DE2055363A1 - Polyester molding compound - Google Patents

Description

dr. W. Schalk dipl.-ing. P. Wirth dipl.-ing. G. Dannenberg DR. V. SCHMIED-KOWARZIK · DR. P. WEIN HOLD ■ DR. D. GUDEL

6 FRANKFURT AM MAIN

OR. ESCHENHEIMER STRASSE 39

Hn / ju gases RP-7818-M

DART INDUSTRIES, INC.

P.O. Box 3157

Los Angeles, California 9OO5VUSA

Polyester molding compound

The invention relates to casting or molding compositions and a casting or molding process. In particular, it relates to a molding compound _; Made of water-stretchable polyester resin that is capable of releasing the water again after being deformed or cast into an object. The invention relates to; ä also to reduce a method of casting or molding, by means of which it is possible, after the water content of the molded article. j

An introduced in the field of molded plastics recently innovation was the introduction of stretchable with water (water-extendible) polyester resins such as those described for example in US Patent 3,256,219, on. which is expressly referred to here. Obviously, such a material has very great economic benefits to the consumer since water is the cheapest resin extender currently available.

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ORIGINAL INSPECTED.

These advantages are further enhanced by the fact that it is possible to extend (blend) these resins with up to 90% water and to incorporate pigments, oil- or water-soluble colors as dyes into the molding compound. Further features _Ψ which further expand the field of application for these resins j concern various properties which the molded ■

Products have and include that they are shipped, sawn,; polished, machined, glued and reinforced with the most varied of fibrous and / or granular fillers · \ This shows that these resins are used for the production of the most varied. Utensils as a substitute for wood, plaster (mortar) ceramics, other plastics etc. can be used.

As already indicated, it is possible to use the water-stretchable polyester resins to produce castings that are either elastic or rigid. In addition, it is possible for any given resin to change the physical properties by changing its water content (i.e. the ratio of water to resin content) 5 to 1.4 % can be expected. This is close to the shrinkage values that are found with other unsaturated polyesters, but if the water-stretchable material is used, the shrinkage is proportional to the percentage of water used and the higher the percentage of water used, the lower it is Expected shrinkage values In connection with the removal of the water from the molded product, a further advantage was found in this regard · Typical shrinkage values for a polyester laden with water ί (50% water and 50 % resin) are in the order of magnitude of 1.0 % _t while for a correspondingly composed product from which the water has been removed by the method according to the invention, a shrinkage value of 0.5%, i.e. a 50% improvement can be expected. It is believed that this improvement occurs independently

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From the amount of water contained in the molding emulsion.

Articles containing water extensible polyester resins are described in U.S. Patent 3,256,219 and include those which are commercially available and which, after casting or molding, have a tendency to rapidly lose water from any exposed surfaces . However, the overall effect of this phenomenon has proven to be minor. Diffusion of water from a depth below 4.76 mm (3/16 inch) is extremely slow and even after prolonged heating at 71 ^° O (160 ^° F) the water is not expelled quickly from these cellular structures and is particularly limited in products that contain between 40 and 7% resin. Although the water extender can be driven off by prolonged heating at temperatures in the vicinity of 100 ° G (212 ° F), this process is not economically satisfactory.

In addition, it is clear that the hardened castings with a water content of 50 to 65% because of their tendency, the water withhold a density of 0.96 to 1.04 g / cm (60 to 65 lbs / ft. ), such as that of water. This is, although lighter than many typical pots, a serious disadvantage for product manufacturers. Even though that the water-extendable resins are very satisfactory in many respects, a major disadvantage is that the weight of the finished cast product is not controlled or can be restricted.

The main aim of the present invention is therefore to provide a modified, Specify water-stretchable polyester resin composition and a molding process in which the water content of a hardened Castings made of this material can be effectively and economically controlled and reduced, so as to reduce the weight

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of the castings. This makes the water stretchable polyesters quite evident through reduction transport costs, etc. are not only more economical, but also a product and a process are added to the shaper Hand given that provides better shrinkage properties within the molded product.

Briefly summarized, the invention relates, inter alia, to a method in which the particle size of a polyester resin / Water composition is carefully controlled during the mixing at which the emulsion is formed. As already noted above, such control can be achieved by incorporating certain surfactants into the Emulsion of these water-stretchable, unsaturated polyester resins introduces. Based on the use of these particular surfactants in amounts between 3 and 7% » based on the weight of the resin, the persistence or breakage of the emulsion during and subsequent to gelation of the material so that the water extender is released. It has been shown that those surface-active Agents that are lipophilic in nature are particularly useful in effectively practicing the invention, and that by manipulating the hydrophilic-lipophilic balance, which is described in more detail below, can to some extent control the amount of water that is passed through a cast or molded object is initially dispensed.

It has also been found beneficial to use with surfactants or aggregates alone to help break the emulsion to release the water extender. This release takes place during and after the gelling of the emulsion

Regardless of the process used to reduce the water content in the finished casting, should

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the surfactant is added to the polyester resin or the water / polyester resin emulsion before it is catalyzed. The exact time of addition does not seem to be critical, but it is thoroughly regulated Mixing is desirable to form a uniform dispersion of the surfactant, etc., within the Emulsion.

As already indicated above, other methods and Additives are used to aid in particle size control «. For example, the misery can be more rapid the shape of the stirrer and the dimensions of the mixer all can be varied to achieve the desired end results. The throughput speeds in a commercially available device such as those from Gray Company, Inc., Minneapolis, Minnesota, available under the trade name Hydra-Cat, can be varied »It has been found that by thorough Controlled mixing kept a predominant water and resin particle size within the emulsion above a minimum value can be, whereby in fact no water is released. In most cases, these can be commercially available Devices, as will be explained in more detail below, are regulated to a large extent in order to ensure the degree of mixing " to delay the emulsion.

As already indicated above, the invention relates to the use of a water-stretchable, unsaturated polyester resin as a casting or molding compound. When _{they are intended to be used,} these resins are mixed with water and various other additives to form a thermosetting emulsion. As would be expected, the properties of any finished cast article containing such resins can be improved by appropriate selection of the resin, the amount of water included, the catalyst system used and the filler,

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if one is used, can be determined. These water-stretchable polyester resins are readily available commercially from Ashland Chemical Company, Reichhold Chemicals Inc., and American Cyanamid and others. Some of them can be obtained from the manufacturers in a pre-activated state, while other manufacturers only supply the resin and leave the formulation to the consumer. So sells, for example, Reichhold Chemicals Inc.'s various activated polyester resins under the trade name Polylite and the company Ashland Chemical Company and American Cyanamid offer various non-activated resins to under the name AROPOL WEP or Laminac ® EPX 295-1. Like ^; Materials are described in U.S. Patents 3,437,615 i

3,437,618 and 3,442,835. !

A water-stretchable polyester resin is preferably a dispersion of an aqueous phase in one of the monomeric ones Continuous phase containing material. ' It is possible to produce stable emulsions with a continuous emulsion from these substances Phase containing monomeric material and a dispersed aqueous phase to produce in which the aqueous phase remains dispersed even during and after the polymerization of the monomer.

A preferred method of making such more stable;

Emulsions is that you as emulsifiers microgels i used "microgels containing a polymer, a solvent ^j medium and a non-solvent, they seem to be gaülertartig i and they are generally prepared by \ a non-solvent for the polymer into a the Introduces polymer containing solution. An emulsion with a dispersed aqueous phase and a continuous phase is stabilized by a microgel which is formed at the interface between the continuous phase and the aqueous phase. The continuous phase must have a component

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hold, der.aus the continuous phase at the phase interface is at least partially eliminated and precipitated.

The properties of typical water-stretchable poly- ' Ester resins are the following:

AROPOL * AROPOL .AROPOL AROPOL AROPOL AROPOL WEP 22 WEP 23 WEP 26 V / EP 27 WEP 41 WEP

Brookfield λ

Viscosity '

(cP) 250+ 400+ 145 + 5 50 + 5 · 60 + 5 30 + 5 specific

Weight - - 1.075 1.039 1.060 1.025 Weight g / cnr

(lbs / gal.) 1.01 1.01 ■ 1.07 ¹ 04 1.06 1.02 (8.40) (8.40 ) (8.94) (8.63) (8.81) (8.52)

Gardner- bright-bern-bright-

Color stone- amber- <3 <O <2 <2 ben colors

Gel time ' g

(Min.) 3+ 3+ 11+ 15+ 13+ 17+ 'Exothermic.

Time peak

(Min.) 8+ 6+ 11+ 31 20 28+ Exothermic

peak, ⁰ C ( ⁰ F) 102 100.5 62.4 '75.8 75.8 75.2

(216) (213) (164) (168) (168) (167)

»AROPOL 21 is similar to AROPOL 22 ■ '

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POLYLITE POLYLITE POLYLITE POLYLITE 52-176 32-177 32 ~ 1? 8 32-179

Brookfield

Viscosity (cP) 400-800 50-100 190-250 100-200

colour

light-amber- light-amber- light-amber- pink-amber-colored stone colored stone colored stone colored

Gel time (min.) 5-7

5-10

2 1 / 2-5 7-15

Brookfield viscosity (cP)

LAMINAC * "EPX 289-4

1.0-1.5

LAMINAO ^ EPX 295-1

0.4-1.0

Weight g / cm "
(lbs / gall)

1, P2 (8.50)

1.02-1.0; (8.50-8.60.

colour

purple

dark red

Gel time (min.)

2+

1-3

Exothermic. Time peak '(min.)

8+

. 7-12

Exothermic peak, ⁰ C ( ⁰ F) 77-82

(170-180)

71-82 (160-180)

Although molded articles made from these resins can be stretched with up to 90 % water, it is believed that the broadest continuous range of use is on the order of 40 to 70 % water based on the total weight of the emulsion.

The viscosity of the emulsion begins to rise rapidly when the Water content a value of 55% »based on the total weight of the emulsion, this can, however, by adding

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small amounts of a styrene monomer or by adding; mineral aggregate fillers or the like to the; Emulsion can be reduced and controlled. i

The formation of this new form emulsion (water ~ in-oil) includes! the addition of water, promoters (if not already incorporated by the resin manufacturer), surfactants, sometimes fillers and catalysts to the resin. This includes the water globules being in the form of a uniform dispersion of fine droplets in the resin which are retained within a matrix of the cured resin if the particle size is not carefully controlled. It has also been found advantageous to include in the emulsion a surfactant and / or an aggregate mineral filler to prevent the release of the water which forms part of the present invention easy to effect _e The main variables that affect the molding composition of the invention and drive the invention! are 1.) the resin, 2.) the amount of water, 3 ·) the surface-active agent and / or the fillers, 4 ·.) the catalyst system and 5 ·) the degree of mixing to regulate the particle size of the emulsion. Each of the last four variables is explained in detail below. _s

The catalyst system includes that used by the consumer Promoter and, in a preferred embodiment, the entire curing system contains cobalt octoate, dimethylaniline (DMA) and methyl ethyl ketone peroxide (MEKP). These particular ingredients are preferred because of their low levels Cost, their high strength, their greater safety and because they can be easily dosed and mixed. Other commercially available promoter systems that are equally effective are given below.

The cobalt octoate and DMA are dissolved in the resin and the activated resin is then emulsified and catalyzed.

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Cobalt octoate initiates the decomposition: of the peroxide for hardening of the resin and the dimethylaniline act synergistically forming a quick gel. Although generally about 0.5% DMA based on the weight of the Resin, are used, longer gel times can be achieved by keeping the levels of dimethylaniline up to 0.1%.

A mixture of hydrogen peroxide and a water-soluble methyl ethyl ketone peroxide is also used in this system recommended, although hydrogen peroxide can also be effective on its own. «The catalyst mixture should be recommended be stirred before use and it can be added to the resin composition either by stirring into the preformed emulsion, by injection into the water stream during continuous mixing or by prior dissolution in the water extender can be added. Another curing system that can be used is Benzoyl Peroxide (BPO) and dimethyltoluidine. It has been found that this system provides the most flexible structures (objects) that it is due to however, its flammability is very dangerous. When using it, it is preferable to dissolve the benzoyl peroxide in one a small amount of warm styrene before you do not use it Resin added To complete the catalysis, dimethyltoluidine (DMT), generally in an amount of about 0.5% »based on the weight of the resin, admitted. An amount of 0.3% BPO, based on the weight of the resin, has been found to be satisfactory.

Cure begins following the addition of the catalyst. It is not uncommon for these water-extended resins to develop 75 to 90% of their strength within the first 60 minutes of cure. The exothermic temperatures (peak) are generally within the range from 60 to 93 ⁰ C (140 to 200 ° P) and depend on the

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Water content and its temperature and the type of resin. if it is desired to accelerate the curing, warm water can be used or the emulsion can be a Amine promoter can be added.

However, curing speeds, water temperatures, etc. must be carefully controlled to avoid excessive Avoid exothermicity which could naturally lead to cracked castings.

Before or during the Endkatalysierung the emulsion with (is moderate to high shear conditions thoroughly mixed ₀ result, the water in the above-mentioned very fine droplets is emulsified in such a manner that the water, the surface active agent and the promoter substantially uniformly with the thereon coated resin A stable and uniform emulsion is desired for good results, but in a very important embodiment of the invention the degree of mixing should be carefully controlled. at these speeds, a minimum release of water is in the usual mixing time achieved. If g are, however, decreased the mixing speed to a range between 1000 and-3500 rpm, varying percentages are emitted in water. It must of course be taken into account that the Aufb au of the mixing chamber, the shape of the mixer paddles and the flow rate all affect the final particle size and are therefore determinants of the mixer speed used. Similarly, when other mixing methods are used, the particle size should be appropriately controlled in order to achieve the best overall effect .

The emulsion particle size theoretically effects the desired one

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Water release and this aspect is particularly important to the present invention. Typical emulsions that produce this effect contain a major proportion of particles with a diameter of more than 1.6 ρ (about 0.0016 mm). However, such emulsions also have numerous particles with a diameter of more than 2.6 η (about 0.0026 mm). Minimal water loss is achieved when there is a higher percentage of particles with a smaller diameter. For example, there is minimal loss when most of the particles are less than 1.6 microns (about 0.0016 mm) in diameter and very few exceed 2.3 microns (about 0.0023 mm) in diameter.

As also already indicated, the addition of certain surface-active agents, emulsifiers, wetting agents or surfactants, which are explained in more detail below, represent one of several ways of carrying out the invention. It should also be noted that the water, the promoters and the surfactants are added to the resin and not the other way around. If of course the resin is preactivated and / or the surfactant or other additives in have already been added to an earlier production stage, so this becomes superfluous in this regard, however, be careful pointed out that care must be taken in adding to the resins and mixing in order to avoid the formation of an inverse Avoid emulsion (oil-in-water).

The surfactants have a tendency to release of water from the molding or casting during its hardening to effect and regulate when used alone or in conjunction with elongated mineral aggregates or similar substances can be used. Accordingly, inert, elongated mineral aggregates, such as those for example are available under the trade name Perlite, used to promote the release of water according to the invention will. It is believed that such an aggregate

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BATH ORIGINAL

Has a tendency to promote or support the formation of large particles in the emulsion and thereby create a network structure creates through which the water can escape during and after curing.

The aggregate (aggregate) mentioned is an inert glass-like substance made from a volcanic one Aluminum - magnesium silicate. Although this material breaks the said emulsion, it should be noted that the As such, control of emulsion particle size must be carefully maintained in order to be effective. It is also important to point out that the smaller the size of the surcharge, the more effectively this affects the emulsion particles. size. The typical, thoroughly mixed, stretchable with water Polyester pulp with no added surfactant, aggregate, or similar additive holds the majority of its emulsified water. Indeed, the tissue-like internal structure of the composition appears to be the water droplets to be physically enclosed and held. The surfactant, aggregate, or other emulsion treating material causes the emulsion to break during curing or a reduction in surface tension, so that the water can escape through the net-like structure of the composition.

When used alone, amounts of from about 3 to about 7 percent, based on the weight of the resin, of these surfactants release virtually all of the water originally used to stretch the resin, if the emulsion particle size is properly maintained. From this it can be seen that if the original emulsion contains 50% water, its removal from the finished cast article results in about a 50% reduction in its weight. In order to further support this release of water, it can be advantageous to remove the molded article from the polyester stretched with water after removal from the mold

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treat in an oven. In this cycle hot, in which a temperature of about 52 to 93 ° C is maintained (125 to 200 ⁰ F) after about a period of 12 hours, the maximum amount will be delivered to water. In addition, such a treatment evidently leads to a lessening of the stresses within the molded article and thereby practically eliminates warpage. It is also believed that modifying the hydrophilic-lipophilic balance of the surfactant used also has an impact on the amount of water released.

Of the many surfactants that are commercially available are available, those with a lipophilic nature are most suitable. This of course means that these surface-active Agents are more oleophilic than hydrophilic. For better identification of the surfactants that can be used Means is based on the published surfactant identification system of Atlas Chemical Company, in which these various agents refer to their hydrophilic-lipophilic balance (HLB) are assessed.

The HLB assessment enables the addition or the additional combination, to be emulsified, assign a number and then an emulsifier or an emulsifier mixture with the the same number. The HLB value of an emulsifier or a surfactant is a term for its hydrophilic-lipophilic balance, d. H. the balance between the size and strength of the hydrophilic (or polar) and the lipophilic (or non-polar) groups of the emulsifier · All emulsifiers consist of a molecule that combines both hydrophilic and lipophilic groups. A lipophilic emulsifier has a low HLB number (below 9.0) and a hydrophilic emulsifier has a high HLB number (above 11.0). The values between 9 and 11 represent

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The HLB value of an emulsifier is related on its solubility, so that an emulsifier with a low HLB value tends to be soluble in oil while an emulsifier with a high HLB tends to be soluble in water.

The number itself in this system is only an indication of the percentage weight of the hydrophilic part of the nonionic emulsifier molecule. Now, when a non-ionic emulsifier to 100% would be hydrophilic, it must have an HLB-V / ert 100 comprise, in this system, such a emulsifier would (does not exist), however, a HLB-7 ^«T ert of 20 assigned, whereby the factor 1/5 is introduced for reasons of convenience. The HLB values for most nonionic emulsifiers can be calculated either from their theoretical composition or from the analytical data. For example, the HLB-7 values for most polyol fatty acid esters can be calculated using the formula:

HLB value = 20 (1 - j.) , Where S = saponification number of the ester

A ■ acid number of the acid formed.

In those cases where the hydrophilic part consists only of ethylene oxide

is (polyoxyethylene stearates) is the following formula: ä

HLB value = E / 5, where E = oxyethylene content in percent by weight. ,

In short, the experimental method for determining the HLB value, which is not precise, consists in mixing an unknown emulsifier in varying proportions with an emulsifier with a known HLB value, and the mixture ^: for emulsifying an oil used with a known required HLB value. The most suitable mixture is one that has an HLB value that is approximately equal to the required HLB value of the oil, so that the HLB value of the!

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unknown substance can be calculated. Of the inventively Useful surfactants are the sorbitan fatty acid esters commercially available under the trade name Arlacel from Atlas Chemical Ind., Inc. These, as well as other non-ionic emulsifiers, are chemical suitable and they have HLB values between about 1 and 9. One such surfactant, sorbitan sesquioleate, is particularly well suited for the use according to the invention, which is explained in more detail below.

From the foregoing it can be seen that the present invention not only provides the prior advantages of can be retained with water-stretchable polyester, but that it is now also possible, by controlled removal of the water-extender, the weight depending on the needs of the consumer to vary »

by

The invention is / the following examples explained in more detail, wherein preferred embodiments of the invention are described.

example 1

2 g of benzoyl peroxide are added to a mixture of 65 g of an unsaturated polyester with an acid number of 40, made from maleic acid, phthalic acid and propylene glycol as part of the continuous phase, which is partially deposited at the phase interface, and 35 6 styrene as a monomeric material in the continuous phase added, which acts "as a catalyst for the preparation of the dispersed phase is then slowly 100 cc of water are added · the mixture is stirred vigorously at a temperature of 10 ⁰ C until a water has inr-oil emulsion formed. The emulsion is mixed with 0.18 g of dimethyl-p-toluidine as an activator, poured into a] x ^ m to form a 15 mm thick plate, and then

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cured by 10 minutes of heating at a temperature of 3O ⁰ C. The plates keep at room temperature practically zurücke The water may be composed of the porous plate by heating to a temperature between 80 and 10O ⁰ C are partially removes all trapped in the cellular structure of water.

Example 2

A porous polyester plate is produced according to the process described in Example 1, but this time "5% by weight of the continuous phase of sorbitan sesquioleate is added to the emulsion. The plate thus formed is similar in appearance and structure to the plate obtained in Example 1, but with more than 65 % of the water is released from the cellular structure at room temperature.

Example 3

For comparison, a stretched polyester with water (AROPOL WEP) for casting and shaping, which is available from Ashland Chemical Company, with the amounts indicated below Termischt to form a water-in-oil \ Emulsion:

50 % water-stretchable polyester resin (AROPOL WEP 21) 1.25% cobalt octoate (12%), based on the weight of the resin, 0.50 % dimethylaniline (DMA), based on the weight of the resin, about 50 % water and

0 »50%, based on the weight of the resin, of a methyl ethyl ketone peroxide / water peroxide mixture.

This stretched with emulsified water and catalyzed Resin is then made into a 3 »50 cm (1 3/8 inch) cubic shape poured. After gelling, it is stretched with water

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Polyester resin cube removed from the mold and its weight is about 46 g. The molded cube is then for 24 hours at a temperature of 60 ⁰ G (140 ⁰ F) in an oven accommodated After removal from the oven, the cube is weighed again and he weighs about 44 g _t that is, it has 2 g V / ater lost · The same cube weighs about 42 g after 3 months of storage under indoor atmospheric conditions. · ',

Another water-in-oil emulsion fc is prepared in a corresponding manner, in which the same constituents are again added to the emulsion in the amounts specified for the comparison sample. In this case, however, 5 % Arlacel ™ C (sorbitan sesquioleate, HLB value 5-7) - based on the weight of the resin - which is available from Atlas Chemical Industries Inc., is added to the emulsion. The addition of this surfactant can increase the emulsion viscosity. The emulsified, water-extended, and catalyzed resin is then poured into various cubic shapes about 3 »50 cm (1 3/8 inch) on each side and allowed to gel. The weight of the cube after removal is around 41 g. A molded cube is then (F 140 ⁰⁾ brought ^ for about 24 hours at 60 ° C in an oven ^ and after its removal his weight is about 23 g · This cube weighs approximately 3 months of storage at normal indoor atmosphere conditions, about 23 g . This shows that practically no water is lost after long periods of time. A second molded cube was removed from the mold and subjected to typical indoor atmospheric conditions for 24 hours and was found to weigh about 25 grams. This indicates a water loss of 20 g compared to the cube originally removed from the mold. Each cube formed from the surfactant-containing emulsion has good physical and surface properties. Any cube from which water is removed can also be painted

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absorb both water and solvent based " Example 4

The following ingredients are used to make a water-extended one Polyester emulsion made:

2000 g water-stretchable polyester resin (AROPOL WEP 21) 25 g cobalt octoate (12%)

4 g dimethylaniline (DMA)
2000 g water λ

A 400 g sample of this emulsion is further modified so that it contains 6 g of the surfactant Arlacel ^{V £ y} G (3% based on the weight of the resin) and 1 g of a methyl ethyl ketone peroxide / hydrogen peroxide mixture as catalyst. Two castings of about 150 g and 189 S are cast from this modified emulsion.

After demolding and after about 2 days of storage in indoor atmospheres, the 150 g casting still weighs about 148 g, which means a water loss of 2 g or 3 % .The 189 g casting weighs after demolding and after about 2 days of storage in an oven at 66 ⁰ C (150 ⁰ P) still about 181 g, which corresponds to a water loss of 8 % » f

Example 5

Another 400 g sample of the emulsion described in Example 4 is modified with 8 g of the surface-active agent Arlacel ^ C and two castings with a weight of about 179 g and 187 g are cast. 179 g casting still around 139 g. The 187 g-casting weighs after 2 days of storage in an oven at 66 ⁰ C (150 ⁰ F) for about 96 g. In any case, a considerable amount of

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To determine the weight reduction, that is, a loss of water caused by the use of a surfactant, which is 44 % under room conditions and 98 % under oven conditions.

Example 6

A water-extended polyester emulsion is formed manufactured in the following way:

50 % of a polyester resin which can be stretched with water / water (WEP) 1.25% based on the weight of the resin, cobalt octoate (12 %) 0.50% based on the weight of the resin, dimethylaniline about 50 % water.

This emulsion is made by adding 5 % (based on the weight of the resin) of a surfactant mixture (ie a mixture of 50% sorbitan trioleate and 50 % polyoxylene sorbitan trioleate with an HLB value of about 6.5), which is 0.50% ( based on the weight of the resin) are added to a methyl ethyl ketone peroxide / hydrogen peroxide catalyst mixture, further modified. In this case about 65 to 75 % of the water added to the emulsion is released during and after the gelling of the compound.

Example 7

An emulsion which corresponds to the emulsion prepared in Example 6 is made with 4% of the detergent JOY® (HLB value about 14) and 2 % of a methyl ethyl ketone peroxide / hydrogen peroxide-Mi-. schung, each based on the weight of the resin, modified. After demolding, the samples lose between 30 and 50 % of water, depending on the subsequent storage conditions.

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250 G G 3.1 S. S. 0.5 S. 12.5 S. 12.5 G 250, 1.25

Example 8

It becomes a catalyzed emulsion composed of the following ingredients manufactured:

Ashland Chemical Co. WEP 21 liobaltoctoat (12%) (1.25 ° / ° <ies weight of the resin) of dimethylaniline (0.2% of the weight of the resin)

Atlas Chem. Ind. Arlacel ^ C (5 % of the weight of the

Resin)

Styrene monomer (5% of the weight of the resin) water

a methyl ethyl ketone peroxide / hydrogen peroxide mixture (0.5% of the weight of the resin).

The addition of the styrofoam monomer leads to a viscosity of the emulsion of about 27 seconds, as a result of which its casting properties are improved. There are cast castings with a weight of • about 200 g and allowed to gel "After removal from the mold is one of these castings long stored for one day in an oven at 66 ⁰ C (15O ⁰ J ^1), then, the casting still weighs about 97 ge After a corresponding 1-day storage under indoor atmospheric conditions, a second casting still weighs about 146 g.

Example 9

A catalyzed emulsion is made from the following ingredients:

200 g 32-177 Polylite ® polyester resin (activated) der Reichhold Chemicals Inc.

10 g Arlacel ^ C of Atlas Chem. Ine · 200 g of water

4 g methyl ethyl ketone peroxide.

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This emulsion is poured into various shapes and allowed to gel for about 14 minutes. After removal from the mold, two of the polyester resin castings stretched with water weigh about 161 g and 175 g, respectively Oven at 66 ⁰ C (150 ⁰ P) still weighs about 86 g.

Example 10

An emulsion is made similar to Example 9, but this time using 32-178 Polylite ™ polyester resin. Different castings are poured and allowed to gel for about 4 minutes. After about 3 days of storage in an oven at etv / a 66 ⁰ C (150 ⁰ F) weighs 171 g-casting still about 89 g. After about 3 days of storage under indoor atmospheric conditions, a “180 g casting still weighs about 150 g.

Example 11

Samples similar to those in Example 3 are prepared, one batch (A) contains about 5 % Arlacel ^vy and a second batch (B) is free from this additive. The following mixing conditions are observed for the parts of each batch, with the following results being obtained:

Batch A

1.) Mixer speed about 2500 rpm, mixing time about 1 minute
Water loss about 95%

2.) Mixer speed about 4000 rpm Mixing time about 1 minute
Water loss about 60 %

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~ 23 -

3o) Mixer speed about 5500 rpm Mixing time about 1 minute
Water loss about 30 %

Batch B

Appropriate mixer speeds and mixing times are used, in each case there will be little or no Detected water loss.

Example 12 - (

Two batches A and B of catalyzed emulsions are made from the following ingredients:

1418 g (50.0 ounces) (50%) of a water extensible Polyester resin (AIiOPOL WEP 21)

17, S5 S (0.63 ounces) (1.25%) cobalt octoate (12 %) 7.1 g (0.25 ounces) (0.5%) dimethylaniline (DMA) 2.8 g (0.1 ounces ) (0.2 %) of a 20% solution of hydroquinone

in methylcellosolve
1418 g (50.0 ounces) (50%) water

71 g (2.5 ounces) (5%) perlite * (PA-130) Batch A |

28.35 S (1.0 ounces) (2 %) perlite * (PA-130) Lot B

Each batch is hand mixed and weighs approximately 7.1 grams (0.25 ounces) (0.5%) methyl ethyl ketone peroxide catalyzed » Then v / ground Batches A and B to about 58 cm (23 inch) long board-like objects weighing about 1162 g (2 lbs. 9 ounces) are cast The object is cut about in the middle to have comparable cross-sections for storage in the oven and for Maintain room temperature · They show the following water losses per cross-section:

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24 hours 48 hours 72 hours 5% perlite (130), 52 ⁰ C (125 ⁹ F) 27.5 %
Room temperature 12.5

2 % perlite (1JO), 66 ⁰ C (15O ⁰ F) 18.6 room temperature 9 »3

Example 15

35 % 42.5% 17, 5 17.5 20, 9 27.9 9, 3 11.7

To determine the influence of a combination of perlite and Arlacel C on a water-stretched polyester material, the following standard emulsion is made:

50% of a water-stretchable polyester resin (AROPOL WEP 21) 1.25 % cobalt octoate (12 %)
0.2% dirnethylaniline (DMA)

0.1% inhibitor (20% solution of hydroquinone in methyl

cellosolve)

50 % water

The various batches are catalyzed with 0.5% methyl ethyl ketone peroxide and for those containing Arlacel C it is added to the resin, while for those containing perlite (i.e. PA-2 *, which has a 0 mesh sieve) it is added to the resin is 42 mm (40 mesh)) happens in the catalyzed emulsion blended * All percentages are based on the weight of the resin based "Each of the different batches prepared sample is exposed after gelling a furnace atmosphere of about 66 ⁰ C (15O ⁰ F). Batch and Sample A contain 5% Arlacel C Batch and Sample B contain 1 % Perlite Batch and Sample C contain 2 % Perlite Batch and Sample D contain 1 % Perlite and 1% ArlacelC Batch and sample E contain 1 % perlite and 2 % ArlacelC the batch and sample F contain 2 % perlite and 1 % ArlacelC the batch and sample G contain 2 % perlite and 2 % ArlacelC

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104.3 - - 15.7 18.3 20.3 20.9 23.5 25.5 14.3 18.4 18.4 12.3 14.4 17.5 22.6 25.7 27.2 18th 22.6 22.2

Water loss in%

Sample 24 hours' 48 hours 72 hours

A B C D E F G

A control sample that contains neither Perlite nor Arlacel shows a water loss of 11.1% after 24 hours, 14.1% after 48 hours and 16.2% after 72 hours _o

* PA-2 and PA-I30 are volcanic silicates produced by the

• Available from Coralux Perlite Corporation of New Jersey are. The density of these materials is between about 0.056 and 0.16 g / ccin (3.5 to 10 lbs / ft. ^) And the particle size distribution of this material is the following:

Tyler standard sieve

clear mesh size in mm PA-2 PA-130 2.35 (8 mesh) • Mt 1.0 (16 ") 12% traces 0.84 (20 ") 23 % 10% 0.55 (30 ") 30 % 9% 0.28 (50 ") d? / 0 40 % 0.15 (100 ") 4% 32% as above, 0.15 (100 mesh) 5 % 15% Example 14

A polyester stretched with water is used for comparison (Aropol WEP) for casting and molding available from Ashland Chemical Company in the amounts indicated

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used to produce a water-in-oil emulsion:

50 % of a water-stretchable polyester resin (WEP-21) 1%, based on the weight of the resin, cobalt octoate (12%) 0.55 % y based on the weight of the resin, dimethylaniline (DMA)

0.35 % Lupersol DSW (from Lucidol Div.-Wallace & Tiernan Co.) based on the weight of the resin

0.50%, based on the weight of the resin, methyl ethyl ketone peroxide

The substances mentioned above are without the methyl ethyl ketone using an air motor by hand; mixed until a good emulsion is obtained «, to check the number of revolutions A tachometer can be used while mixing. After emulsification, photomicrographs are taken of a sample of the emulsion and the other samples are catalyzed to study water loss. The photomicrographs are taken at about 1160X which is obtained by photographing a standard scale. Then the particle sizes are determined using a graduated eyepiece magnifier and the percentage is determined the particles in the different size ranges are made by counting.

The mixed at about 2 rpm 5OO comparative emulsion has particle sizes within the range of 0.3 to 0.5 microns and in the furnace at a temperature of etv / a 71 ° C (160 ⁰ P) sample held shows after 48 hours only a Water loss of about 5% by weight.

A corresponding emulsion mixed at about 2500 rpm and containing about 4.5 % Arlacel 0, based on the weight of the resin, has a donut-like structure and has a particle size distribution within the range of about 1.0 to 2.6 microns « The weight loss after storage for 48 hours in an oven at 7 * 1 ⁰ C (160 ⁰ P) is again about

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5%. It is determined that greater than 60 % of the particles are less than 1.6 microns in size, that less than 40% of the particles are greater than 1.6 microns, and that less than 15% of the particles are greater than 2.3 Microns are.

Example I5

A dosing and mixing unit for a water-extended polyester (model 951-919) commercially available from the company Gray Company Ine · is available using modified mixer blades for the production of a water-in-oil emulsion used from the following components:

50 % of a water-stretchable polyester resin (Aropol 21) 50 % water

5.0%, based on the weight of de3; Resin, Arlacel ^ C,

2.0%, based on the weight of the resin, promoter B * for the Resin Aropol WEP

0.4%, based on the weight of the resin, catalyst * for Aropol WEP resins

* These systems are commercially available from Ashland Chemical Company.

This device provides an emulsion under the specified conditions (2.41 to 3.81 kg / cm (20 to 40 psig) at the pumps) which, when poured and cured, released virtually all of the water present in the original emulsion casting to preheat the molds to a temperature of about 38 ° C (100 ⁰ F) "After the molding or casting the emulsion, the molded articles are for about 4 hours in an oven at a temperature of about 93 ° C (200 ⁰ F ) treated to accelerate the expulsion of the water from it. It turns out that these objects then have good physical properties and good surface properties, which make them very receptive to painting.

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Claims (1)

Claims 1. Thermosetting molding compound used for casting objects is particularly suitable, characterized in that it is an unsaturated, water-stretchable polyester resin and 3 to 7% by weight, based on the weight of the resin, of a surfactant Contains agents having an HLB value between about 1 and 9, the surfactant having the property has, after activation, after stretching, emulsification and catalysis, to produce such particle sizes in the molding compound, that the water extender used is easily released from the molded article after molding. 2. Thermosetting molding compound, which ι for casting objects is particularly suitable, characterized in that it is in the I. essentially of an unsaturated, water-stretchable j Polyester resin, a promoter from the group dimethyltoluidine \ and cobalt octoate and dimethylaniline and a surface! active agent with an HLB value between about 1 and 9, the surfactant having the property of activating, stretching, emulsifying and catalyzing in the; ! To produce molding compound such particle sizes that the water extender used can easily be removed from the | molded article is released. 3. Molding composition according to claim 2, characterized in that they 25 to 90 wt .-% water, based on the weight of the! Molding compound contains. j 4-, molding compound according to claim 3, characterized in that they use benzoyl peroxide as a catalyst. a methyl ethyl ketone peroxide / hydrogen peroxide mixture or contains hydrogen peroxide 5 · Molding composition according to claim 2, characterized in that it contains the surface-active agent in an amount within the Range from about 3 to about 7 weight percent based on weight 109821/2246 of the water-stretchable polyester resin, contains, 6. Molding composition according to claim 2, characterized in that it also contains monomeric styrene. 7. Molding composition according to claim 2, characterized in that the surface-active agent is non-ionic and a compound from the group consisting of sorbitan sesquioleate, trioleate, monooleate and monolaurate. 8. A thermosetting molding composition, characterized in that it ί essentially of an unsaturated stretchable water-polyester resin of cobalt octoate and dimethylaniline, as well as a nonionic surfactant having an HLB value between about 1 and 9, wherein the surfactant has the characteristic has, after activating, stretching, emulsifying and catalyzing the molding composition to produce particle sizes such that the water extender used is easily released from the molded article after molding. 9. Molding composition according to claim 8, characterized in that it contains sorbitan sesquioleate as a surfactant. G 10. Molding composition according to claim 8, characterized in that it also has a methyl ethyl ketone peroxide / hydrogen peroxide mixture contains » 11. Molding composition according to claim 8, characterized in that it contains the surfactant in an amount within of the range from about 3 to about 7 wt .-%, based on the Weight of the water-stretchable polyester resin. 12. Thermosetting molding compound suitable for casting characterized in that it consists essentially of an un- 1 0982 1/2246 ^BAD original ~ 30 - saturated, water-stretchable polyester resin, a Promptor from the group of dimethyltoluidine and cobalt octoate and dimethylaniline, a nonionic surfactant having an HLB value between about 1 and 9 and one There is aggregate filler, wherein the surfactant and the aggregate filler have the property after Activating, stretching, emulsifying and catalyzing the molding composition to produce such particle sizes that the used Water extender is easily released from the molded article after molding. 13. Thermosetting molding compound which is suitable for casting or molding objects, characterized in that it an unsaturated water-stretchable polyester resin and an additive for breaking an emulsion with the same Property and contains a sufficient amount so that after activation, emulsification and catalyzing in the Molding compound such particle sizes are produced that the water extender used after molding from the molded Object is easily released. 14. Activated, emulsion-extended, and catalyzed thermosetting Molding compound suitable for casting objects and containing a polyester resin that can be stretched with water, characterized in that the majority of the emulsion particles have a size within the range of about 1 to about 4.5 microns. 15. Molding composition according to claim 14, characterized in that they use water as the stretching material in an amount between about 25 and about 90%, based on the weight of the molding compound, contains. 16. Molding compound according to claim 13 »characterized in that use them as a finely divided additive to break the emulsion 109821/2246 contains inorganic mineral aggregate the major part of which has a particle size of 0.33 mm or more (50 mesh). 17 · Molding process, characterized in that a) a water-extensible polyester resin, water and a suitable catalyst are mixed together to form an emulsion in which a major proportion of the particles have a size within the range of about 1.0 to about 4.5 microns and g b) the catalyzed emulsion before its gelation in a Introduces shape so that a suitably shaped article is formed. j 18. Molding process, characterized in that one a) a water-stretchable polyester resin, a promoter, and a catalyst therefor, a surfactant and water mixes together to form a Emulsion in which a major proportion of the particles have a size within the range of about 1.0 to about 4.5 Micron and % b) the catalyzed emulsion before its gelation in a Introduces shape so that a suitably shaped article is formed. Molding method according to claim 18, characterized in that that the gelled article is heated to help remove the water therefrom. 20. Molding method according to claim 18, characterized in that about 3 to about 7 wt .-% of a non-ionic in the emulsion 109821 / 22Λ6 ~ 52 - surfactant based on the weight of the resin; and 25 to 90 weight percent water based on the weight the molding compound, are incorporated. 21. Molding method according to claim 19, characterized in that ni
(120 to 210 ⁰ F) is heated. that the object is at a temperature of about 49 to 99 ° 0 22. Molding process, characterized in that one with a) a / water stretchable polyester resin, a promoter for this and water mixes with each other to form an emulsion in which a larger proportion of the particles one Has size within the range of about 1.0 to about 4.5 microns, b) adding a suitable catalyst to this emulsion and mixed with _c) the catalyzed emulsion in an appropriate manner introduces manufactured form and allows the emulsion to gel to form an article, d) removing the gelled object from the mold and e) The object is heated in order to remove the water from it to support. · 23. The method according to claim 18, characterized in that the promoter is dimethyltoluidine or cobalt octoate and dimethylaniline and the non-ionic surface-active Means sorbitan sesquioleate, trioleate, monooleate or monolaurate used. 24. The method according to claim 23, characterized in that one 109821/2246 of the emulsion from about 3 to about 7 weight percent surfactant
Means based on the weight of the water extensible
Polyester resin, added 25 · The method according to claim 22, characterized in that a non-ionic surface-active agent or a mineral additive with the ingredients mentioned in step 1 mixed. 109821/2246 ORlQlNAL INSPECTED