in a resole resin provide a cure system that is extremely sensitive to small amounts 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 for more than 7 days at 70°F. The ester functionality that cures the phenolic resole resin can be imparted by lactones, cyclic organic carbonates, carboxylic acid esters, or mixtures thereof.

Generally, the ester functional curing agent is:
Low molecular weight lactones such as beta or gamma butyrolactone, gamma valerolactone, caprolactone, beta propiolactone, beta butyrolactone, beta isobutyrolactone, beta isopentyl lactone, gamma isopentyl lactone and delta pentyl lactone are preferred. Examples of suitable cyclic organic carbonates include propylene carbonate: nytylene 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.

[0032] Carboxylic acid esters that can be used in the present invention include phenol esters and aliphatic esters. Aliphatic esters are those of short to medium chain length, such as about 1 to 1
Esters of 0 carbon mono- or polyvalent saturated or unsaturated alcohols with short to medium chain lengths, such as aliphatic, saturated or unsaturated mono- or polyvalent carboxylic acids of about 1 to 10 carbons, are preferred. Suitable aliphatic esters are esters of mono-, di- or tri-hydric alkyl alcohols with mono- or di-unsaturated mono-, di- or trihydric carboxylic acids. The carboxylic acid may be substituted with hydroxyl, cyano, chlorine or bromine.

The aromatic ester can be obtained by esterifying a monovalent or polyvalent aromatic phenol group to prepare its formate or acetate. Furthermore, this aromatic ester has 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 phenolic compounds located ortho and/or para to the phenolic hydroxyl group or the esterified phenolic hydroxyl group. It may further contain a methylol group. Such phenolic esters and methods for their preparation are disclosed in U.S. patent application Ser.
(corresponding to the patent application filed on December 22, 1988), and cites both the US patent and the UK patent. Esterified phenolic compounds are phenols with one or more nuclei having one or more esterified methylol groups, where the one or more esterified methylol groups are phenolic hydroxyl groups or esterified. It is understood that it is bonded to the aromatic ring carbon atom at the ortho or para position of the phenolic hydroxyl group. The acid moiety of the phenolic ester can be the same as the acid moiety 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; Glutal 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,
2',6,6'-tetraacetyloxymethylbisphenol A diacetate. However, it is not limited to the above. Acetate esters derived from aliphatic alcohols having 1 to 5 carbon atoms; benzyl alcohol;
Formate and acetate esters of Arua, Arua-dihydroxyxylenol, phenol, alkyl-substituted phenols, dihydroxybenzene, bisphenol A, bisphenol F and low molecular weight resols are preferred. It is sometimes advantageous to use mixtures of ester-functional curing agents.

Gaseous esters such as formic acid C1-C2 alkyl esters can be used as ester-functional hardeners in low density products or in applying binders to fabric or paper substrates. When gaseous esters are used as curing agents, the esters are generally not mixed with resin binders or aggregates, but instead are supplied 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 improves the tensile strength and crimp strength of the cured composition. Such amounts also increase the rate of curing of the phenolic resole resin in the presence of the magnesium curing agent. This amount varies over a wide range, from about 5 to 40%, preferably from about 10 to 25%, by weight of the phenolic resole resin. With respect to the above magnesium hardeners, the exact amount will depend on the particular ester hardener used, the particular magnesium hardener and amount used, the use concentration and storage temperature of the composition, and the desired result.

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

Phenolic resole resins suitable for use in the present invention have less than about 1% by weight, preferably less than 0.5% by weight, of water-soluble sodium or potassium. Typical phenolic resole resins contain phenol and formaldehyde in a molar ratio ranging from about 1:1 to 1:3 (phenol:
It is a phenol-formaldehyde resin produced by reacting with phenol (formaldehyde). A preferred molar ratio for use in the present invention is about 1 mole of phenol to 1 mole of aldehyde.
The range is from 1 to 2.2 mol, especially the molar ratio of phenol:aldehyde is from 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 amounts of free phenol are about 2 to 25% by weight of resin.
The preferred level is 5 to about 12%. The molecular weight of this resin is approximately 200 to 500 as a weight average molecular weight.
It varies in the range of 0, preferably 300 to 2000. Other things being equal, the higher the molecular weight and the lower the free phenol, the shorter the gelation or curing time and the higher the strength. Weight average molecular weight

(Mw) is determined using gel permeation chromatography and phenolic and polystyrene standards. A sample for measuring molecular weight is prepared as follows. A resin sample is dissolved in tetrahydrofuran, slightly acidified with 1N hydrochloric acid or sulfuric acid, and dried over anhydrous sodium sulfate. The resulting salts are 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, from about 50 to 90% by weight of the phenolic resole resin. Preferably, the resin solids content is about 50 to 80% of the phenolic resole resin.

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 approximately 3 at 25°C.
,000 cps, especially about 250 to 2,000 cps at 25°C.
Preferably, it varies in the cps range. The viscosity measurements in the present invention are made using Brookfield RV at 25°C.
It is given in centipoise (cps) measured with a F viscometer or a Gardner-Holdt viscometer at 25°C. Gardner-Holdt viscosity in centistokes (generally 1.2
) to get cps at 25℃.

[0043] When aggregate is used in the crude raw material batch composition, the amount of resin based on the aggregate is based on the weight of the aggregate,
It can vary within a wide range, preferably from about 3 to 20% by weight, especially from 5 to 15%.

The liquid portion of the resin is water or a mixture of water and a non-reactive solvent. The resin may contain a variety of optional modifiers or additives such as silane, hexa or urea. Solvents added to the water include alcohols of 1 to 5 carbon atoms, diacetone glycol, glycols of 2 to 6 carbon atoms, mono- and dimethyl or butyl ethers of glycols, low molecular weight (200-60O) polyethylene glycols and their methyl ethers, 15-carbon phenolic compounds, phenoxychetanol, 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.

Typical water contents of the resins used in this invention vary from about 5 to 20% by weight of the resin and can therefore be referred to as water-soluble.

When the compositions of the present invention include siliceous aggregates such as silica sand, crushed candles, and silicates, or aggregates such as alumina, the use of organofunctional silane contact promoters is recommended.

The organofunctional silane is used in an amount sufficient to improve resin-to-aggregate contact. Typical usage levels for these silanes are 0.1 to 1.5% by weight of resin. Examples of useful silanes are those represented by general formula 1. Formula 1: (RO)3-Si-CH2-CH2-CH2-X
In the above formula, R=C3 or C2H5. Other useful silanes not represented by Formula 1 include 2-(3,4-epoxycyclohexyl)nityltrimethoxysilane, bis(trimethoxysilylpropyl)ethylenediamine,
N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride and secondary aminosilane [(R
O3)Si-CH2CH2CH2]2NH.

Accelerators A wide variety of materials are found for accelerators. Accelerating the curing of the phenolic resole resin shortens the time from mixing the composition until it is sufficiently cured and ready for use. Without the use of accelerators, phenolic resole resins with or without fillers or aggregates, magnesium hardeners, and optional ester-functional hardeners often cure to form sheets or bars of such compositions. The time it takes to break when bent is within 24 hours at 23.9°C (75°F).

In the case of ionizable compounds, it is the anion, eg C1-, that makes the material a promoter. That is, although cations such as Na-, H-, Li-, etc. have a slight effect on the degree of gelation or curing, they do not change the fact that anions are accelerators. Salts containing the following cations are particularly suitable as promoters of the present invention. namely, sodium; potassium; lithium; calcium; magnesium: ammonium; and lower alkyl substituted ammonium compounds such as 1 to 4 in each alkyl group.
carbon atoms. The aforementioned 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 act as promoters.

The promoters of the invention are slightly soluble in the reaction medium. Its solubility is different from its solubility in water, especially when the reaction medium contains a significant amount of ester and contains about 15% water.
This is true if it contains only the following: However, for general purposes, the solubility of promoters in water is greater than or equal to 0.1% by weight, preferably greater than or equal to 1.0% by weight at 25°C, except for promoters containing reactive organically bound chlorine or bromine. be. 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, in salt form, such as acid addition salts of basic nitrogen compounds, or in combination with a phenolic resin, a magnesium hardener and optional ingredients. It may also be in a form that simply provides a promoter anion when mixed with an ester. When the acid form is used in the presence of a magnesium curing agent, an acid salt is formed in situ. For example, when added to the phenolic resole resin and curing agent composition of the present invention, a magnesium salt is formed, and the acid or salt provides the appropriate anion.

Ionizable accelerators, such as those that provide anions such as chloride ions, sulfamate ions, etc., to the curable mixture increase the magnesium solubility, ie, increase the amount of soluble magnesium leaving 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 that binds to the anion of the ionizable promoter should be selected so as not to render the anion insoluble. This means that
This also applies to the use of other materials, such as acid addition salts of amines, which may insolubilize some of the accelerator anions, such as various calcium-containing compounds that can be used in conjunction with the magnesium curing agent in curing phenolic resole resins. To avoid this insolubilization, either the accelerator anion is insolubilized by the material, or the curable mixture contains a large amount of accelerator anion so that a sufficient amount of anion exists to solubilize the magnesium curing agent. It is necessary to remain. When calcium is the cation of the accelerator compound or when using a calcium-containing curing agent, the accelerator anion is 25
It must form a water-soluble calcium compound having a water solubility of 1% by weight or more at °C.

In the case of a compound that dissociates in water or alcohol to give an anion, the anion-giving compound described below is an accelerator and is added in an aqueous solution of the magnesium curing agent, phenolic resole resin, and other components in the curable mixture. Increasing the amount of magnesium seems to be effective. The above anions are chloride ion, nitrate ion, sulfate ion, sulfite ion, hydrogen sulfite ion, hydrogen sulfate ion, phosphite ion, hypophosphite ion, cyanate ion, bromide ion, formate ion, and thiosulfate ion. be. 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 the need for further addition of magnesium oxide or 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 a reactive chlorine or bromine is bonded to an organic group. In the case of acid addition salts of amines, the salts must have a water solubility of greater than 1% by weight at 25°C. Compounds containing reactive chlorine or bromine bound to an organic group include covalently bound chloride or bromide, especially in the presence of oxides or hydroxides of magnesium or calcium, such as water, alcohols, phenolic resins or amines. It means a material that releases chloride ions or bromide ions through a solvolysis reaction or a nucleophilic substitution reaction with a hydroxyl compound.

As examples of compounds giving accelerators in acid form, mention may be made of 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,
Examples include ammonium sulfate, potassium bromide, potassium sulfamate, monosodium phosphite, choline formate, and the like.

[0054] Lithium carbonate improves 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 have a phenol resol resin content of about 10% or more, for example 10 to 25%.
of free phenol, with a weight average molecular weight 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 resol resin composition cured at room temperature.

Examples of promoter compounds containing reactive chlorine or bromine attached to organic groups 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-triazine, e.g. -6 carbon alkoxy or alkylamino, 6-10 carbon aryloxy and arylamino and other heterocyclic polychlorides such as 2,4-dichloropyrimidine; dichlorodiphenylsilane, silicon chlorides or bromides such as silicon tetrachloride; silicon tetrabromide, phenylchloride silane, 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-dichloropropionaldehyde, 2,3-dichloroprobionitrile, α,α'-dibromoxylene, α,α'-dichloro xylene, 2-chloromethyl-m-dioxolane and chlorides such as acetyl chloride, pivaloyl chloride, benzoyl chloride, isophthaloyl chloride, terephthaloyl chloride and sulfur-chlorine compounds,
For example, sulfonyl chloride compounds of benzene and tolunin,
These include 1,3-benzenedisulfonyl chloride and methanesulfonyl chloride. Furthermore, it is also possible to use compounds which liberate promoter anions or compounds such as hydrogen chloride in water or alcohol, such as dichlorophenylphosphine.

Furthermore, certain strongly basic tertiary amines can also serve as accelerators. Examples of such accelerators include 1, 3,
5-tri(lower alkyl)hexahydro-1,3,5-
Triazines in which the 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 2,4,6
-tris(di-lower alkylaminomethyl)phenol (each alkyl group having 1 to 3 carbon atoms) and compounds of the formula: However, in the above formula, (i) R1 and R2 are each selected from the group consisting of alkyl having 1 to 3 carbon atoms,
R1 and R2 when combined with the nitrogen to which they are attached represent a member selected from the group consisting of piperidino, piperazino, morpholino, thiomorpholino and pyrrolidino. (ii) X is (-CH2-)n, - where n is 1 to 6;
is selected from the group consisting of CH=CH-CH2-, -C, and (iii)
R3 and R4 are each selected from the group consisting of hydrogen, alkyl of 1 to about 3 carbon atoms, and R3 and R4, when combined with the nitrogen to which they are attached, are piperazino, morpholino, thiomorpholino, piperidino and selected from the group consisting of pyrrolidino. Acid addition salts of the basic amine promoters or other anions that are not retarders, where the acid comprises one of the promoter anions described above, as well as lithium carbonate are useful promoter compounds. Other anions that are not retarders include formate, trifluoroacetate, chloroacetate, benzoate, benzenesulfonate, and substituted benzoates in which the substituent is an alkyl, halogen, or nitro group of 1 to 4 carbon atoms. ions and substituted benzenesulfonate ions. Yet another group of promoters are certain chelating agents, such as heptane-2,4-dione; pentane-2,4-dione, also called acetylacetone; 2,2'-bipyridine;
Benzoylacetone; 2-acetylcyclopentanone;
and 2-formylcyclopentanone.

The amount of accelerator used in the present invention varies widely depending on the activity of the particular accelerator, the degree of acceleration desired, room or ambient temperature, the surface area and amount of lightly calcined magnesium oxide, and the type and amount of ester hardener. It is subject to change. That is, the amount of accelerator sufficient to promote gelation and curing of the phenolic resole resin can vary over a wide range, from about 0.1 to 5% based on the weight of the phenolic resole resin. However, it is preferred that the amount of accelerator is about 0.5 to 5%, especially 1.0 to 5% of the weight of the resin. While chloride is an effective accelerator when used in amounts as low as 0.1% of resin weight, other accelerators generally require higher amounts.

Fillers, Aggregates and Modifiers The compositions of the present invention can contain fillers, modifiers and aggregates commonly used in phenolic resole resins. The aggregate is granular,
It is a granular material in the form of powder or flakes. Suitable aggregates include magnesite, alumina, zirconia, silica, zircon sand, olivine sand, silicon carbide, silicon nitride, boron nitride, bauxite, quartz, chromite and corundum. However, it is not limited to the above. Depending on the application, low density bone materials such as vermiculite, perlite and pumice are suitable. High-density aggregates suitable for other uses 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 weight of the resin formulation. The amount of filler can be equal to the resin. Glass, phenolic or ceramic medium microspheres can also be used in amounts up to about 20% of the resin formulation. Other optional modifiers, particularly for use in polymeric concrete, include steel fibers, alkali-resistant glass fibers, polyester fibers, carbon fibers, woven silicon carbide fibers,
There are fibers such as asbestos fibers, wollastonite fibers, and aromatic polyamide fibers such as KEVLER® amide fibers sold by DuPont and polypropylene fibers. The amount of this fiber can vary over a wide enough range to improve the strength of the composition, and is used in the composition, for example, in an amount of about 2 to 5% of the aggregate weight.

The raw material batch composition prepared by combining the curable resin binder, aggregate, curing agent(s) and accelerators includes a non-reactive solvent, silane, hexamethylenetetramine, clay, graphite, oxidation Further, any of a number of optional modifiers or additives including iron, carbon pitch, silicon dioxide, metal powders such as aluminum, magnesium, silicon, surfactants, dispersants, air scavenging agents and mixtures thereof. May be contained. Air removal agents such as defoamers, such as dimethylpolysiloxane, can be used in amounts sufficient 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 a further example of an air extraction agent, Air Products and Chemicals
and Chemicals, Inc. ) of Surfinol, such as Surfinol DF-110L, Surfinol 104 and Surfinol GA. can be mentioned. For casting applications and applications using sand binder overlays or silica sand as aggregate, silane-based adhesion promoters such as gamma-aminopropyltrinitoxysilane are preferred additives. For refractory applications, clays, 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 weight of the composition.

Uses The method and composition of the invention can be used in shapes such as bonding refractory aggregates to produce bricks and castable monolithic shapes; coated abrasives; providing concrete with resistance to acids, oils and organic solvents. Polymer concrete (also referred to as resin-filled aggregate) for protective overlays or repairs; production of precast shapes such as pipes, tiles, wall panels etc. where hydrolysis, solvent, acid and heat resistance is desired;
and is particularly useful in the preparation of impregnated papers for automotive oil and air filters. Fireproof shapes include firebricks and integral refractories. Conventional fire-resistant 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; teiric nitride, boron nitride: boxide; quartz; corundum, zircon sand; olivine sand; 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 aggregate, 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 refractories such as bricks, the refractory material composition is pressed into a desired shape and thermally cured, or the pressed composition is left to harden at room temperature and then thermally cured.

[0061] Some refractory applications may require preformed shapes other than brick-like shapes. These "integrated refractories" are cast by placing a liquid flowable binder-aggregate system into a mold and then filling the mold with vibration. Once the binder-aggregate system has cured at room temperature, the mold is removed and the shape is thermally cured and ready for use, either before or after transfer to the monolithic refractory use site.

Calcium aluminate of hydraulic refractories is
constitutes the current bonding technology for monolithic refractories. However, the melt of molten metals such as iron, steel and aluminum chemically reacts with the hardened cement to dissolve, soften or simply weaken the hydrated cement phase, which increases the permeability of the hardened refractory shape. A problem arises. For this reason, the lifespan of refractory shapes is severely limited. After room temperature curing, this monolithic shape can be thermally hardened 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 use of polymer concrete was in the repair of Portland cement concrete. Today, polymer concrete has numerous uses, such as those mentioned above. The binder compositions of the invention are particularly advantageous for these applications. The binder composition of the present invention is not highly alkaline, does not have high levels of sodium or potassium and therefore does not affect the aggregate, and can be cured within a reasonable time at indoor or outdoor temperatures or at ambient temperatures. It is. One use for the compositions of the invention is as a coating or topping applied to rigid surfaces such as concrete. That is, there is provided a room temperature curable flooring 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 present invention does not adversely affect the concrete.

A preferred application of the composition of the present invention is a shaped article manufactured by casting, curing at room temperature or room temperature, and then thermally curing. The following methods and examples are provided to enable those skilled in the art to more fully understand the invention presented herein. Unless otherwise specified, all parts and percentages in the Examples and other parts of the specification and claims are by weight, and temperatures are in °C (°F).

Method of Preparing Polymer Concrete and Testing Its Compressive Strength.
(obart) Mixer with industrial grade sand No. 4 (Vulcan Materials)
Materials Co. )) Also referred to as coarse sand in this application 990.0g Industrial grade sand No. 10 (Vulcan Materials)
In this application, it is also referred to as medium-diameter sand.
360.0g
Oklahoma Mill Creek Foundry Sand (U
．． S. (Silica) Also referred to as fine sand in this application
150.0g

as well as
Magchem 50 (65
m2/g) 22.5g Martin Marietta Magnesia Specialties
It was filled with lightly calcined magnesia manufactured by A.A. Specialties. 180.0 g of Resin A containing 1.8 g of 3-glycidoxypropyltrimethoxysilane was added. This resin-aggregate was mixed for a total of 2 minutes (
1 minute on medium setting and 1 minute on high setting)
This mixture was then transferred to a mold containing 15 cylindrical cavities 1-1/2 inches deep and 1-1/2 inches in diameter. Each cavity was lined with a thin polyester film to facilitate removal of the cured specimens. Next, the filled mold was placed on a Syntron vibration table (Syntron Vibra).
ting Table), set it to 5.1 and set it to 2.
Vibrate for a minute. The surface was smoothed slightly with a trowel. This mold is then heated to constant temperature (22,2 ± 1,1 (72 ± 2°F) - constant temperature (
51±2%). After 24 hours, the cured specimens were removed and stored for testing or later evaluation. The compressive strength of polymer concrete is determined by Tinius-Olsen
Measurements were made using a tensile testing machine at a low speed of 3.8 mm/min (0.15 inch/min). Number of pounds at breakage is 1.77
The value divided by is the compressive strength in psi.

Polymer Concrete Preparation Method and Tensile Strength Test Method A 5.5 liter (5 quart) Hobart mixer was
1.0g industrial grade sand no. 4, 324.0g
Industrial grade sand No. 10 (both manufactured by Vulcan Materials) 135.0 g of Oklahoma Mill Creek Foundry Sand (U.S. Silica) and 13.5
g of Magchem 50 (Martin Marietta Specialties) was filled. Resin A containing 1.62 g of 3-glycidoxypropyltrimethoxysilane was added to this mixture for 1 hour.
62.0g was added. This resin/aggregate mixture was heated for 2 minutes.
Mixing was performed at medium speed for 1 minute and at high speed for 1 minute. This mixture was then transferred to an aluminum mold (previously sprayed with mold release agent) and
Length 76.2 mm (3 inches), thickness 25.4 mm (1
Dogbone-shaped specimens with a neck width of 25.4 mm (1 inch) were formed by casting. The spread mold was pre-placed on a polyester film on an aluminum tray. It was filled into a dogbone mold and vibrated for 2 minutes on a Syntron vibration table at a setting of 5.1. The surface was smoothed slightly with a trowel. Next, this assembled device was placed at constant temperature (22.2±11℃11) and constant humidity (5℃).
1±2%) was transferred to a room and cured. Samples were removed from the molds after 24 hours and stored for testing or later evaluation. Tensile strength was measured using a Tinius-Olsen tensile tester at a slow speed of 3.8 mm/min (0.15 in/min). Digital readouts indicate readings in psi.

Determination of soluble magnesium produced by the reaction of resin A with magnesia hardener with/without ester hardener and with/without additives. Resin A 6.0g water in a vial (28 x 95mm)
0.5gγ-
Butyrolactone 1.5g

(sometimes referred to as 2-methoxyethyl ether in the examples or tables of this application), mix gently to make the solution uniform, and add 0.75 g of lightly calcined magnesia (Martin Marietta). Magchem 50) from Magnesia Specialties was added. S/P Vortex
x) Mixer (American Scientific
The mixture was thoroughly mixed for 1 minute using a 900000000000 setting for 1 minute. 1.5 g of homogeneous dispersion was mixed with 4.5 g of N,N. Dimethylformamide (DM
F) and immediately transferred to a vial containing 0.5 g of methanol. After thorough mixing for 1 minute, the contents were transferred to a centrifuge tube and centrifuged for 5 minutes. This relatively clear liquid was filtered through a Teflon microfilter. A certain amount of clear solution was weighed into a platinum dish, and it was incinerated by heating to 600° C. in a muffle furnace. The residue was treated with hydrochloric acid, diluted appropriately, and analyzed for magnesium by atomic absorption spectrometry. The above new mixed solution/magnesia dispersion (1.5g
/vial) to another empty vial and placed in a 25°C water bath. Add 4.5 g of DMF at the appropriate time,
The resin was completely dispersed after stirring for 2-3 minutes. Next, 0.5 g of methanol was added and mixed again before centrifugation and analysis as described above. % Magnesium in initial sample = Actual % Magnesium x 4.27 (corrected for solvent dilution) Flow measurement width of resin/hardener/magnesia/aggregate mixture 7
．． 6cm (3”) deep 5.1cm (2”) domed 1
A 50 ml glass bowl was lightly sprinkled with mold release agent and filled in three parts with a composite mixture obtained from resol, ester hardener, lightly calcined magnesia hardener and aggregate (silica sand or dead calcined magnesia refractory). did. Tap each ingredient with a pestle after each addition. The bowl and contents were transferred back onto polyester film taped to a Cintron vibrating table. Next, set the table to 8 (the maximum setting is 3)
/4) for 20 seconds. The diameter (in inches) of the resulting hemisphere was measured, and the % flow was calculated using the following formula. Gelation Assay 6.0 grams of Resin A or Resin B (as shown in the table or examples) in a glass vial (28 x 95 mm) with a screw stopper.
Additives (as shown in the table or examples); 0.5 grams of water; and 1.5 grams of gamma-butyrolactone. After thoroughly mixing this solution, the surface area is 65 m2.
Add 0.75 g of lightly calcined magnesia/g. American Scientific Products S/P
Mix this mixture thoroughly using a vortex mixer at setting 9 for 1 minute. Immediately transfer 5 grams of this mixture to a glass test tube (18 x 155 mm). A crowbar with a magnetized head attachment was introduced into the mixture and attached to a Sunshine gel time meter, which was rotated. During the test, the test tubes were immersed in a 25°C water bath. For measurement of gelation time with Resin C, 5.0 g of a mixture obtained by mixing 8.0 g of Resin C, 1.2 g gamma-butyrolactone and 1.6 g of lightly calcined magnesia with a surface area of 65 m / g was used. . Solvents were used optionally. Gelation measurement at 25℃
Alternatively, it was carried out at 60°C (chloroform boiling point). The 100° C. gelling time of Resin D was obtained by mixing 8.4 g of Resin D, an organic curing agent 2-methoxyethyl ether with an ester equivalent of 0.008 l, and 0.16 g of lightly calcined magnesia with a surface area of 25 m / g. 5.0 g of the mixture was used. The total weight of ester curing agent and 2-methoxyethyl ether was kept constant. The gelation time of resin E is 3.85 g of resin and 1.16 g of ethyl lactate or 4.0 g of resin E.
and 1.0 g of triacetin were used.

Properties of Phenol Resin Phenol resole resin E is manufactured by Borden Chemical Company (B
Orden Chemical Company)
is a commercial product sold under the trade name Alphaset. Resin E is used in this invention for comparative purposes. This resin has a solid content of approximately 50% and a water content of approximately 50%.
0%, viscosity at 25°C is 150 cps, pH is 13
It is. Phenol resole resin (also simply referred to as Resin A) is a mixture of phenol (P) and 50% formaldehyde (F).
) is reacted with sodium hydroxide as a catalyst at an F/P molar ratio of 1.25, and is further blended to prepare a phenol formaldehyde resol resin. Resin A is obtained by blending this resin intermediate with acetic acid, ethanol, methanol and N,N-dimethylformamide (DMF). Resin A has a Gardner hot viscosity of 2,560 at 25°C.
centistokes, or about 3000 cps at 25°C
solids: 68%; free phenol: 7%; lower alkyl alcohol: 10%; water: 12%; DMF: 4%; pH is 5.9; weight average molecular weight is 4,000.

Phenol resole resin B (also simply referred to as resin B) is a more alkaline and water-dilutable analog of resin A, which is acetic acid and N,N-dimethylformamide (
DMF) is not included, but instead ethanol is blended so that the ethanol content is 7.5% and potassium hydroxide is 0.75% based on resin B, and the pH of the final resin solution
is 8.9, weight average molecular weight is 4,000, solid content is 67% based on resin weight (B.O.R.), water is 18%.
% and 7% free phenol.

Phenol resol 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 viscosity of 250 cps at 25°C; solids content 68.6% B. O. R
．． ; free phenol 15.7%B. O. R. water 11.7
%B. O. R. The pH is 8.9; the weight average molecular weight is 290.

Phenol resole resin D (also simply referred to as resin D) is prepared by reacting phenol (P) and 50% formaldehyde (F) at an 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 (dipropylene glycol monobutyl ether from The Dow Chemical Company) to form the final resin. Final resin has a solids content of 78%;
Free phenol 16%; Water 8%; Dowanol DPnB8
%; Contains 1.3% potassium, pH 9.2; 25°C
The viscosity of is 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 in the presence of a magnesium curing agent and an ester curing agent were evaluated based on the weight of the resin (unless otherwise specified). B.O.R.) 2%
Tested at the level of Cure rate is determined by measuring gelation rate using the method described above entitled "Gelation Measurement Method." 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 additives, and its gel time was 48 minutes. In the case of the low molecular weight homolog of Resin A shown with the subscript [(a)] in Table 1, the composition also contained no additives and its gel time was 67 minutes. That is, additives with a gel time of less than 48 minutes that do not have a time suffix [(a)] indicate accelerators and have a time suffix [(a)].
Additives not marked with gel times exceeding 48 minutes indicate retarders. The results of this example are shown in Table 1. Some of the important results shown in Table 1 are as follows.

Chloride is the most effective accelerator. Approximately 2
Organic materials containing chlorine or bromine that react with water or alcohol to liberate chloride or bromide ions at 5° C. and a pH of about 5 to 9 act as reactivity promoters. Fluoride salts and acidic fluoride salts are retarders. Phosphate powder and phosphate salts are effective retarders. Surprisingly, phosphorous powder, sodium phosphite and hypophosphorous acid are accelerators.

[0075]

[Table 1]

Examples 2 and 3 In these examples, tests were conducted to determine the effect of lightly calcined magnesia or hydroxide magnesia, esters, and additives on the compressive strength of polymer concrete. These examples were conducted according to the polymer concrete preparation and testing methods described above. Table 2
In the data on polymer concrete shown in Table 3, unless otherwise specified, the compressive strength is measured at room temperature (R .T.) Measured on a cured test piece. The following can be seen from Tables 2 and 3. (a) Compared to the control sample, the fluoride retarder increased the R. T. Although decreasing in strength, this relative effect becomes even more dramatic after 8 hours. Lithium carbonate and calcium formate have a daily R. T. Although increasing strength, lithium fluoride (which has very low solubility) is ineffective. (b) Replacing magnesia with a chemically equivalent amount of magnesium hydroxide dramatically reduces compressive strength. However, magnesium hydroxide responds to accelerator and retardant effects. Chloride is R.I. for 24 hours. T. Increases compressive strength, but lowers fluoride. (c) When replacing γ-butyrolactone ester with an equal weight of an inert high-boiling solvent (glycol ether), the R. T. Strength decreases dramatically. 3 days dry R. T.
After hardening, soaking in 10% acetic acid for 4 days gives strength to R. T. It is lower than when it is 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. After curing and soaking in hot (90° C.) water for 4 days, the strength is significantly higher than systems using inert solvents in place of esters or magnesium hydroxide in place of magnesia. (e) Sulfamate is a good accelerator, but has a negative effect on strength (8 or 24 hours) with Resin A. However, sulfamate
Improved strength is shown when using resins with low molecular weights and high free phenol contents, such as 10 to 25% free phenol based on the weight of the resin. This situation can be seen from Example 10 and Table 10. The moderate accelerator LiCO3 shows a 24% strength increase after 24 hours.

[Table 2]

[Table 3]

[0076]

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

[Table 4]

[0077]

[Example 5] This example uses the previous 25°C room temperature (R.T.)
Experiments were carried out to demonstrate the effect of additives that were accelerators or retarders during curing on the solubilization of magnesium in the reaction mixture. This example was conducted according to the "Method for Determination of Soluble Magnesium from the Reaction of Magnesia Hardener with/Without Ester Hardener and with/without Additives and Resin A" described above. The results are shown in Table 5. The %B. listed after the additives. O. R. The value is the percentage of additive based on weight of resin (B.O.R.). It is found that chloride promotes the solubilization of magnesium in the reaction mixture and fluoride reduces it. A similar effect is observed in mixture 4-6 without ester, in which the inert solvent 2-methoxymethyl ether is used instead of 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 diamino compounds including acrylic compounds and cyclic compounds were tested as accelerators. The results of this example are shown in Table 6. Mixture 8 is a combination of TRIS and chloride. Shows an additional promoting effect.

[Table 6]

[0079]

Example 7 Tests were conducted to demonstrate the effect of various additives in combination with certain esters on gel time. This gelation time test was conducted according to the above-mentioned "Method for Measuring Gelation." The test results shown in Table 7 demonstrate the effect of various additives as accelerators or retarders at various temperatures and in combination with various esters and resins.

[Table 7]

[0080]

Example 8 This example was conducted to determine the effect of magnesia/lime ratio and additives on the gelation time of resols and esters. The results of this example are shown in Table 8. In resin A, replacing the MgO curing agent by up to 33% with CaO does not substantially affect the gelation time (mixed product 1).
-4), it can be seen that a 1:1 ratio (mixture) poses a problem. In contrast, Resin C (low molecular weight and high free phenol) allows M
The proportion of gO that can be replaced by CaO is less than 20% (10 mixtures vs. 8 control mixtures). The previously cited U.S. Pat. No. 4,794,051 to Gupta states in column 4, lines 45-53 and 34-37 that magnesium oxide and magnesium hydroxide are too slow curing agents and that calcium and magnesium Although it has been stated that the use of mixtures with a ratio of 10:1 to 0.1:10 is preferred, the above results are contrary to this. Furthermore, the Gupta compositions are said to be
While remaining thermoplastic for 4 to 100 hours or more (column 60, line 23 of the above-mentioned Gupta patent), the phenolic resole resin and curing agent mixtures of the present invention without a retarder cure in less than 24 hours. I have to point out that.

[Table 8]

[0081]

Example 9 This example was conducted to demonstrate the effect of additives on the gel time of Resin E, a highly alkaline phenolic resole resin with 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. Typically, for Resin E, ethyl lactate induces curing of the resin, as shown by the gelation of Mixture 1. However, all additives containing chloride, which are accelerators of the magnesium hardener, either acted as retarders or had no effect in this case. Table 9 shows that for this resin, most of the additives are retarders, especially the acidic fluorides. The delayed action of ammonium chloride in the present mixture is in sharp contrast to the magnesium hardener system of the present invention.

[Table 9
]

[0082]

Example 10 This example presents a series of experiments in which compositions containing certain accelerators have increased tensile strength compared to the same compositions without accelerators. The results of this example are shown in Table 10. The composition of Example 10 includes (a) a refractory magnesia bone village consisting exclusively of grains with a sieve size of 14 to 48:
(b) Resin F, 10% of the aggregate weight; (c) Gamma-butyrolactone, 15% of the resin weight (B.O.R.) and M.A.
GOX98 Premium, consisting of 30% of the weight of resin F, is manufactured by Premier Refrac
tories and Chemicals,In
c. ) is a lightly calcined magnesium oxide hardener with a surface area of 100 m2/g. The amount of accelerator used was at the level of 1% by weight of resin (B.O.R.). The tensile strength numbers given in Table 10 for this example are 3
This is the average value of the samples, and the value in parentheses is the median value. Resin F is a phenol formaldehyde resol resin having the following properties. That is, solid content, resin weight 6
4.12%; 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) approximately 200; 25
M1/4 on the Gardner-Holdt scale at °C
Viscosity of 325 centistokes, converted to approximately 390
It is centipoise. In the production of resin F, formaldehyde/phenol was charged into a reactor at a molar ratio of 0.93,
25.2% by weight of phenol remains unreacted in the resin after distillation, which reduces the water to about 6%, thus increasing the molar ratio of formaldehyde charged to the reactor to greater than 1. React under certain conditions. Tensile specimens of resin-bonded magnesia refractories were prepared and tested as follows. Resin F and magnesium hardener were intimately mixed with the refractory magnesia. The accelerator, if used, was 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. Next, a 150 gram sample of this mixture was 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. The specimen was 76.2 mm (3 in.) long, 25.4 mm (1 in.) thick with a neck width of 25.4 mm (1 in.) and was heated at 22.2°C ± 1.1°C (72°F). ±2°F) and 51%
24 hours under constant temperature and humidity (R.T.) of ±2% (relative humidity)
After standing for an hour, Tinius-Olsen (Tinius-Olsen)
Olsen) tensile testing machine. A part of the dogbone specimen was kept under constant temperature and constant temperature conditions (R.T.) for 2 hours.
After being exposed for 4 hours, it was heat treated at 110° C. for 2 hours, allowed to cool to room temperature, and then fractured. From Table 10, the addition of the accelerator sulfamate increases room temperature tensile strength compared to the same composition without the sulfamate additive; and the addition of lithium carbonate increases the same composition without the sulfamate additive. It can be seen that both the room temperature tensile strength and thermosetting tensile strength increase compared to the above.

[Table 10]

[0083]

Example 11 In this example, the compressive strength at various times of a polymer concrete composition was determined using 2% accelerator N, N, N', N '
- the same composition containing tetramethyl-1,3-propanediamine and optionally on a resin weight basis (B.O.
R. ) was compared with one further containing 0.1% of antifoam agent SAG10. SAG10 is an antifoaming agent that also functions as an air removal agent and is manufactured by Union Carbide.
It is a 10% emulsion of dimethylpolysiloxane sold by Carbide Corporation. The method for testing the compressive strength of Example 11 and the basic composition or standard mix is that described above under the title "Method of Preparing and Testing Compressive Strength of Polymer Concrete." The results of this example are shown in Table 11. From Table 11, it can be seen that the compressive strength at room temperature (R.T.) of the standard mixture or control is greater than the compressive strength of the standard mixture after inclusion of 2% accelerator on a weight basis of resin (B.O.R.). Furthermore, this 2% accelerator-containing product has a standard mixture + 2% (B.O.R.
) Accelerator + 0.1% (B.O, R.) It can be seen that the compressive strength is smaller than that of the air removal agent. Table 11 also shows that the compressive strength of the standard mixture when the accelerator and air extraction agent are included in the composition is greater than the compressive strength of the standard mixture + accelerator aged at room temperature for 1 day. ing.

[Table 11]

[0084]

Example 12 This example shows the gelation time of Resin A according to the previously described method and composition entitled "Gelation Measurement" also referred to in the Standard or Control Compositions. The results of this example are shown in Table 12. Run 1 of Table 12 is the standard composition described in the above method; Resin A, 6 g; water 0.5; gamma-butyrolactone, 1.5 g; and a lightly calcined magnesium oxide hardener with a surface area of 65 m2/g. (Mg
O50), consisting of 0.75 g.

Experiment 2 in Table 12 shows that 2% B. O. R. Figure 2 shows the increase in gel time of a standard composition with the addition of the curing agent N,N,N',N'-tetramethyl-1,3-propanediamine. Run 3 in Table 12 shows the extension of the gel time required for the composition of Run 2 when the ester curing agent, gamma-butyrolactone, is replaced with an inert solvent. Run 4 of Table 12 uses a relatively low surface area lightly calcined magnesium oxide hardener, namely Magchem 2.
Even with the addition of 0M, the surface area of gamma-butyrolactone and 6
This shows that the Experiment 2 composition containing 5 m2/g of lightly calcined magnesium oxide hardener had little effect on further shortening the gel formation time. Magchem 20
M has a surface area of 10 m2/g. Experiment 5 in Table 12 shows that the addition of a lightly calcined magnesium oxide hardener (Magchem 20M) with a relatively low surface area (10 m2/g) has a relatively small effect on reducing the gelation time of the composition of Experiment 3. Show that.

[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 includes Example 12, Table 12 and Table 13 below.
and to demonstrate the synergistic effect obtained using both a magnesium hardener and an ester hardener in the presence of an accelerator. That is, in Experiment 2 of Table 12, gelation required only 48 minutes for the composition containing both the accelerator and the ester hardener and magnesium hardener. Table 12
Run 3 of the same table was the same as Run 2 of the same table except that it did not include an ester curing agent, but allowed 115 minutes to gel. Table 13 shows that a composition identical to the Experiment 2 composition of Table 12, except without the magnesium hardener or ester hardener, did not gel after 14 days. Table 1
No. 3, the accelerator without the magnesium curing agent or the ester curing agent had little effect on increasing the viscosity of Resin A compared to the case where the accelerator was used 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. A solution of 8.0 g of resin A, 0.67 g of water and 2.0 g of gamma-butyrolactone was added to a solution of 65 m2/
1.0 g of lightly calcined magnesium with a surface area of 1.0 g was added. After stirring this mixture vigorously for 1 minute, mix 5
．． 0 g into two small cylindrical plastic vials (width 22
22.2℃±1
．． It was left at 1°C (72°F±2°F) for 4 days. The cured mass was removed from the vial and weighed. This hardened mass was transferred to cylinder No. 1 and no. It is called 2. Next, these were heated at 105°C for 2 hours, weighed, and then
The mixture was further heated at 35°C for 2 hours and reweighed. Cylinder No.
．． 1 and no. Lightly calcined magnesia 1 with a surface area of 10 m2/g in the same amounts of various ingredients as used in the preparation of 2.
．． The method described above was followed except that 0 g was added to bring the total amount of magnesia to 2.0 g for 8 g of Resin A. These samples were transferred to cylinder no. 3 and no. It is called 4. Compressive failure was measured with a Tinius-Olsen tensile tester. The results are shown in Table 14. Table 14 shows that the sample with additional magnesia has less weight loss and higher crush strength than the sample with 50% less magnesia. The gelation time of the magnesia mixture is No. 1 and no.
2 is 67 minutes, while No. 2 is 67 minutes. 3 and no. 4 is 6
As can be seen from Table 1 and Mixture 1, the effect on gelation time was small. Following a method similar to this example, various accelerators such as ammonium sulfamate, sodium chloride, pentane-2,4-dione, and 2,2'-bilipyridine are added to a composition containing magnesia mixed with surface area, resulting in a gel Strength can be further increased while reducing the time required for curing, ie, curing the binder, crude batch, and other compositions of the invention.

[Table 14]

Claims (88)

[Claims] 1. A method of accelerating the curing of a phenolic resin binder composition, comprising: A. A curable phenolic resole resin having a pH of about 4.5 to 9.5; B. Magnesium hydroxide and surface area approximately 10m2/g
a magnesium hardener selected from the group consisting of lightly calcined magnesium oxides as described above, provided that the amount of said hardener is sufficient to increase the hardening rate of said resin;
and C. (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. Compounds that contribute anions to the mixture; (2) 2,4-di(dialkylaminomethyl)phenol, 2,6-di(dialkylaminomethyl)phenol and 2,6-di(dialkylaminomethyl)phenol having 1 to 3 carbon atoms in each alkyl group; selected from the group consisting of 4,6-tris(dialkylaminomethyl)phenol; (3) 1,3,5-tri(lower alkyl)hexahydro 1 in which each lower alkyl group has 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,
a chelating agent selected from the group consisting of 4-dione, 2,2'-bipyridine and benzoylacetone; and (7)
A compound of formula (a) in which R1 and R2 are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R1 and R2 are the nitrogen atoms to which they are bonded; (b) X is (-CH2-)n (n is an integer from 1 to 6); (c) R3
and R4 are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and R3 and R4, when combined with the nitrogen to which they are attached, are piperazino, morpholino, thiomorpholino. , piperidino, and pyrrolidino; wherein the amount of accelerator is sufficient to promote curing of the mixture; How to do it. 2. The method of claim 1, wherein the resin has a pH of about 5 to 9 and the curing agent is magnesium oxide. 3. The method of claim 1, wherein said resin is a condensation product of phenol and formaldehyde. 4. The curing agent comprises particles of two or more different surface areas, about 25 to 75% by weight of which have a surface area of 50 m2/g or more, and about 25 to 75% by weight of which have a surface area of about 10 m2/g or more.
3. The method of claim 2, having a surface area of from 25 m2/g. 5. The accelerator is a compound that provides the mixture with an anion selected from the group consisting of cyanate, formate, hypophosphite, nitrate, phosphite and sulfamate anions. Method of Section 2. 6. The method of claim 2, wherein the promoter is pentane-2,4-dione. 7. The method of claim 2, wherein the cation that combines with the anion to form said compound is a sodium cation. 8. The method of claim 5, wherein the anion is a sulfamine dispersion anion. 9. The method of claim 8, wherein the resin has a weight average molecular weight of about 150 to 500 and contains about 10 to 25 weight percent free phenol. 10. The cation that combines with the anion to form the compound is hydrogen, sodium, potassium,
6. The method of claim 5, wherein the cation is selected from the group consisting of lithium, calcium, magnesium, ammonium, and alkyl-substituted ammonium in which each alkyl group has 1 to 4 carbon atoms. 11. The promoter contains 1 to 3 promoters in each alkyl group.
selected from the group consisting of 2,4-di(dialkylaminomethyl)phenol, 2,6-di(dialkylaminomethyl)phenol and 2,4,6-tris(dialkylaminomethyl)phenol having 4 carbon atoms. The method of claim 2 12. The accelerator is in the form of an acid addition salt of an amine, the acid addition salt has a water solubility of 1% by weight or more, and the anion of the acid is a cyanate anion, a formate anion, or 12. The method of claim 11, wherein the anion is selected from the group consisting of phosphite anion, nitrate anion, phosphite anion, and sulfamate anion. 13. The accelerator contains 1 in each lower alkyl group.
3. The method of claim 2, wherein the 1,3,5-tri(lower alkyl)hexahydro-1,3,5-triazine having from 3 to 3 carbon atoms. 14. The method of claim 2, wherein the promoter is lithium carbonate. 15. The promoter is 1,4-diazabicyclo[
2.2.2. ] The method of claim 2, wherein octane is used. 16. The method of claim 2, wherein the promoter is a chelating agent selected from the group consisting of pentane-2,4-dione, heptane-2,4-dione, 2,2'-bipyridine, and benzoylacetone. 17. The accelerator is a compound of the formula, with the proviso that A. R1 and R2 are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R1 and R2, when combined with the nitrogen to which they are attached, are piperidino, piperazino, morpholino, thio. represents one selected from the group consisting of morpholino and pyrrolidino; B. X is (-CH2-)n (n is an integer from 1 to 6)
, -CH=CH-CH2, C. R3 and R4 are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and when combined with the nitrogen to which they are attached, R3 and R4 are piperazino, morpholino, thio. 3. The method of claim 2, characterized in that it represents one selected from morpholino, piperidino and pyrrolidino. 18. The accelerator is an acid addition salt of an amine,
The acid addition salt has a water solubility of 1% by weight or more at 25°C, the anion of the acid is an anion that does not retard the curing of the phenolic resole resin by the magnesium curing agent, and the amine has 1% in each alkyl group. 2,4-di(dialkylaminomethyl)phenol, 2,6-di(dialkylaminomethyl)phenol having 1 to 3 carbon atoms; 1, 2,6-di(dialkylaminomethyl)phenol having 1 to 3 carbon atoms in each alkyl group;
3,5-tri(lower alkyl)hexahydro-1,3,
5-triazine; 2,2'-bipyridine; 1,4-diazabicyclo[2.2.2. ] Octane and a compound of the chemical formula, provided that A. R1 and R2 are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R1 and R2, when combined with the nitrogen to which they are attached, are piperidino, piperazino, morpholino, thiomorpholino and Represents one selected from the group consisting of pyrrolidino; B. X is (-CH2-)n (n is an integer from 1 to 6)
, -CH=CH-CH2, C. R3 and R4 are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and when R3 and R4 are combined with the nitrogen to which they are attached, piperazino, morpholino, thiomorpholino, 3. The method of claim 2, wherein the compound is selected from the group consisting of piperidino and pyrrolidino. 19. The method of claim 18, wherein the acid addition salt is a sulfamic acid addition salt. 20. The method of claim 17, wherein the acid addition salt is a nitric acid addition salt. 21. The composition of claim 2, which is cured at room temperature. 22. The composition of claim 2, which is thermally cured with allowed viscosity increase. 23. A method for accelerating curing of a phenol resol resin composition, comprising: A. the pH is about 5 to 9, the solids content is about 50 to 90% by weight of the resin, and the viscosity is about 10% at 25°C.
0 to 4,000 cps curable phenolic resole resin; B. C. A magnesium hardener selected from the group consisting of magnesium hydroxide and lightly calcined magnesium oxide having a surface area of about 10 m2/g or more, comprising about 5 to 50% by weight of the resin; C. an ester-functional curing agent comprising about 5 to 40% by weight of the resin; and D. Accounting for about 0.5 to 5% by weight of the resin, (1)
having a water solubility of 1% by weight or more at 25°C, and cyanate anion, formate anion, hypophosphite anion,
A compound which provides the mixture with an anion selected from the group consisting of nitrate anion, phosphite anion and sulfamate anion; (2) 2,4-di(dialkyl) having 1 to 3 carbon atoms in each alkyl group; (3) 1, in which each lower alkyl group has 1 to 3 carbon atoms; 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,
a chelating agent selected from the group consisting of 4-dione, 2,2'-bipyridine and benzoylacetone; and (7)
A compound having the chemical formula, where (a) R1 and R2 are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R1 and R2 together with the room atoms to which they are bonded are When combined, represents one selected from the group consisting of piperidino, piperazino, morpholino, thiomorpholino and pyrrolidino; (b) X is (-CH2-)n (n is an integer from 1 to 6); (c)
R3 and R4 are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and when R3 and R4 are combined with the nitrogen to which they are attached, piperazino, morpholino, thiomorpholino, A promoter selected from the group consisting of piperidino and pyrrolidino. 24. The resin has a temperature of about 200 to 3.0 at 25°C.
24. The method of claim 23 having a viscosity of 0.00 cps and wherein the curing agent is magnesium oxide. 25. The method of claim 23, wherein the resin is a condensation product of phenol and formaldehyde in a molar ratio of 1 mole of phenol to 1.1 to 2.2 moles of formaldehyde. 26. The method of claim 23, wherein the promoter is pentane-2,4-dione. 27. Consisting essentially of two or more grains of magnesium oxide having different surface areas, from 25 to 75
25. The method of claim 24, wherein the weight percent has a surface area of 50 m2/g or more and the 25 to 75 weight percent has a surface area of 10 to 25 m2/g. 28. The method of claim 24, wherein the accelerator is 2,4,6-tris(dialkylaminomethyl)phenol. 29. The method of claim 25, wherein the promoter is a compound that contributes a sulfamate anion to the mixture. 30. The method of claim 25, wherein the promoter is lithium carbonate. 31. The cation that combines with the anion to form the promoter compound is hydrogen, sodium,
26. The method of claim 25, wherein the cation is selected from the group consisting of potassium, lithium, calcium, magnesium, ammonium, and lower alkyl substituted ammonium having 1 to 4 carbon atoms in each alkyl group. 32. The method of claim 24, wherein the ester-functional curing agent is selected from the group consisting of lactones, cyclic organic carbonates, carboxylic acid esters, and mixtures thereof. 33. The method of claim 32, wherein said ester is a lactone. 34. The method of claim 33, wherein said lactone is gamma-butyrolactone. 35. The method of claim 32, wherein said ester is an ester of a carboxylic acid. Claim 36: A. the pH is about 5 to 9, the solids content is about 50 to 90% by weight of the resin, and
A curable phenolic resole resin having a viscosity of about 100 to 4,000 cps at °C; B. C. A magnesium hardener selected from the group consisting of magnesium hydroxide and lightly calcined magnesium oxide having a surface area of about 10 m2/g or more, comprising about 5 to 50% by weight of the resin; C. A calcium-containing compound selected from the group consisting of calcium oxide, calcium hydroxide, and calcined dolomite, wherein the calcium-containing compound is less than 50% by weight of the magnesium hardener, said calcium-containing compound replacing an equivalent weight of the magnesium hardener. compound; and D
．． Accounting for about 0.5 to 5% by weight of the resin, (1)
A compound having a solubility in water of 1% by weight or more at 25° C. and providing an anion to the mixture that increases the amount of water-soluble magnesium in the mixture, provided that the anion is a cyanate anion, a formate anion, or a hypophosphite anion. , nitrate anion, phosphite anion, and sulfamate anion; (2) 2,4-di(dialkylaminomethyl)phenol having 1 to 3 carbon atoms in each alkyl group; (dialkylaminomethyl)phenol and 2,4
, 6-tris(dialkylaminomethyl)phenol; (3) 1,3,5-tri(lower alkyl)hexahydro-, in which each lower alkyl has 1 to 3 carbon atoms;
1,3,5-triazine; (4) 1,4-diazabicyclo[2.2.2]octane; (5) pentane-2,4-dione, heptane-2,
a chelating agent selected from the group consisting of 4-dione, 2,2'-bipyridine and benzoylacetone; and (6)
A compound having the formula: (a) in which R1 and R2 are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R1 and R2 are combined together with the nitrogen to which they are attached; (b) X is selected from the group consisting of (-CH2-)n (n is an integer from 1 to 6); and (c)
R3 and R4 are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and when R3 and R4 are combined with the nitrogen to which they are bonded, they are piperazino, morpholino, thiomorpholino. , piperidino and pyrrolidino. 37. The curing agent is magnesium oxide,
Claim 3 wherein the amount of calcium compound is about 1 to 25% by weight of the magnesium hardener and the mixture contains about 5 to 40% by weight of the resin.
Composition of 6. 38. The composition of claim 36, wherein said resin is a condensation product of phenol and formaldehyde. 39. The composition of claim 37, wherein the promoter is pentane-2,4-dione. 40. The composition of claim 38, wherein the anion provided by the compound is a sulfamate anion. Claim 41: A. the pH is about 5 to 9, the solids content is about 50 to 90% by weight of the resin, and
A curable phenolic resole resin having a viscosity of about 100 to 4,000 cps at °C; B. C. A magnesium hardener selected from the group consisting of magnesium hydroxide and lightly calcined magnesium oxide having a surface area of about 10 m2/g or more, comprising about 5 to 50% by weight of the resin; C. an ester-functional curing agent comprising about 5 to 40% by weight of the resin; and D. Accounting for about 0.5 to 5% by weight of the resin, (1)
having a water solubility of 1% by weight or more at 25°C,
A compound that provides the mixture with an anion selected from the group consisting of cyanate anion, formate anion, hypophosphite anion, nitrate anion, phosphorite anion, and sulfamate anion; (2) 1 to 3 in each alkyl group; selected from the group consisting of 2,4-di(dialkylaminomethyl)phenol, 2,6-di(dialkylaminomethyl)phenol and 2,4,6-tris(dialkylaminomethyl)phenol having 4 carbon atoms. (3) 1,3,5-tri(lower alkyl)hexahydro- in which each lower alkyl group has 1 to 3 carbon atoms;
1,3,5-triazine; (4) Lithium carbonate; (5) 1,4-diazabicyclo[2.2.2. ] Octane; (6) Pentane-2,4-dione, heptane-2,
a chelating agent selected from the group consisting of 4-dione, 2,2'-bipyridine and benzoylacetone; and (7)
A compound having the formula: (a) in which R1 and R2 are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R1 and R2 are combined together with the nitrogen to which they are attached; (b) X is selected from the group consisting of (-CH2-)n (n is an integer from 1 to 6); (c) R3
and R4 are each hydrogen selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R3 and R4, when combined with the nitrogen to which they are attached, are piperazino, morpholino, thiomorpholino, piperidino. and pyrrolidino. 42. The resin has a viscosity of 20 at 25°C.
42. The composition of claim 41, wherein the cps is 0 to 3,000 cps and the curing agent is magnesium oxide. 43. The resin contains 1. each of formaldehyde.
42. The composition of claim 41, which is a condensation product of phenol and formaldehyde in a molar ratio of about 1 mole to 1 to 2.2 moles of phenol. 44. The amount of magnesium oxide curing agent varies from about 10 to 40% based on the weight of the resin, and the ester-functional curing agent is a group consisting of lactones, cyclic organic carbonates, carboxylic acid esters, and mixtures thereof. and the accelerator is selected from 1. based on the weight of the resin.
43. The composition of claim 42, varying from 0 to 5%. 45. The accelerator is a compound that provides the mixture with an anion selected from the group consisting of cyanate, formate, hypophosphite, nitrate, phosphite, and sulfamate. Composition of item 44 46. The cation that combines with the anion to form the compound is selected from hydrogen, sodium, potassium, lithium, calcium, magnesium, ammonium, and alkyl-substituted ammonium having 1 to 4 carbon atoms in each alkyl group. 46. The composition of claim 45, wherein the composition is a cation selected from the group consisting of: 47. The promoter comprises 2,4-di(dialkylaminomethyl)phenol, 2,6-di(dialkylaminomethyl)phenol and 2,4-di(dialkylaminomethyl)phenol having 1 to 3 carbon atoms in each alkyl group. , 6-tris(dialkylaminomethyl)phenol. 48. The composition of claim 44, wherein the promoter is a 1,3,5-tri(lower alkyl)hexahydro-1,3,5-triazine having 1 to 3 carbon atoms in each alkyl group. thing. 49. The composition of claim 44, wherein the accelerator is pentane-2,4-dione. 50. The promoter is 1,4-diazabicyclo[
2.2.2. 45. The composition of claim 44, which is octane. 51. The composition of claim 44, wherein the promoter is a chelating agent selected from the group consisting of pentane-2,4-diosyl, heptane-2,4-dione, 2,2'-bipyridine, and benzoylacetone. thing. 52. The accelerator is a compound having the formula: wherein A. R1 and R2 are each selected from the group consisting of alkyl having 1 to 3 carbon atoms;
1 and R2 when taken together with the nitrogen to which they are attached represent selected from the group consisting of piperidino, piperazino, morpholino, thiomorpholino and pyrrolidino; B. X is (-CH2-)n (n is an integer from 1 to 6)
, -CH=CH-CH2-, C. R3 and R4 are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and when combined with the nitrogen to which they are attached, R3 and R4 are piperazino, morpholino, thio. 45. The composition of claim 44, characterized in that it represents one selected from the group consisting of morpholino, biperidino and pyrrolidino. 53. The composition of claim 44, wherein the promoter is lithium carbonate. 54. The accelerator is an acid addition salt of an amine,
the salt has a water solubility of 1% or more at 25°C, and the anion of the acid is selected from the group consisting of cyanate anion, hypophosphite anion, nitrate anion, phosphite anion, and sulfamate anion. is a thing, and
2,4-di(dialkylaminomethyl)phenol, in which the amine has 1 to 3 carbon atoms in each alkyl group;
, 6-di(dialkylaminomethyl)phenol and 2
, 4,6-tris(dialkylaminomethyl)phenol; 1 in each alkyl group;
1,3,5-tri(lower alkyl)hexahydro-1,3,5-triazine having from 3 carbon atoms; 2,
2'-bipyridine; 1,4-diazabicyclo[2.2.
2. ] Octane; and the chemical formula provided that in the above formula, A. R1 and R2 are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and when combined with the nitrogen to which they are attached, R1 and R2 are piperidino, piperazino, morpholino, thio. represents one selected from the group consisting of morpholino and pyrrolidino; B. X is (-CH2)n (n is an integer from 1 to 6),
-CH=CH-CH2-, C. R3 and R4 are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and when combined with the nitrogen to which they are attached, R3 and R4 are piperazino, morpholino, thio. 45. The composition of claim 44, wherein the composition is selected from the group consisting of: morpholino, piperidino, and pyrrolidino. 55. The composition of claim 54, wherein the acid addition salt is a sulfamate salt. 56. The magnesium oxide curing agent comprises particles of two or more different surface areas, about 25 to 75% by weight thereof.
45. The composition of claim 44, wherein the composition has a surface area of 50 m2/g or more, and 25 to 75% by weight thereof has a surface area of about 10 to 25 m2/g. 57. The composition of claim 44, wherein said resin is a condensation product of phenol and formaldehyde. 58. The composition of claim 44, wherein the ester functional curing agent is a lactone. 59. The composition of claim 44, which is cured at room temperature. 60. The composition of claim 59 which is thermally cured. Claim 61: A. Aggregate B. the pH is about 5 to 9, the resin solids content is about 50 to 60% by weight of the resin, and the viscosity is 25°C.
A curable phenolic resole resin C. D. A magnesium hardener selected from the group consisting of magnesium hydroxide and lightly calcined magnesium oxide having a surface area of 10 m2/g or more, comprising about 5 to 40% by weight of the resin; D. an amount of an accelerator sufficient to accelerate the curing of the mixture, provided that the accelerator comprises (1) a cyanate anion, a formate anion, a hypophosphite anion, a nitrate anion, a phosphite anion, and a sulfamate anion; (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,
a chelating agent selected from the group consisting of 4-dione, 2,2'-bipyridine and benzoylacetone; and (7)
A compound having the formula: (a) in which R1 and R2 are each selected from the group consisting of alkyl having 1 to 3 carbon atoms, and R1 and R2 are combined together with the nitrogen to which they are attached; (b) X is selected from the group consisting of (-CH2-)n (n is an integer from 1 to 6); and (c)
R3 and R4 are each selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and when combined with the nitrogen to which they are attached, R3 and R4 are piperazino, morpholino, thio. Morpholino,
A crude batch composition comprising a mixture of: selected from the group consisting of piperidino and pyrrolidino. 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 the aggregate; and the mixture has a pH sufficient to increase its cure rate. 62. The composition of claim 61, comprising an amount of ester-functional curing agent. 63. The composition of claim 62, which is cured at room temperature. 64. The magnesium hardening agent is about 10 to 2
63. The composition of claim 62, wherein the composition is magnesium oxide having a surface area of 0.00 m2/g and the mixture contains a sufficient amount of fibers to improve the flexural strength of the composition upon curing. 65. The aggregate is sand and the composition comprises about 0.1 to 1.5% silane adhesion promoter and about 0.005 to 0.1% air scavenging agent, based on the weight of the resin. 65. The composition of claim 64, comprising: 66. The composition of claim 62 which is thermally cured. 67. The aggregate is selected from the group consisting of refractory grade magnesia, alumina, zirconia, silica, silicon carbide, silicon nitride, boron nitride, bauxite, quartz, corundum, zircon sand, olivine sand, and mixtures thereof. 63. The composition of claim 62. 68. The composition of claim 62, wherein the phenolic resole resin is a condensation product of phenol and formaldehyde, and the composition contains a filler. 69. Claim 67 further comprising about 5 to 25% graphite by weight of the aggregate and about 1 to 5% by weight of the aggregate metal powder selected from the group consisting of aluminum, magnesium, and silicon. Composition of. 70. The composition of claim 69, which is cured at room temperature. 71. The composition of claim 69 which is thermally cured. Claim 72: A. A curable phenolic resole resin having a pH of about 5 to 9, a resin solids content of about 50 to 90% by weight of the resin, and a viscosity of 100 to 4,000 cps at 25°C; B. a magnesium hardener selected from the group consisting of magnesium hydroxide and lightly calcined magnesium oxide having a surface area of about 10 m2/g or more, provided that the amount of said hardener is sufficient to increase the curing rate of said resin; ; C. D. an ester-functional curing agent representing about 5 to about 40% by weight of the resin; D. An accelerator that provides the mixture with an anion that increases the water-soluble magnesium in the mixture and accounts for about 0.1 to 5% of the weight of the resin, provided that the anion is a hydrogen sulfite anion, a hydrogen sulfate anion, a bromide anion, or a chloride anion. 1. A crude batch composition comprising a mixture of: selected from the group consisting of a thiosulfate anion, a sulfate anion, a sulfite anion, and a thiosulfate anion. 73. The resin has a temperature of about 200 to 3, at 25°C.
73. The composition of claim 72, wherein the composition has a viscosity of 0.000 cps, the magnesium hardener is magnesium oxide, and the composition comprises one selected from the group consisting of aggregates and fillers. 74. The mixture contains a calcium-containing compound selected from the group consisting of calcium oxide, calcium hydroxide, and calcined dolomite, and the amount of the calcium-containing compound is about 1 to 25% by weight of the magnesium hardener.
73. The composition of claim 72, wherein the calcium-containing compound replaces a substantial amount of the magnesium hardener on a weight basis. 75. The anion is provided by an acid addition salt of an amine, and the acid anion is selected from the group consisting of bisulfite anion, bisulfate anion, bromide anion, chloride anion, sulfate anion, sulfite anion, and thiosulfate anion. 74. The composition of claim 73, which is selected. [Claim 76]Claim 7 that the ester is a lactone.
Composition of 3. 77. The composition of claim 73, wherein the ester is an ester of a carboxylic acid. 78. The composition of claim 73, wherein the anion is provided by a reactive organochlorine or organobromine containing compound. 79. The composition of claim 73, wherein the anion is a chloride anion. 80. The composition of claim 73, wherein the anion is a sulfate anion, a hydrogen sulfate anion, or a hydrogen sulfite anion. 81. The composition of claim 73, which is cured at room temperature. 82. The composition of claim 73, which is allowed to increase in viscosity at ambient temperature and is subsequently thermally cured. Claim 83: A. A curable phenolic resole resin having a pH of about 5 to 9; B. A sufficient amount of a lightly calcined magnesium oxide hardener to increase the cure rate of the resin, provided that the hardener contains particles of two or more different surface areas, about 25 to 75% by weight of which have a surface area of 50 m2/g or more. and 25 to 75% by weight thereof has a surface area of about 10 to 25 m2/g. 84. The composition of claim 83, comprising a sufficient amount of ester functional curing agent to increase the cure rate of said mixture. 85. The amount of magnesium oxide is 5% in the resin.
the amount of ester is about 5 to 40% by weight of the resin, and the magnesium curing agent consists essentially of particles of two or more different surface areas, about 25% of which
84. The composition of claim 83, of which 75% by weight has a surface area of 50 m2/g or more and 25% to 75% by weight thereof has a surface area of about 10 to 25 m2/g. Claim 86: Claim 84 wherein the phenol resole resin is a condensation product of phenol and formaldehyde.
Composition of. 87. The composition of claim 83, which is cured at room temperature. 88. The composition of claim 83, which is allowed to increase in viscosity at room temperature and is subsequently thermally cured.