CA1080380A

CA1080380A - Molding compound

Info

Publication number: CA1080380A
Application number: CA239,117A
Authority: CA
Inventors: Thomas E. Philipps; Kevin M. Foley; Frank P. Mccombs; Reuben H. Bell; Robert L. Muto; Anil K. Rastogi; Watter D. Cottrell (Jr.); Ernest E. Lawson (Jr.)
Original assignee: Owens Corning Fiberglas Corp
Current assignee: Owens Corning
Priority date: 1974-11-18
Filing date: 1975-11-06
Publication date: 1980-06-24
Also published as: DK513675A; AU502444B2; DE2550779A1; BE835555A; ES442645A1; FI753200A7; NO753810L; SE7512565L; JPS51102092A; NL7513274A; AU8626075A; IT1049472B; FR2291165A1; BR7507453A; GB1522995A

Abstract

ABSTRACT OF THE DISCLOSURE

A molding composition comprises (A) a mixture of (1) a thermosetting resin of at least one of the phenol-formaldehyde condensates, phenol-aminoplast-formaldehyde condensates, amino-plast-formaldehyde condensates, resorcinol-formaldehyde conden-sates, or resorcinol-formaldehyde-urea condensates and (2) cement, wherein the cement is present in an amount within the range of from about 1 to about 20 parts by weight of cement per part by weight of the water content of the thermosetting resin; or (B) a condensate resin formed from cement, formaldehyde, and at least one of phenol, aminoplasts or resorcinol, wherein the weight of the cement is from one to twenty parts by weight of cement per part by weight of the water used to form the resin and three-fifths of the weight of the formaldehyde used to form the resin.
Preferably, the amount of cement is from 1 to 9 parts by weight of cement per part by weight of the water, and the weight ratio of thermosetting resin to cement ranges from 1:1 to 1:4. The composition optionally may include an organo-silane or amino-alkylsilane coupling agent and a clay, and also other known fill-ers and mold release agents.

Description

lO~ o This invention concerns thermosetting resins containing stoichiometric amounts of cement.
The production of phenolic moldings is an old art, having involved, over the years, the use of two different types of phenol-formaldehyde condensate: novolacs and resoles. The novo-lacs were produced by condensing formaldehyde and phenol in a mole ratio of about 1:1 or slightly less, and usually in the pre-sence of an acidic condensing agent. Condensation was carried -essentially to completion, so that the novolac became water in-soluble and could be separated from associated water and used to formulate a molding compound by mixing with a curing agent, usu-ally hexamethylenetetraamine,and other additives such as fillers, reinforcements, and mold release agents. Moldings were then pro-duced in matched molds by the "heat pressure" method disclosed in an early Baekeland patent.
Moldings have also been made by a casting technique from resoles: partial condensates of formaldehyde and phenol in a higher mole ratio, usually at least about 1.5:1; condensation is caused by heating, usually in the presence of a fixed alkali con-densing agent. Condensation is interrupted at a desired endpoint by discontinuing heating and acidifying to a desired pH at which room temperature condensation i5 comparatively slow. The casting can then be produced from the partial condensate by add-ing a "hardener", e.g., a solution of hydrochloric or phosphoric ~ -acid in glycerine or in a glycol, and pouring the resulting com-position into a mold. Cure proceeds at ambient or a slightly higher temperature. A detailed discussion of phenol-formaldehyde condensates appears in The Chemistry of PhenoZic Resins, Martin, published by John Wiley & Sons, Inc. in 1956, and the literature references cited therein.

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~osv3~0 The prior art (for example, U.S. Patent 3,502,610, Thomp-son, issued March 24, 1970) also suggests that laminates, coat-ings, moldings, and expanded foams can be produced from a poly-hydric phenol-aldehyde resin containing 2-6 percent hydraulic cement, based on the weight of the polyhydric phenol. The cement is said to lower the viscosity of the resin, and to give it high temperature strength and fire-retarding properties.
This invention concerns thermosetting resins containing stoichiometric amounts of cement. The resin can be produced prior to admixture with the cement, or the cement may be mixed with the monomers prior to production of the resin. Stoichiome-tric amounts as used in this application means that sufficient cement is present to react with all water initially present in the system plus any water of reaction formed during the cure of the system.
According to this invention, a molding composition com-prises (A) a mixture of (1) a thermosetting resin of at least one of the phenol-forma:Ldehyde condensates, phenol-aminoplast-formal-dehyde condensates, aminoplast-formaldehyde condensates, resor-cinol-formaldehyde condensates, or resorcinol-formadehyde-urea , condensates and (2) cement, wherein the cement is present in an amount within the range of from about 1 to about 20 parts by weight of cement per part by weight of the water content of the thermosetting resin; or (B) a condensate resin formed from cement, formaldehyde, and at least one of phenol, aminoplasts or resorci-nol, wherein the weight of the cement is from one to twenty parts by weight of cement per part by weight of the water used to form the resin and three-fifths of the weight of the formaldehyde used to form the resin. Preferably, the amount of cement is from 1 to 9 parts by weight of cement per part by weight of the water, and ~ 2 . : -~- .. ., :
- . - : , . . : -108V38o the weight ratio of thermosetting resin to cement ranges from 1:1 to 1:4. The composition optionally may include an organo-silane or amino-alkylsilane coupling agent and a clay, and also other known fillers and mold release agents.
In one embodiment, the resin is produced prior to admix-ture with cement. Hereinafter we will refer to this embodiment as a "resin system". In another development, the cement is mixed with the monomers prior to the production of the resin. Herein-after, we will refer to that embodiment as a "monomer system".
Both of these systems produce compounds having excellent fire resistance, low smoke-producing properties, and physical proper-ties comparable to conventional phenolic molding compounds.
Another feature of the invention concerns the improvement of the strength properties of these molding systems by the addi-tion to the molding compounds of coupling agents of at least one of (a) an organo silane containing at least two hydrolyzable si-lane groups wherein the distance between any two hydrolysis sites on a glass fiber is greater than the distance between any two hydrolyzable silane groups in the organo silane, or (b) an amino-alkylsilane.
Yet another feature of the invention concerns improvement -in the mold flow properties and reduced surface bleeding of these systems through the provision of a composite resin, cement, and clay.
The thermosetting resin can be a phenol-formaldehyde con-densate, a phenol-aminoplast-formaldehyde condensate, an amino-plast-formaldehyde condensate, a furfural condensate, a furfuryl alcohol condensate, a resorcinol-formaldehyde condensate, or a resorcinol-formaldehyde-urea condensate. As a ~, - 3 -, _, . ~

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substitute for the phenol derivative in the thermosetting resin, any suitable polyhydroxy aromatic com-pound such as resorcinol can be employed. It also has been found (see the examples) that the inclusion of urea can be advantageous because of (a) the moderating effect the urea has on the reaction rates, and (b) because urea acts as a fire retardant.
The mole ratio of formaldehyde to phenol can be varied within wide limits in producing the resins for this inventions.
Indeed, in one sense, there is no upper limit on this ratio be-cause Portland cement has been found to cure formaldehyde to aninfusible condition. As a practical matter, the mole ratio of formaldehyde to phenol should range from 1:1 to 5:1. Most de-sirably, this ratio ranges from 1.5:1 to 3:1.
It has been found that the relative proportions in which the hydraulic cement or cements, phenol and formaldehyde can be used in practicing the instant invention can be varied within -comparatively wide limits. In one series of experiments, where the formaldehyde to phenol ratio was held constant at 3:1, it was found that a curable, workable phenol-formaldehyde condensate could be produced when the amount of Portland cement charged varied from one to twenty parts by weight of cement per part by weight of the water used to form the resin and three-fifths of the weight of the formaldehyde used to form the resin. Prefer-ably the weight of hydraulic cement is from about one-and-a-half to about five times this sum.
The ratio by weight of the thermosetting resin to cement ~ -ranges from 1:1 to 1:4.
The resins of this invention are well suited for use as --: ;
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molding compounds and especially well suited for use in a closed mold. Setting or curing of the cement occurs by hydration. Set-ting the large amount of cement in the resins of this invention requires the presence of large amounts of water. During molding, the cement will rid the molding compound of any water resulting from condensation or curing. The same is not true of the resins disclosed in U.S. Patent No. 3,502,610 (mentioned earlier) which contain only small amounts of hydraulic cement. These resins can only be used in open molds where the water can escape to the atmosphere.
The molding compounds also have good flame resistance and low smoke-producing properties. They can be used, for example, -to form shingles, appliances such as bathtubs, and coatings.
Hydraulic cements are broadly defined as powder mixtures made from silica, alumina, lime, iron oxide, and magnesia, which harden when mixed with water. Hydraulic cements include port-land, calcium-aluminate, magnesia, natural, masonry, pozzolan, and slag cements. For the purpose of this application, the term ~-"cement" will be understood to include all hydraulic cements and all cement products. Cement products, as used herein, include those construction materials in which the active or hardening constituents are magnesium or calcium derivatives. Commonly used cement products include lime products and gypsum products.
As indicated previously, this invention can be carried out using either of two systems.
The two systems are the monomer system and the resin sys-tem. In both systems the amount of cement added is within the range of from about 1 to about 20 parts by weight of cement per 1 part by weight of the total water in each system.
In the monomer system, the resin is formed in contact . . .
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lV~(~380 with cement. Depending upon the percent of water in the aldehyde-water solution used, it may be necessary to either add additional water or remove some of the water of reaction. The total water in this system is adjusted to be within the range of from about .15 to about 5 moles of total water per 1 mole of the aldehyde in the system.
In the resin system, the resin is produced prior to its admixture with cement. In this system, the total water is deter-mined, water adjustment is made, and cement is added accordingly.
The addition or removal of water may or may not be necessary.
The total water in this system is determined as follows. A
sample of the resin is placed in an aluminum weighing dish and an initial weight is recorded. The aluminum weighing dish and its contents are then put in an over and dried at about 110C for a period of about 3 hours. The aluminum weighing dish is removed from the oven, allowed to cool to room temperature, and a final weight recorded. The remaining resin is a cured solid mass.
Next, the percent solids of the resin is determined by dividing the final weight by the initial weight. Assuming stoichiometric proportions of all ingredients and substantially 100~ reaction, water is assumed to comprise the total percentage of volatiles tlOO -percent solids). There~ore, the percent volatiles multi-plied by the initial weight of the resin gives the total water in the resin system.
The molding compounds of this invention can contain 0.01 to 10.0 weight percent of the coupling agents based on the total weight of the molding compounds. Preferably this amount ranges from 0.01 to 5.0 weight percent.
With regard to the coupling agents, a particularly suit-able aminoalkylsilane is gamma-aminopropyltriethoxysilane which fi~ - 6 -~:: f~
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108V3~0 is commercially available from Union Carbide under the product designation "A-1100" and from General Electric under the product designation "SC-3900". Also suitable is N-beta (aminoethyl) gamma-aminopropyltrimethoxysilane commercially available from Union Carbide under the product designation "A-1120" and from Dow Corning under the product designation "Z-6020". -The organo silane containing at least two hydrolyzable silane groups having the formula:
(RO) 3 SiR'Si(OR) 3 wherein each R is an alkyl or aryl group containing from 1 to 10 carbons and R' is an alkylene or phenylene group containing from 1 to 15 carbons. A particularly suitable second silane coupling agent is bis (B-trimethoxysilylethyl) benzene (CH30)3SiCH2CH2 ~ -CH 2 CH 2 S i ( OCH 3 ) 3 ) .
A clay is a naturally-occurring sediment or sedimentary rock composed of one or more minerals and accessory compounds, the whole usually being rich in hydrated alumina or in iron oxide, predominantly in particles of collodial or near-collodial size, and commonly developing plasticity when sufficiently pul-vèrized and wetted. Modern studies have organized the clay min-erals into ~our crystalline groups and one noncrystalline group:
(1) the kaolin group, (2) the montmorillonite group, (3) the variously named illite, bravasite, or hydromica group, (4) atta-pulgite, and (5) allophane, which is the noncrystalline group.
The clays which can be utilized in this invention are of the kaolin crystalline group. More specifically, kaolins which have been employed are classified as ceramic clays. Ceramic clays will be understood to include: residual kaolin clays, sedimen-tary kaolin clays, ball clays, fire clays, and clays prepared for porcelain enamels. Old Mine #4 Ball Clay, available from ~. . , ~V8V3~0 Kentucky-Tennessee Clay Co., located in Mayfield, Kentucky, is particularly suited for use in this invention. Old Mine #4 Ball Clay has a raw color of medium gray and a fired color, cone 12, of light gray white. Typical chemical analysis data of Old Mine #4 Ball Clay shows:
Ingredient Percen~ by Weight Silicon Dioxide (SiO2) 52.1 Aluminum Dioxide (Al203) 31.1 Titanium Dioxide (Tio2) 1.6 Iron Oxide (Fe2O3) 0.8 Calcium Oxide (CaO) 0.4 Magnesium Oxide (MgO) 0.3 Potassium Oxide (K2O) 1.0 Sodium Oxide (Na2O) 0.3 Loss on Ignition 12.4 ~ -Total 100.0 -99% of the particles comprising Old Mine #4 Ball Clay are finer than 20 microns, and 68% of the particles are finer than 1 micron.
The amount of ceramic clay which can be employed in a molding compound of this invention is within the range of from about 5 to about 40 percent by weight of the total weight of the molding compound, clay included. Preferably, ceramic clay is present in an amount within a range of from about 10 to about 20 percent by weight of the total weight of the molding compound. -; The molding compounds of this invention can be molded by any suitable molding method~ They are particularly suitable for use as sheet molding compounds (SMC) or a bulk molding compound (BMC). When so used, the molding compound is employed in an amount from about 10 to about 95 percent by weight of the total 108l~380 composition, reinforcing the glass fibers in an amount up to about 80 percent by weight of the total composition, and fillers in an amount to make up the balance of the total composition.
Preferred fillers are calcium carbonate and alumina.
In both SMC and BMC it is preferred that a mold release agent be added in an amount up to about 5 percent by weight of the sheet or bulk molding compound. A particularly suitable mold release agent is zinc stearates.
The following examples illustrate the invention.

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V31~0 IngredientsParts by Weight ~ol Ratio Formaldehyde127.90 3.1 Phenol 67.10 Calcium Oxide3.78 Dicyandiamide3.35 Urea (liquid)20.06 The phenol and formaldehyde were charged to a --reactor, blended and heated to a temperature of 110 F. The calcium oxide catalyst then was added over a two-hour period while maintaining the temperature at 110 F. The temperature of the reactants was increased to 125F over a 30-minute period and then maintained at that temperature for an additional 90 minutes. The temperature then was raised to 140F during a time period of 30 minutes and maintained at that temperature until the free formaldehyde content ranges from 7.0 to 7.2 percent by weight. The dicyandiamide was added over a 30-minute period at 140 F and the reaction was cooled to 105F
over the next 1/2-hour period. The urea was added at 105F and neutralization followed when the temperature dropped below 100F by addition of a mixture of 20 percent by weight of phosphoric acid and 80 percent by weight of sulfuric acid to a pH ranging from 7.2 to 7.3.
Physical properties of the Example I resin are as follows:
Stroke Cure 77 seconds -Free Phenol 1.2 percent lV~3~380 EXAMPLE I I
The followinq materials were mixed in a stainless steel vessel:
Weight grams Resin of Example I 5000 Portland Cement 2500 Gypsum Cement 2500 Alumina Trihydrate 2000 Zinc Stearate 20Q

The resulting composition was co-deposited with chopped glass fiber strand on amoving polyester film approximately 24 inches in width and of indefinite length. A second polyester film, also 24 inches in width and of indefinite length, was brought into contact with the upper surface of the sheet-like mass of deposited glass fibers and resin-cement mixture and was moved with the mass and the first sheet. Sheets of the mass, approxi-mately 24 inches by 20 inches by 1/8 inch, were cut from the mass, leaving the polyester films on each of the two major sides thereof. Moldings were produced from these sheets between matched flat dies: five minutes at 300F and 2000 pounds per square inch.
Sheets produced as described above were tested for flexural modulus, for flexural strength, for tensile strength, and for notched Izod impact strength: (1) as molded, and

(2) after they had been autoclaved for 16 hours. Results of this testing are summarized in the following Table.
In the Examples, flexural strength and flexural modulus were determined according to ASTM Specification D79n, tensile strength was determined according to AsTrq Specification D638, and impact strength was determined according to ASTM

Specification D256.
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TABLE
Flexural Flexural Tensile ~lotched Izod Strength Modulus Stren~th Impact Strength psi x 103 psi x 106 psi x 103 ft., lbs./in.
As molded ll.99 1.107 4.37 8.92 After 16 hours of autoclaving7.65 0.759 2.41 6.5 These results demonstrate that the thermosetting resins of this invention possess physical properties which make them ~ery desirable for use as molding compounds. The molded articles were found to be fire resistant and low smoke producing.
They were easily cured in a closed mold.
EXA~PLE III
':
A phenol-urea-formaldehyde condensate was produced from 1240 parts phenol, 2600 parts 52 percent formaldehyde, 2500 parts Portland cement, 1290 parts urea, 2500 parts gypsum cement, 2500 parts alumina, 400 parts zinc stearate and 800 parts ice. The phenol, formaldehyde, urea and 100 parts of the Portland cement were charged to a stainless steel vessel equipped with a propeller type agitator and an indirect heat exchanger. This charge was agitated for 18 hours, during which time cooling water was circulated through the indirect heat exchanger to maintain the temperature of the charge at about 68C. After the preliminary 18 hour reaction period, the rest of the Portland cement, the gypsum, the alumina, the zinc stearate and the ice were added to the reactant products in the vessel. The resulting composition, which was 2 phenol~
formaldehyde condensate was co-deposited with chopped glass fiber strand (The fibers were made of a glass containing about 54 percent SiO2, 14 percent A1203, 4.5 percent MgO, 17.5 percent CaO and 10 percent B203. They were coated with a polyester size containing a lubricant and gammaaminopropyl-triethoxysilane.) on a moving polyester film approximately 24 .

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inches in width and of indefinite length. A second polyester film, also 24 inches in width and of indefinite length was brought into contact with the upper surface of the sheet-like mass of deposited glass fibers and phenokformalde~yde condensate, and was~moved Withthe mass and the first sheet. Sheets called "Sheet Molding Compound", of the mass of condensate and glass fibers approximately 24 inches by 20 inches by 1/8 inch were cut from the mass, leaving the polyester films on each of the two major sides thereof. Moldings were produced from these sheets between matched flat dies: five minutes at 300F. and 283 pounds per square inch.
Sheets produced as described above were tested for fleYural modulus, ~ST~: n-790) for flexural strength, for tensile stren~th, (ASTM D-638) and for notched Izod impact strength:(ASTM D-256) (1) as molded; (2) after they had been autoclaved for 16 hours at 227F.; and (3) after they had been immersed in boiling water for two hours. Results of this testing are summarized in the following Table for several ratios of glass fibers to phenol-formaldehyde condensate.

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It has heen found that the phenolic condensate produced as descri~ed ahove has a shelf life sufficiently long, ~ -under ordinary ambient conditions, that Sheet ~olding Compound produced therefrom within four hours is satisfactory, and the sheet molding compound, itself, has a shelf life greater than three weeks. It will be appreciated that this is adequately long to make ordinary use of the material for producing sheets or other moldings entirely feasible.
The data in the foregoing Table show an unexpected result: a comparatively slight decrease in the strength of the moldings, as indicated by the data, after two hours of autoclaving at 227F. and after two hours in boiling water, indicates that the glass fibers were not appreciably affected by the cement. This is unexpected because glass fibers of the indicated composition, distributed in reinforcinq relationship -with a hydrated mixture of equal parts of Portland and C.ypsum cements, would be at least virtually destroyed by sixteen hours of autoclaving at 227F. The data in the foregoing Table, on the other hand, indicate not more than slight deterioration of -the fibers during either autoclaving or boiling. -To demonstrate the excellent fire resistance of moldings produced according to the method of Example III, panels were produced and were tested forflame spread, fuel con-tributed and smoke developed in comparison with panels which presently are being produced commercially. The panels according to the invention were produced from a phenol-urea-formaldehyde condensate produced as described in Example III, above, from the charge there set forth plus 20 parts 1,2-bis-trimethoxysilyl-~thane. Sheets were produced as described in Example IV from the resulting condensate and glass fibers (The glass fibers were made i~ - 16 -.~! r ':. ' . . .. , ' .: . . .

V3~0 of a glass havin~ the composition set forth in Example 1 above, and coated with a polyester size containing gammamethacryloxy-propyltrimethoxysilane.) codeposited with the condensate in such proportions that the glass fibers constituted suhstantially 22 percent of the condensate and fibers. Panels 21 inches by 24 inches by 1/8 inch were then molded from the resulting sheets:
290 F for 5 minutes at 60 tons pressure. These panels were tested, ASTM E-84 tunnel test against panels which are presently being marketed, with the following results:

Panels Produced Present According to Commercial the Invention Panels Flame Spread 20 90 to 110 Fuel Contributed 0 25 to 50 Smoke Developed 2 400 to 500 In each case, a low number for the E-84 tunnel test indicates better performance than does a higher number.
EXAMPLE IV
This example demonstrates the monomer system in which was employed a com~ination of cements. he following ingredients were employed.
Ingredients Weight, grams ~ole Ratio Phenol 94 52% Formaldehyde Solution in Water 144.2 2.5 Portland Cement 171.3 Gypsum Cement 171.3 Deionized Water 45 The ingredients can be mixed in any order and by any suitable mixing procedure. However, it is preferred to add the cements in two steps to enable the resulting exothermic reaction to be controlled thus avoiding immediate set-up of the cem~nts.

~ - 17 -:lO~V~o In this example, 94 grams of phenol, 144.2 grams o a 52% solution of formaldehyde in water, 45 grams of water, and 10 grams of ~o~tland cement were added to a beaker at room temperature.
The mixture was stirred and the exothermic reaction proceeded immediately.
The beaker was water-cooled to prevent heating to a temperature over 60 C. The mixture was permitted to cool to room temperature at which time the remaining 161.3 grams of Portland cement and 171.3 grams of gypsum cement were added to the beaker with stirring. The resulting product was recovered as a molding compound. The gypsum cement used was commercially available from United States Gypsum under the trade name "Hydracal B-ll".
EXAMPLE V
.
8.7 grams of gamma-aminopropyltriethoxysilane were ---added to 580.8 grams of the monomer system of Example I. The addition was made at room temperature in a beaker with stirring.
The resulting product was recovered as a molding compound.
The gamma-aminopropyltriethoxysilane was "~-1100" available from Union Carbide.
EXAMPLE VI
8.7 grams of bis(B-trimethoxysilylethyl) benzene, a silane coupling agent with two hydrolyzable silane groups, were -added to 580.8 grams of the monomer system of Example I. The addition was made at room temperature in a beaker with stirring.
The resulting product was recovered as a molding compound.
EXAMPLE VII
4.35 grams of gamma-aminopropyltriethoxysilane and 4.35 grams of bis(B-trimethoxysilylethyl)benzene, a silane coupling agent with two hydrolyzable silane groups, were added to 580.8 grams of the monomer system of Example I. The addition was made at room temperature in a beaker with stirring. -The resulting product was recovered as a molding compound. The ~ - 18 -, ~ ~ . -. , -.

3t~0 gamma-aminopropyltriethoxysilane was "A-llO0" available from Union Carbide.
EXAMPLE VIII
5000 grams of the resin of Example I, 2500 grams of Portland cement, and 2500 grams of gypsum cement were added to a stainless steel vessel at room temperature with stirringO The resulting product was recovered as a molding compound.

EXAMPLE IX
5.25 grams of gamma-aminopropyltriethoxysilane were added to 350 grams of the resin system of ~xample YI. The addition was made at room temperature in a beak.er with stirring.
The resulting product was recovered as a molding compound. The gamma-aminopropyltriethoxysilane was "A-llO0" available from Union Carbide.

EXA~PLE X
5.25 grams of bis(B-trimethoxysilylethyl)benzene, a silane coupling agent with two hydrolyzable silane groups, were added to 350 grams of the resin system of Example VI. The addition was made at room temperature in a beaker with stirring.
The resulting product was recovered as a molding compound.
EXAMPLE XI
2.62 grams of gamma-aminopropyltriethoxysilane and 2.62 grams of bis(B-trimethoxysilylethyl)benzene were added to 350 grams of the resin system of Example VI. The addition was ~-made at room temperature in a beaker with stirring. ~he ~ -resulting product was recovered as a molding compound.
EX~MPLE XII
This example will demonstrate the incorporation of a resin system into sheet molding compound (SMC). The following ingredients were employed.

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v;~o INGREDIENTSWEIGHT, Gl~AMS
Resin of Example VI10,000 gamma-aminopropyltrieth-oxysilane 10 bis(B-trimethoxysilyl-ethyl)benzene 10 Alumina 2,000 Zinc Stearate 200 The above ingredients can be mixed in any order and by any suitable mixing procedure. However, in this example, they were mixed as follows. The resin was first charged to a stainless steel mixing vessel at room temperature. The gamma-aminopropyltriethoxy silane and the bis ~ -trimethoxy-silylethyl)benzene were added next with stirring. While the stirring was continued and room temperature maintained, the alumina was added followed by the zinc stearate.
The resulting composition was co-deposited with chopped glass fiber strand on a moving polyethylene film approximately 24 inches in width and of indefinite length. A
second polyethylene film also 24 inches in width and of indefinite length, ~as brought into contact with the upper surface of the sheet-like mass of deposited glass fibers and resin-cement mixture and was moved with the mass and the first ~:
sheet. Sheets of the mass, approximately 24 inches by 20 inches by 1/8 inch, were cut from the mass, leaving the polyethylene films on each of the two major sides thereof. ~oldings were - -produced from these sheets between matched flat dies, moldings being conducted for five minutes at 300F and 1000 pounds per -square inch. ~ -Sheets produced as described above were tested for flexural modulus, for flexural strength, for tensile strength, ~-. ,~ .

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~v~o and for notched Izod impact strength, both (1) as molded, and (2) after the sheets had been autoclaved for 16 hours at a temperature of 227 F. Results of this testing are summarized in the following Table and are compared to a control in which the sheets were produced from a molding compound which employed the same resin system without coupling agent.

TABLE
ControlEXAMPLE XII
Flexural Strength, psi x 10 (as molded) 11.99 19.43 10 Flexural Strength, psi x 103 (after 16 hours of autoclaving) 7.65 10.95 Flexural Modulus, psi x 106 (as molded) 1.107 1.706 Flexural Modulus, psi x 106 (after 16 hours of autoclaving) 0.759 1.309 Tensile Strength, psi x 103 (as molded) 4.37 7.75 Tensile Strength, psi x 103 (after 16 hours of autoclaving) 2.41 4.37 Notched Izod Impact Strength Foot/Pounds/Inch (as molded) 8.92 7.20 In the examples, flexural strength and flexural modulus were determined according to ASTM Specification D790, tensile strength was determined according to ASTM Specification D638, and impact strength was determined according to ASTM
Specification D256.
These results demonstrate that the molding compounds of this invention possess physical properties which make them very desirable for use as molding compounds. The molded articles were found to be fire resistant, to be low smoke producing, and to have improved strength. In addition, the molded articles were easily cured in a closed mold.

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l~V3~0 EXAMPLE XIII
This example demonstrates a preferred mode of preparing a molding compound of this invention and its incorporation into sheet molding compound (SMC). The following ingredients were employed:
Parts by Weight Ingredients per 100 parts Resin of Example I 35.2 Portland Cement 17.6 Gypsum Cement 17.6 Ceramic Clay 14.0 Glass Fibers 14.0 Zinc Stearate 1.4 gamma-aminopropyltriethoxysilane .1 tetraethoxysilane .1 The above ingredients can be mixed in any order and by any suitable mixing procedure. However, in this example, they were mixed as follows. The resin was first charged to a stainless steel mixing vessel at room temperature. Next, the total amount of portland cement, and the total amount of gypsum cement, was added sequentially at room temperature with stirring.
While stirring was continued and room temperature maintained, the ceramic clay and the zinc stearate were added followed by the two coupling agents. The product was recovered as a molding -compound. The ceramic clay used was Old Mine #4 Ball Clay. The gypsum cement used was Hydracal B-ll commercially available from United States Gypsum Corp. The gamma-aminopropyltri-ethoxysilane used was A-1100 and the tetraethoxysilane used was Tetraethyl Orthosilicate, both commercially available from Union Carbide Corporation.

The ingredients were deposited on a moving ,, ~ - 22 -10~ 0 polyethylene film approximately 24 inches in width and of indefinite length. A second polyethylene film also 24 inches in width and of indefinite length, was brought into contact with the upper surface of the sheet-like mass of deposited glass fibers and resin-cement mixture and was moved with the mass and the first sheet. Sheets of the mass, approximately 12 inches by 18 inches by 1/8 inch, were cut from the mass, leaving the polyethylene films on each of the two major sides thereof. Moldings were produced from these sheets between matched flat dies, moldings being conducted for three minutes at 300F and 926 pounds per square inch. In the resulting molded article we noticed very little surface bleeding.
EXAMPLE XIV
This example demonstrates a method of preparing a molding compound of the invention. The following ingredients were used: -Parts by Weight Ingredients per 100 parts Resin of Example I 35.2 Portland Cement 17.6 Gypsum Cement 17.6 Ceramic Clay 14.0 Glass Fibers 14.0 Zinc Stearate 1.4 gamma-aminopropyltriethoxysilane 0.1 tetraethoxysilane 0~1 -The above ingredients were mixed using the same mixing procedure as in Example XIII. The glass fibers were added with continued stirring at room temperature after the addition of the silane coupling agents. The stirring was continued until the glass fibers were evenly dispersed.

~ - 23 -o The resulting compound was recoYered as a bulk molding compound (BMC). The individual glass fibers used had a length within the range of from about 1/8" to about 1 1/4"
and a diameter within the range of from about .00025" to about .000299". The ceramic clay used was Old Mine ~4 Ball Clay. The gypsum cement used was Hydracal B-ll. The gamma-aminopropyltriethoxysilane used was A-1100 and the tetra-ethoxysilane was Tetraethyl Orthosilicate.
A charge of the resulting compound weighing about 1000 grams was placed into a heated mold. A flat sheet molding, approximately 12 inches by 18 inches by 1/8 inch was produced between matched flat dies. The molding was -conducted for three minutes at 300F and at a pressure of 926 pounds per square inch. -In the resulting molded article was observed good ~ -mold flow and very little surface bleeding.
EXAMPLE XV
The following example demonstrates the use of the monomer system to prepare a molding compound of ~he invention.
In this example the thermosetting resin is produced in contact with cement to form a resin-cement molding compound. The resulting resin-cement molding compound is then further modified and incorporated into sheet molding compound(SMC).
The following ingredients are employed.

Parts by Weight Mole Ingredients per 100 parts Ratio Phenol 9.5 52% Formaldehyde Solution in Water 14.6 2.5 Portland Cement 17.2 Gypsum Cement 17.2 ~ - 24 -Deionized Water 4.5 Glass Fibers 23.0 Ceramic Clay 12.6 Zinc Stearate 1.2 gamma-aminopropyl-triethoxysilane .1 tetraethoxysilane .1 The ingredients can be mixed in any order and by any suitable mixing procedure. However, it is preferred to add the cements in two steps to enable the resulting exothermic reaction to be controlled thus avoiding immediate set-up of the cements.
In this example, the total amounts of phenol 52%
formaldehyde-water solution, and deionized water are first charged to a stainless steel mixing vessel at room temperature.
Approximately 10~ of the total amount of portland cement is then added. The mixture is stirred and the exothermic reaction proceeds immediately.
The mixing vessel is then water-cooled to prevent heating to a temperature over 50C. The mixture is permitted 20 to cool to room temperature at which time the remaining ~ -~
amount of portland cement, the total amount of gypsum cement, the total amount of gamma-aminopropyltriethoxysilane, and the total amount of tetraethoxysilane are added to the vessel with stirring. The resulting product is a resin-cement molding compound.
While stirring is continued, the above resin-cement molding compound is modified by the addition of the total amounts of ceramic clay and ~inc stearate. The ceramic clay used is Old Mine #4 Ball Clay.

The ingredients are deposited on a moving poly-~ - 25 -, V~V

ehtylene film approximately 24 inches in width and of indefinite length. A second polyethylene film also 24 inches in width and of indefinite lenqth, is brought into contact with the upper surface of the sheet-like mass of deposited glass fibers and resin-cement compound and is moved with the mass and the first sheet. -~
The resulting product is recovered as sheet molding compound (SMC).
EXAMPLE XVI (Control) In this example the same ingredients were used as in Example XIII except that alumina was used as a filler instead of ceramic clay. The mixing procedure was the same as in Example II and the resulting molding compound was incorporated into SMC in the same manner as in Example XIII. In the resulting molded articles was observed noticeable surface bleeding in comparison with moldings of Example XIII in which wasobserved very little surface bleeding.
EXAMPLE XVII (Control) . .
In this example the same ingredients were used as in Example XIV, except that alumina was used as a filler instead of ceramic clay. The mixing procedure was the same in Example XIV and the resulting bulk molding compound was molded in the same manner as in Example XIV. In the resulting molded article was observed poorer mold flow and noticeable surface bleeding in comparison to moldings of Example XIV in which was observed good mold flow and very little surface bleeding.

~ - 26 -

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A molding composition comprising:
(A) a mixture of: (1) a thermosetting resin of at least one of the phenol-formaldehyde condensates, phenol-aminoplast-formalde-hyde condensates, aminoplast-formaldehyde condensates, furfural condensates, fufuryl alcohol condensates, resorcinol-formalde-hyde condensates, or resorcinol-formaldehyde-urea condensates, and (2) cement, wherein said cement is present in an amount within the range of from about 1 to about 20 parts by weight of cement per part by weight of the water content of the thermosetting resin;
or (B) a condensate resin formed from cement, formaldehyde, and at least one of phenol, aminoplasts or resorcinol, wherein the weight of the cement is from 1 to 20 parts by weight of cement per part by weight of the water used to form the resin and three-fifths of the weight of the formaldehyde used to form the resin;
wherein the cement is a hydraulic cement or cement product, and the weight ratio of cement to thermosetting resin ranges from 1:1 to 4:1.

2. A molding composition as defined in claim 1, wherein the amount of cement is from 1 to 9 parts by weight of cement per part by weight of the water.

3. A molding composition as defined in claim 1, wherein the ratio of cement to thermosetting resin ranges from 1:1 to 3:1.

4. A molding composition as defined in claim 1, wherein the thermosetting resin is a phenol-formaldehyde condensate or a phenol-aminoplast-formaldehyde condensate having a mole ratio of formaldehyde to phenol of at least 1:1.

5. A molding composition as defined in claim 1, 3 or 4, wherein the amount of cement is from 1.5 to 5 parts by weight of cement per part by weight of the water.

6. A molding composition as defined in claim 1, 2 or 4, wherein the ratio of cement to thermosetting resin is 2:1.

7. A molding composition as defined in claim 1, 2 or 3, wherein the thermosetting resin is a phenol-formaldehyde conden-sate or a phenol-aminoplast-formaldehyde condensate having a mole ratio of formaldehyde to phenol of from 1:1 to 5:1.

8. A molding composition as defined in claim 1, 2 or 3, wherein the thermosetting resin is a phenol-formaldehyde conden-sate or a phenol-aminoplast-formaldehyde condensate having a mole ratio of formaldehyde to phenol of from 1.5:1 to 3:1.

9. A molding composition as defined in claim 1, 2 or 4, wherein said cement is a Portland cement, calcium-aluminate ce-ment, magnesia cement, or slag cement.

10. A molding composition as defined in claim 1, 2, or 4 wherein said cement is a gypsum cement.

11. A molding composition as defined in claim 1, 2, or 4, wherein said cement comprises a mixture of hydraulic cement and gypsum cement.

12. A molding composition as defined in claim 1, 2, or 4, wherein said cement is Portland cement.

13. A molding composition as defined in claim 1, inclu-ding 0.01 to 10.0 weight percent of a coupling agent based on the total weight of the molding compound, wherein the coupling agent is an (a) organo silane containing at least two hydrolyzable si-lane groups wherein the distance between any two hydrolysis sites of a glass fiber is greater than the distance between any two hy-drolyzable silane groups in the organo silane, or (b) amino-alkylsilane.

14. A molding composition as defined in claim 13, where-in said organo silane coupling agent has the general formula (RO)3SiR'Si(OR)3 wherein each R is an alkyl or aryl group containing from 1 to 10 carbons, and R' is an alkylene or phenylene group containing from 1 to 15 carbons.

15. A molding composition as defined in claim 13, where-in said amino-alkylsilane coupling agent is gamma-aminopropyltri-ethoxysilane.

16. A molding composition as defined in claim 13, 14, or 15, wherein the weight percent of said coupling agent ranges from 0.01 to 5.0%.

17. A molding composition as defined in claim 13, 14, or 15, wherein the weight percent of said coupling agent is 0.15%.

18. A molding composition as defined in claim 1, inclu-ding a ceramic clay.

19. A molding composition as defined in claim 18, where-in said clay is a residual kaolin clay, sedimentary kaolin clay, ball clay, fire clay, or clay prepared for porcelain enamel.

20. A molding composition as defined in claim 19, where-in said clay is present in an amount within the range of from about 5 to about 40 percent by weight of the total composition.

21. A molding composition as defined in claim 1, inclu-ding glass fibers.

22. A molding composition as defined in claim 4, 13, or 18, including glass fibers.

23. The sheet molding compound of claim 21 comprising a phenol-formaldehyde condensate, Portland cement, gypsum cement, ball clay, glass fibers, zinc stearate, and at least one silane coupling agent.

24. The sheet molding compound of claim 23 wherein:
(a) the mole ratio of formaldehyde to phenol is from about 1 to about 5 moles of formaldehyde per mole of phenol;
(b) water is present in an amount of from about .15 to about 5 moles of water per mole of said formaldehyde;
(c) cement is present in a total amount of from about 1 to about 20 parts by weight cement per part by weight of said water;
(d) ball clay is present in an amount of from about 5 to about 40 percent by weight of said sheeting molding compound;
(e) glass fibers are present in an amount greater than 0 up to about 60 percent by weight of said sheet molding compound;
(f) zinc stearate is present in an amount up to about 5 percent by weight of said sheeting molding compound; and (g) coupling agent is present in a total amount up to about 5 percent by weight of said sheet molding compound.

25. The sheet molding compound of claim 23 comprising 35.2 weight percent of a phenol-formaldehyde condensate, 17.6 weight percent of Portland cement, 17.6 weight percent of gypsum cement, 14.0 weight percent of ball clay, 14.0 weight percent of glass fibers, 1.4 weight percent of zinc stearate, 0.1 weight percent of gamma-aminopropyltriethoxysilane, and 0.1 weight per-cent of tetraethoxysilane.

26. A bulk molding compound comprising the molding com-position of claim 21 and comprising a phenol-formaldehyde conden-sate, Portland cement, gypsum cement, ball clay, glass fibers, zinc stearate, and at least one silane coupling agent.

27. The bulk molding compound of claim 26 wherein:

(a) the mole ratio of formaldehyde to phenol is from about 1 to about 5 moles of formaldehyde per mole of phenol;
(b) water is present in an amount of from about .15 to about 5 moles of water per mole of said formaldehyde;
(c) cement is present in a total amount of from about 1 to about 20 parts by weight cement per part by weight of said water;
(d) ball clay is present in an amount of from about 5 to about 40 percent by weight of said bulk molding compound;
(e) glass fibers are present in an amount greater than 0 up to about 60 percent by weight of said bulk molding compound;
(f) zinc stearate is present in an amount up to about 5 percent by weight of said bulk molding compound; and (g) coupling agent is present in a total amount up to about 5 percent by weight of said bulk molding compound.

28. The bulk molding compound of claim 26 comprising 36.2 weight percent of a phenol-formaldehyde condensate, 17.6 weight percent of Portland cement, 17.6 weight percent of gypsum cement, 14.0 weight percent of ball clay, 14.0 weight percent of glass fibers, 1.4 weight percent of zinc stearate, 0.1 weight percent of gamma-aminopropyltriethoxysilane, and 0.1 weight per-cent of tetraethoxysilane.

29. A molded article formed under heat and pressure from a molding composition as defined in claim 1 and a mat of randomly-oriented glass fibers.