DE2540618A1 - ADDITIVES TO MOLDING COMPOUNDS BASED ON THERMAL CONDENSATION RESINS FOR THEIR SHAPING PROCESSING - Google Patents

Description

Neynaber Chemie GmbH 285 ¹ I Loxstedt, December 9, 1975

dr.ans-sü P.O. Box 1120

Patent application D 5174

"Additives for molding compounds based on thermosetting condensation resins for their shaping processing "

The invention relates to reactive additives to molding compositions based on thermosetting condensation resins for their shaping processing with a content of reaction products of amino-substituted aromatic compounds with epoxyalkanes and / or carboxylic acids.

Thermosetting molding compositions contain, as essential components, binders, which are exposed to the effect of heat and Can be crosslinked under pressure with polycondensation. The most important binders are pre-dosed resins, either phenolic resins of the resole or novolak type obtained by condensation of phenol, cresols, xylenols, naphthols or polyhydric Phenols with formaldehyde, polymeric formaldehyde or other aldehydes, or aminoplast resins, obtained by Condensation of urea, guanidine, substituted ureas, melamine, substituted melamines or aniline with Formaldehyde, polymeric formaldehyde, furfural or other aldehydes. A molding compound can also contain various binders contain side by side, 2. B. a phenolic resin novolak and a melamine-formaldehyde resin.

In addition to the characteristic binders, hardenable molding compounds also contain crosslinking agents such as hexamethylenetetramine, Hardening accelerators such as magnesium oxide, fillers such as chalk, asbestos, cellulose or wood flour, pigments, plasticizers, Stabilizers and lubricants.

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Sheet 2 for patent application D 5174 2 5 H O 6 1

The lubricants are of decisive importance for the processability of thermosetting molding compounds. In the shaping processing by pressing, transfer molding or injection molding, they should. improve the flow of the masses to ensure proper mold filling. In addition, they have the task of facilitating the removal of the cured finished part from the mold, thus making the cumbersome treatment of the mold with an external mold release agent superfluous. The interaction of improved flowability and internal mold release effect should help the finished parts to have a closed and smooth surface.

With the aim of a homogeneous distribution, the lubricants are expediently already used during the manufacture of the resins, at the latest but added in the preparation of the molding compounds to molding powders, chips, granules or tablets, for sticking the masses and premature hardening on preparation rolling mills, granulating extruders or tablet presses to prevent.

So far, stearic acid and other fatty acids, metallic soaps made from fatty acids such as Calcium stearate, zinc stearate, magnesium stearate and aluminum stearates different basicity and natural waxes such as beeswax or carnauba wax, synthetic Waxes such as montanic acid ester, cetyl palmitate, stearyl stearate or ethylenediamine di-stearate, paraffin waxes of various kinds Origin, mineral oils and tar oils used.

The lubricants previously used or proposed are unable to fully satisfy. This is especially true when all stages of resin production, molding compound preparation and shaping processing are taken into account. This is the case with the lubricants mentioned difficult to achieve proper distribution in the molding compound. This is especially true when the precondensed Resins are obtained in the form of an aqueous solution or dispersion. The hydrophobic character of the mentioned lubricants

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Sheet 3 for patent application D 5174

then prevents even distribution. A use of hydrophilic lubricants, such as. B. ÄO adducts aliphatic Mono- to polyfunctional alcohols or their carboxylic acid esters result in good distribution in the Molding compound, but the use in higher doses leads to exudation from the molded part during the hardening reaction. One tries to reduce the disadvantages of exudation during the pressing process by adding low amounts used by lubricants, their influence on the flowability of curable molding compounds is no longer sufficient, in order to avoid premature hardening due to priiction heat, especially in injection molding processing.

Another disadvantage of the lubricants used hitherto is that they are sufficient to form a Mold release effect must experience an enrichment on the surface of the pressed part, which is caused by the deformation applied pressure is generated; This brings about a good demolding that is enriched on the surface However, lubricant is not fully ejected with the compact. Rather, it leaves behind on the surface of the Metal molds Residues that accumulate in the course of many successive pressing processes, causing dimensional changes the molds and thus the pressed parts. It is particularly disadvantageous that these lubricant residues are thermally cracked in the metal mold and therefore strong discoloration in the production of light-colored pressed parts cause.

So far it has not been possible to meet all processing requirements with one lubricant. The metal soaps of fatty acids cause the best mold separation, but their influence on the melt viscosity is particular Too low for plasticization during injection molding. Attempts have also been made by combining several

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Sheet 1} for patent application D 5: 17 * 1 20hUu I Q

Lubricant, ζ. B. of metal soaps and mineral oils, various To unite effects. However, this added to the already existing difficulties in tolerability of the individual lubricants nor their mutual displacement effects.

As can be seen above, it has not There is a lack of attempts at shaping processing thermosetting condensation resin molding compounds occurring Difficulties to cope with. Despite all efforts, this task has so far not been more satisfactory Way to be solved.

It has now been found that the disadvantages outlined above can be avoided if one for the shaping Processing of molding compounds based on thermosetting condensation resins, additives used, which are marked by a content of compounds of the formula, 2

- CHX - O ^ -jpY, (I)

1 2
in which R and R are identical or different and are hydrogen, methyl, methoxy,

R ³ R ^{3 p3}

N -, ^ N- ('> - or "N - <' ^x > - CH ₉ - group

represent, R ^{3 is} a methyl, phenyl or Z 4- 0-CHX-CH ₅ -j

* - ^c ^ m

A radical means X is hydrogen and / or an alkyl group with 1-26 carbon atoms, Y and Z are hydrogen or an R CO radical are, where R is a hydrocarbon radical with 12-26 Denotes carbon atoms, and the sum of η and m can assume values from 0 to 100, with the proviso that at least one of the radicals Y and Z is an R CO group,.

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Satt 5 for patent application D 5174 ^ OhUü | Q

when η is less than or equal to 10 and X is hydrogen or a Are alkyl radical with 1-9 carbon atoms, and that the compounds of formula I are at least one unsubstituted contain ortho or para position.

For the preparation of the additives according to the invention, for example, the following aromatic compounds are used by substituted amino groups containing free hydrogen atoms are used:

Aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, s-triaminobenzene, methylaniline, diphenylamine, benzidine, ^, V-diaminodiphenylmethane or as-dimethyl-p-phenylenediamine.

In addition to ethylene and propylene oxide, there are also 1,2-epoxyalkanes with 4-26 carbon atoms such as 1,2-epoxybutane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxypentadecane, 1,2-epoxyoctadecane and 1,2-epoxytetracosane. But it can also be used 1,2-epoxyalkane mixtures were prepared by processes known per se from commercially available olefin mixtures. Such mixtures of olefins can obtained for example by the aluminochemical method according to Ziegler will.

The acid component of the compounds to be used as additives according to the invention are, for example, from the fatty acids available from natural fats and oils such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and fatty acid mixtures such as stearic acid-palmitic acid mixtures, Tallow fatty acid and coconut fatty acid mixtures, also branched-chain carboxylic acids such as Isopalmitic acid or isostearic acid and substituted Fatty acids such as phenylstearic acid, hydroxystearic acid or ricinoleic acid are possible.

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Additives of the formula I according to the invention are, for example: aniline · 18 XO, aniline · 5 XO · 13 PO, aniline · 32 XO, aniline · 10 PO, aniline · 66 XO, aniline · 33 XO · 33 PO, aniline · 32 XO monostearic acid ester , Aniline 1,2-epoxydodecane, phenylstearic anilide, o-toluidine 100 PO, p-toluidine isostearic anilide, p-phenylenediamine 70 XO, p-phenylenediamine 30 XO HO PO, o-phenylenediamine 2 PO-monolauric acid ester, as- Dimethyl-p-phenylenediamine linoleic anilide, benzidine · 14 XO · 8 PO-distearic acid ester, benzidine-tetracosanoic acid anilide, 4,4'-diaminodiphenylmethane monostearic acid anilide, 4, V-diaminodiphenylmethane diisopalmitic acid anilide and 4,4'-diaminodiphenyl methane. 60 XO.

Of the compounds of the formula I, particularly advantageous lubricants according to the invention are, on the one hand, the addition products from II to 100 mol, preferably 40 to 70 mol, of ethylene oxide and / or propylene oxide to amino-substituted ones aromatic compounds, preferably aniline, and on the other hand the anilides of 1-2 moles of a carboxylic acid with 14-20 Carbon atoms with amino-substituted aromatic compounds, in particular with 4,4'-diaminodiphenylmethane or as-dimethyl-p-phenylenediamine.

The additives according to the invention are added to the molding compositions to be processed or the resin dispersions in an amount from 0.1 to 10 percent by weight, preferably 0.2-3 percent by weight, based on the total mass of the condensation resin, added. The means cause even with very small amounts added, z. B. 0.1 weight percent, good flowability and mold release and show advantageously even at relatively high added amounts in contrast to the known processing aids have no adverse effects on the nature of the molded products.

The decisive advantage of the lubricants according to the invention is their ability to react with the components of the resin mixture under curing conditions for thermosets and am Becoming part of the thermoset resin itself at the end of the hardening process. Because of this, they also show

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Sheet 7 for patent application D 51721 2 5 40

With a high dosage, no exudation during shaping processing and when using the finished part. However, the lubricant properties of the new additives are retained until the final hardening.

The new additives can already be used during manufacture the binder, i.e. the phenol novolak, phenol resole, urea-formaldehyde condensate or melamine-formaldehyde condensate can be added. They then partly take part in the condensation reactions and become part of the precondensates bound or in turn form reactive methylol compounds. Because of these reactions, a Excellent compatibility of the additives in the resin batches. Even with the resin condensation in aqueous Solution, as is customary with urea or melamine-formaldehyde molding compounds, ensures perfect homogenization.

However, the products according to the invention can also be used in any processing stage after the resin has been produced are added to the molding compounds, for example when kneading aqueous urea or melamine-formaldehyde resin solutions with cellulose, when grinding aminoplast molding compounds in the ball mill, when rolling aminoplast molding compounds or when mixing the new additives with powdered)! Phenol novolak fillers and other additives before granulation in a twin screw system. Such interfering procedures are considerably facilitated to see that the new means include liquid products and solids with graded melting points, so that additives with optimal properties can be selected for each process.

The new lubricants lead in the preparation stages of thermosetting molding compounds based on condensation resins to make work considerably easier. They prevent the masses from sticking to or on kneader blades Mixing rollers and thus enable trouble-free input

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Sheet 8 for patent application D 517I1 254061Q

processing of fillers; In addition, because they are tack-free, they switch premature curing to thermally overloaded conditions Molding mass fractions.

A new possibility of incorporation which can be used for the additives according to the invention is that the agents be used in the form of their reaction products dispersed in water with formaldehyde. The additives are precondensed to methylol compounds. Since this is carried out in the aqueous phase, one obtains as precursors aqueous dispersions of the additives according to the invention in the form of their methylol compounds. These can be especially easily with the resins also present in aqueous dispersion or solution ■ such. B. melamine-formaldehyde precondensate ions, mix.

When used for shaping, the additives according to the invention develop an excellent internal lubricating effect, by reducing the viscosity of the melt. This results in better filling of the mold, more precise dimensional accuracy and increased freedom from internal tension. In addition, the absence of tack, known as the external sliding effect, prevents the new additives sticking the cured pressed parts to the mold surfaces, so that the pressed parts trouble-free can be demolded.

The following examples are intended to explain the subject matter of the invention in more detail without, however, restricting it thereto.

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Examples
A) Manufacturing

example 1

93 »1 g (1 mol) of aniline and 20 ml of 30% sodium methylate solution were placed in an autoclave with a stirrer. The autoclave was flushed with nitrogen and then evacuated ^{at approx. 70 ° C. for 10 minutes.} The mixture was then ^{heated to 150 °} C. and 2904 g (66 mol) of ethylene oxide were added at this temperature. The result was a light-colored, solid product A which was perfectly flaked with a flaking roller. Melting point: 59 ° C, cloud point of the 5% solution (NaCl) approx. 97 ° C, OH number: 31.

The following products were manufactured in the same way:

Product compound m.p. (° C) OH number

B - aniline -32 EO C aniline · 5 EO · 13 PO

D ■ 4,4 ^f -diaminodiphenylmethane · 30 ÄO

Example 2

In a three-necked flask equipped with a stirrer I501 g (1 mole) of the adduct of 32 mol of ethylene oxide with 1 mole of aniline, 284 g (1 mole) of stearic acid and 18 g of p-toluenesulfonic acid at l80 ° C - heated 190 ⁰ C until a total of ca. 18 g of water were deposited. After cooling, a solid, waxy product E was obtained. Melting point: 55 ° C, OH number: 34.

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56 52 fluid 117 49 102

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Example 3

In a three-necked flask equipped with a stirrer, 198 g (1 mol) of 4, V-diaminodiphenylmethane and 2QH g (1 mole) of stearic acid at a temperature of 200 ° - reacted 25O ⁰ C, was, until the deposition of the water of reaction terminated. The product F obtained has a melting range of 143 ° - 15O ⁰ C.

The following products were also manufactured in the same way:

Product compound m.p. ( ⁰ C) "

G Lauric anilide 76 - 78 H- Palmitic anilide 88 - 90 I stearic anilide 92-95

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B) use

Example 4

In a high-speed mixer, phenolic resin molding compounds of the following composition (in parts by weight) were prepared to give a powdery consistency:

Mass 1: 45 »5 parts by weight of phenol-formaldehyde resin

4.5 "hexamethylenetetramine 50.0" wood flour 1.0 "magnesia

Mass, 2: 101.0 parts by weight of mass 1

1.0 "zinc stearate

Mass 3: 101.0 parts by weight of mass 1

1.0 ". Substance A (reaction product of 1 mol of aniline and 6.6 mol of ethylene oxide)

Mass 4: 101.0 parts by weight of mass 1

1.0 "substance F (reaction product of 1 mol 4,4'-diaminodipheny! Methane and 1 mole of stearic acid)

All measurements were made in a "Brabender Plastograph" tested for their flow behavior, with the following conditions

were complied with:

Kneading chamber with a 30 cm volume and a jacket temperature of 120 ⁰ C, feed rate 28 g, paddle speed 30 rpm.

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The kneading diagrams of drawing 1 can clearly be seen that by using the inventive Substances the level of the kneading resistance of the mass due to the lubricating effect is lowered.

Example 4

In order to demonstrate the compatibility of substances A and F in phenolic resin compositions, the 4 molding compositions No. 1-4 press plates produced at curing temperatures of 170 ° C. The plates using mass 1 (without lubricant), 3 and 4 (with lubricants according to the invention) showed no deposit formation whatsoever, but showed the press plate using Compound 2, strong deposit formation due to exudation of the zinc stearate.

Example 5

Melamine resin molding compounds were mixed in a high-speed mixer the following composition (in parts by weight) prepared in powder form:

Mass 5 x 60 parts by weight melamine resin powder 40 "chalk

Mass 6: 100 parts by weight of mass 5

1 "zinc stearate

Mass 7-100 parts by weight mass 5

1 "Substance A (reaction product

from 1 mole of aniline and 66 moles of ethylene oxide

Mass 8: 100 parts by weight of mass 5

1 "Substance E (reaction product

from 1 mol of aniline, 32 mol of ethylene oxide and 1 mol of stearic acid)

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The ¹ l compositions were tested for their flow behavior in a "Brabender Plastograph", the following conditions being observed.

Kneading chamber with 30 cm fit and a jacket temperature ^
number 20 rpm.

temperature of 135 ° C, feed quantity 32 g, blade rotating

The kneading diagrams in drawing 2 clearly show that the substances according to the invention have the kneading resistance lower due to their lubricating effect.

Example 6

To ensure the compatibility of substances A and E in melamine * - Resin masses were detected by the 4 molding masses No. 5 ~ 8 press plates at curing temperatures of 160 ° C manufactured. The plates using mass (without lubricant), 7 and 8 (with inventive Lubricants) "showed no deposit formation, however, the press plate using compound 6 showed strong Formation of deposits due to exudation of the zinc stearate.

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Claims (6)

Claims 1. Additives to molding compounds based on thermosetting condensation resins for their shaping processing, characterized by a content of compounds of the formula - CHX - Y, (I) 1 2 in which R and R are identical or different and are hydrogen, methyl, methoxy, N -, or Represent group, R a methyl, phenyl or ) -CHX-CH, The remainder is, X is hydrogen and / or is an alkyl group with 1-26 carbon atoms, Y and Z are hydrogen or an R CO radical, where R is a Hydrocarbon radical with 12 - 26 carbon atoms, and the sum of η and m values from 0 to 100 can assume, provided that at least one η
of the radicals Y and Z is an R CO group if η is less than or equal to 10 and X is hydrogen or an alkyl radical having 1-9 carbon atoms, and that the compounds of the formula I contain at least one unsubstituted ortho or para position. 2. Additive according to claim 1, characterized by a content of compounds of the formula I, produced by the addition of 11-100 mol, preferably ¹ IO -70 mol, of ethylene oxide and / or propylene oxide onto aniline. ORIGINAL INPEQTED 709812/1034 Blatte5 for patent application D ^ iJ I ^ 2 SA 0 S 1 S 3. Additive according to claim 1, characterized in that it contains compounds of the formula I by reacting 4,4'-diaminodiphenylmethane and 1-2 moles of a carboxylic acid with 14-20 carbon atoms. 4. Additive according to claim 1, characterized in that it contains compounds of the formula I by reacting as-dimethyl-p-phenylenediamine and 1 mole of a carboxylic acid with 14-20 carbon atoms. 5. Use of the additives according to claim 1 in an amount of 0.1-10 percent by weight, preferably 0.2-3 Percentage by weight, based on the total amount of the condensation resin. 6. Use of the additives according to claim 1, characterized characterized in that the agents are used in the form of their reaction products with formaldehyde which are dispersed in water will. - 16 - 709812/1034