DE2361909A1 - ANTI-RELEASE AGENT FOR FILLING MATERIALS IN HARDABLE LIQUID CASTING RESIN MIXTURES IN THEIR COMPONENTS - Google Patents

Description

Fr / Pk 509 Leverkusen. Bayerwerk

Dec 12, 1973

Anti-settling agent for fillers in curable liquid cast resin mixtures or in their components

The invention relates to agents that prevent the settling of solid insoluble additives such as fillers and pigments in curable liquid casting resin mixtures or in the components of the liquid casting resin mixtures delayed or prevented .

Curable liquid casting resin mixtures containing fillers and / or pigments or the components of the casting resin mixtures often show the disadvantageous phenomenon of settling of the solid additives after a relatively short period of time Storage times, especially if the casting resins or their components are of low viscosity. The withdrawal symptoms can lead to solid sediments in the containers that cannot be removed by stirring. Fillers or pigments are cast resin compounds to reduce the volume shrinkage, the reduction of the flammability, the Reduction of material costs to increase hardness

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and thermal conductivity, to reduce the temperature increases that occur inside large castings during hardening, for coloring the castings, etc. added.

It is known, flowable epoxy resin compositions containing fillers 0.5-30% by weight of a polyepoxy polyhydroxy ether from diglycidyl ethers of polyhydric phenols and polyhydric phenols which, in addition to epoxy groups, contain hydroxyl groups contain to add to reduce the settling rate of the dispersed pigments or fillers. A disadvantage this process is based on the fact that these additives are only effective in relatively highly viscous epoxy resins. (Cf. U.S. Patent 3,352,809). Another disadvantage lies in the high viscosity of these additives.

The object of the present invention was to find means which prevent or reduce the settling of solid, insoluble additives such as fillers, pigments, etc. ⁱⁿ liquid casting resin mixtures or their components so that the solid, insoluble additives are easily distributed evenly again by simple stirring can, ie that no coherent, solid, immovable sediment is formed. The agents should be of a relatively low molecular weight and represent low-viscosity liquids or, in the case of solid agents, have a low melt viscosity. In addition, the agents should not adversely affect the properties of the moldings produced from the casting resins.

The object was achieved in that the liquid casting resin mixtures or the components of the casting resin mixtures Stearyl or oleyl (i.e. 1-octadecane or 1-cis 9-octadecene derivatives such as stearylamines, stearic acid, stearyl alcohol, metal stearates etc. or oleylamines, oleic acid, oleyl alcohol, Metalloleates, etc. may be added.

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The invention thus provides anti-settling agents for solid, insoluble additives in curable liquids Cast resin mixtures or the components of the cast resin mixtures, characterized in that as anti-settling agents 1-octadecane or l-cis-9-octadecene derivatives are used will.

1-Octadecane derivatives (stearyl derivatives) are preferred. Examples of 1-octadecane derivatives are: stearic acid, mono-, di- and trivalent metal stearates Metals such as alkali metals, Na, K ,. Li; Alkaline earth metals such as Mg, Ca; of Zn, Pb, Cu and Al; Stearyl alcohol; Alkyl stearates with 1-18 carbon atoms in the unbranched alkyl radical, sterylamine, alkylstearylamines with 1-4 carbon atoms in the unbranched Alkyl radical, distearylamine, tristearylamine, stearon, stearic acid amide. Preference is given to sterylamine, N-methylstearylamine, Distearylamine, tristearylamine, stearyl alcohol are used.

Examples of l-cis-9-octadecene derivatives (oleyl derivatives) are listed: oleic acid, metalloleates of mono-, di- and trivalent metals as mentioned for the stearyl derivatives, Oleyl alcohol, alkyl oleates with 1-18 carbon atoms in the unbranched Alkyl radical, oleylamine, alkyloleylamines with 1-4 carbon atoms in the unbranched alkyl radical, dioleylamine, dioleyl ketone, oleic acid amide. Preference is given to using oleyl alcohol, oleylamine, dioleylamine, methyloleylamine.

The anti-settling agents are used in quantities of 0.1 - 5% by weight, preferably 0.3 to 3 wt .- ^, based on casting resin or Cast resin component, used.

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The term liquid casting resins, casting resin mixture, the components of the liquid Gießharzmischungen comprises liquids which at 25 ° - have to 50,000 cPoise 120 ⁰ C a viscosity of 5th

Liquid casting resin mixtures include, for example, epoxy resin-hardener mixtures, di- and / or polyisocyanate-polyol mixtures or mixtures of unsaturated polyester polymerizable monomers. Accordingly are the components of the cast resin mixtures: epoxy resin and hardener; Di- and / or polyisocyanate and Polyol; unsaturated polyester and polymerizable Monomer.

Cast resin mixtures based on epoxy resin hardeners are preferred.

Epoxy resins include, for example, aliphatic, cycloaliphatic, aromatic or heterocyclic polyepoxides understood that contain on average more than one epoxy group per molecule.

The polyepoxide compounds to be used can be polyglycidyl ethers polyhydric phenols, for example from pyrocatechol, resorcinol, hydroquinone, from 4,4'-dihydroxydiphenylmethane, from 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, from 4,4'-dihydroxydiphenyldimethy! methane, from 4,4'-dihydroxydiphenylcyclohexane, from 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, from 4,4'-dihydroxydiphenyl, from 4,4'-dihydroxydiphenyl sulfone, from tris (4-hydroxyphenyl) methane, from the chlorination and bromination products of the aforementioned diphenols, from novolaks (i.e. from reaction products of monohydric or polyhydric phenols with aldehydes, especially formaldehyde, in the presence of acidic Catalysts), from diphenols, which by esterification of moles of the sodium salt of an aromatic oxycarboxylic acid with

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one mole of a dihaloalkane or dihalo dialkyl ether were obtained (see British patent 1 017 612), from ' Polyphenols produced by the condensation of phenols and long-chain haloparaffins containing at least 2 halogen atoms (see British Patent 1,024,288). There may also be mentioned: polyepoxide compounds based on aromatic amines and epichlorohydrin, e.g. N-di- (2,3-epoxypropyl) -aniline, N, N'-dirnethyl-N, N'-diepoxypropyl-4,4'-diamino-diphenylmethane, N, N'-tetraepoxypropyl-4,4'-diaminodiphenylmet'han, N-Diepoxypropyl-4-aminophenylglycidether (cf. British patents 772 830 and 816 923).

The following are also possible: glycidyl esters of polyvalent aromatic, aliphatic and cycloaliphatic carboxylic acids, for example diglycidyl phthalate, diglycidyl adipate and glycidyl esters of reaction products of 1 mole of an aromatic or cycloaliphatic dicarboxylic acid anhydride and 1/2 mol of a diol or l / n mol of a polyol with η hydroxyl groups or diglycidyl hexahydrophthalate, which can optionally be substituted by methyl groups.

Glycidyl ethers of polyhydric alcohols, for example from 1,4-butanediol, 1,4-butenediol, glycerol, trimethylolpropane, Pentaetythritol and polyethylene glycols can also be used. Of further interest are triglycidyl isocyanurate, Ν, Ν'-diepoxypropyloxamide, polyglycidyl thioether from polyvalent thiols, such as from bismercaptomethylbenzene ', Diglycidyl trimethylene trisulfone, polyglycidyl ether based on hydantoins. Finally, epoxidation products of polyunsaturated compounds should be mentioned, such as vegetable oils and their conversion products, epoxidation products of di- and polyolefins, such as butadiene, vinylcyclohexene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, polymers and Copolymers that still contain epoxidizable double bonds

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contain, e.g. based on polybutadiene, polyisoprene, butadiene-styrene copolymers, divinylbenzene, dicyclopentadiene, unsaturated polyesters, as well as epoxidation products from olefins, which by Diels-Alder addition are accessible and are then converted into or from polyepoxides by epoxidation with per compounds Compounds which contain two cyclopentene or cyclohexene rings linked via bridging atoms or bridging atom groups. Polymers of unsaturated monoepoxides may also be mentioned, for example of glycidyl methacrylate or allyl glycidyl ether.

As hardeners, all common hardeners are, for example, di- and polycarboxylic acid anhydrides, for example phthalic anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Methyl-endomethylene-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Tetrahydrophthalic anhydride or mixtures thereof are suitable. Acid saturated polyesters, polyamines, Polyamide amines, aniline formaldehyde resins, phenol formaldehyde resins, Boron trifluorine adducts with amines, phenols, Alcohols with carboxylic acids, etc. in question.

Modifying agents such as plasticizers, elasticizing agents such as Polyglyko-Ie, Polyether glycols, polysulfides, polyesters with terminal OH groups, reactive and non-reactive diluents, soluble dyes or accelerators are added.

The hardening of the epoxy resin-hardener mixture takes place after known methods, the choice of curing conditions such as curing temperatures, amounts of hardeners, etc. dem A person skilled in the art is sufficiently familiar.

It is also possible to use mixtures of polyepoxides and monoolefinic unsaturated dicarboxylic anhydrides such as

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Maleic anhydride as well as CV, ß-momoolefinically unsaturated to use liquid monomers such as styrene and polymerization catalysts as liquid casting resin mixtures.

"The liquid cast resin mixtures based on unsaturated Polyester, polymerizable monomers contain as unsaturated Polyester, for example, polymerizable condensation products of aliphatic and / or aromatic Polycarboxylic acids, such as adipic acid, succinic acid, maleic acid, itaconic acid, aconitic acid, phthalic acid, isophthalic acid, Terephthalic acid, hexahydrophthalic acid,

Methylhexahydrophthalic acid, trimellitic acid, pyromellitic acid or their anhydrides and polyalcohols such as Ethylene and propylene glycol, 1,3-butanediol, 1,4-butanediol, Hexanediol, diethylene glycol, tripropylene glycol, glycerine, trimethylolpropane and their reaction products with alkylene oxides.

The above-mentioned polycondensation products containing carboxylic acid groups are prepared by known processes, as described, for example, in "Methods of Organic Chemistry" Houben-Weyl, k. Edition, 1961, Volume 14 / II.

The above casting resin compositions are cured at room temperature or at elevated temperatures after addition of polymerization catalysts, such as benzoyl peroxide, Dicumyl peroxide, tert-butylcumyl peroxide, methyl ethyl ketone peroxide, Polymerization accelerators such as tertiary amines, cobalt or vanadium salts, e.g. cobalt naphthenate or Cobalt octoate by known methods.

In the case of the di- and / or polyisocyanate-polyol casting resin mixtures, the di- and / or polyisocyanates hexamethylene-1,6-diisocyanate, tolylene diisocyanates (2,4 or 2,6 isomers or mixtures thereof), diphenylmethane-4,4 ' -diisocyanate or isomeric diphenylmethane diisocyanate mixtures, isocyanate- Le A 15 341 - 7 -

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prepolymer, i.e. reaction products of the above isocyanates with diols and / or polyols (molar ratio of isocyanate group to OH groups 1: 0.1 to approx. 1: 0.8) and as polyols, Ethylene glycol, diethylene glycol, polyethylene glycols, propylene glycols, dipropylene glycols, polypropylene glycols, Glycerine, trimethylopropane, cyclohexanediols, polyester with terminal hydroxyl groups, etc. can be used. Curing can be done at room temperature or elevated Temperatures optionally take place in the presence of accelerators.

Solid additives that are insoluble in the cast resin mixtures or their components are fillers and pigments in powder form, for example quartz flour, chalk, ground dolomite, aluminum oxides, aluminum hydrates, satin white (3 CaO.Al ₂ O ₃ .3CaSO ^ .31H ₂ O, powdered glass , Silicas, slate flour, asbestos flour, talc, gypsum, mica, graphite, antimony trioxide, metal powder, such as copper bronze, aluminum powder, iron powder; titanium dioxide, lithopone, barite, zinc oxide, zinc sulfide, cadmium sulfide, white lead, iron oxides, azo pigments, phthalocyanine pigments, The amounts of these additives in the total casting resin mixture can be 30-90% by weight, preferably 40-70% by weight.

The additives, such as fillers and pigments, can be the casting resin mixture or the components of the casting resin mixture be added, for example the carboxylic acid anhydride hardeners, the polyols, the epoxy resins.

The addition and mixing of the anti-settling agents of the invention to the liquid casting resin or its components takes place before, during or after the addition of the fillers or pigments, preferably before adding the fillers or pigments.

The anti-settling agents according to the invention prevent the fillers from settling or even reduce it after storage of several months to such an extent that no solid, but at most easily agitated sediments are formed.

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After hardening, the cast resin mixtures result in valuable plastics that can be used on the ElektroisoliergeMet, tool, Model and gauge construction, in the laminating resin sector for the production of coverings, coatings, molding compounds, etc., find great interest.

Example 1 ;

100 weight parts of a commercially available Hexahydrophthalsäurediglycidylesters (epoxy equivalent 172, viscosity 600 cP at 25 ⁰ C)-Tln part by weight of stearic acid and mixed with 0.8 part by weight Tln methylstearylamine and 0.4 at 60 C then with stirring, with 150 wt .-Tln quartz powder. After standing at 50 ^° C. for 24 hours, there was practically no sedimentation phenomenon, in particular no sedimentation formed. Even after three months of storage at room temperature, no solid sediment forms, but only a slight sedimentation, which can be dispersed by simple stirring. The parallel test without an anti-settling agent leads to a solid, hard sediment after just 24 hours of storage, which can no longer be stirred up.

Example 2 ;

100 weight parts of methylhexahydrophthalic anhydride (viscosity at 25 ⁰ C, 60 cP) are added at 70 ⁰ C with 2 parts by weight of distearyl amine, and then stirred with 100 parts by weight quartz flour and 50 parts by weight of dolomite flour. After standing at 50 ^° C. for 24 hours, there was only slight settling on the surface of the dispersion, and no sediment was formed. The parallel experiment without anti-settling agents leads to a rock-hard soil that can no longer be stirred up.

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Example 3 :

100% by weight of a liquid epoxy hardener (viscosity at t = 25 ⁰ C -v 100 cP) of 50% by weight of hexahydrophthalic anhydride, 30% by weight of methylhexahydrophthalic anhydride and * 10% by weight of a polypropylene glycol (molecular weight 2000, which from Propylene glycol 1,2 as the starting component and propylene oxide as an addition component) are stirred at 70 ° C. with 1 part by weight of methylstearylamine. 150 parts by weight of quartz flour are then stirred in. After 5 months of storage at room temperature in a closed vessel, no solid, immovable sediment has formed. The filler, which is slightly compacted towards the bottom, can be stirred evenly within a few seconds by simply stirring.

Without the addition of the anti-settling agents, the same is obtained Storage time a firm, hard, thick sediment that. can no longer be dispersed by stirring.

100 weight parts of the above hardener filler mixture (40 weight parts curing agent mixture + 60 weight parts quartz powder) are placed in a 100 ⁰ C hot melt (viscosity 400 cP) of 100 parts by weight of at Tln Room temperature solid bisphenol diepoxide (epoxy equivalent 370) stirred in and stored at 60 ° C. for 12 hours. There is no sedimentation. Directly after storage at 120 ^° C., the casting resin mixture can be cured to form a molded plastic part within 16 hours. The filler is evenly distributed in the molded part.

Example 4 :

104 weight parts of styrene are mixed diglycidyl hexahydrophthalate at room temperature with l68 parts by weight of TiN (viscosity 600 cP at t = 25 ⁰ C). Thereafter, 4 parts by weight of a 1% solution of tert. Add butyl catechol in styrene. 98 g of maleic anhydride are ^{melted at 55 °} C. and added to the previously prepared solution with stirring.

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After cooling to room temperature, a clear liquid of low viscosity is obtained which, ^{measured at 25 °} C., gives a value of 5.9 cP. After standing for 2 days at room temperature, the viscosity is unchanged.

750 parts by weight of quartz flour and 6 parts by weight are added to the mixture Stearyl alcohol added and stirred. After 24 hours of storage, no sedimentation phenomena can be observed, especially not the formation of sediment. If stearyl alcohol is not added, it is after 24 hours Storage a hard-to-stir sediment of quartz flour can be found.

The casting resin mixture, in the filler and anti-settling agent are evenly distributed, is made with 6 parts by weight of a paste of 3 parts by weight of benzoyl peroxide and 2 parts by weight of dibutyl phthalate and finally 2.5 parts by weight of dimethylbenzylamine mixed with stirring at room temperature.

An easily pourable liquid with a viscosity of 2100 cP at 25 ° C. is obtained. The mixture is poured into a plate form made of light metal, which in turn was also at room temperature. The plate form is placed in a heating cabinet at a temperature of 60 ^° C. and removed and removed from the mold after 15 hours. A hard, bubble-free plastic sheet is obtained in which the filler is evenly distributed. After a post-curing time of 24 hours at 140 ° C, standard

2 bars have a flexural strength of 1440 kg / cm measured according to DIN 53 452 and a dimensional stability according to Martens of 162 ° C (measured according to DIN 53 458).

Example 5 :

100 parts by weight of a commercially available unsaturated polyester resin (Viscosity at 25 ° C = 1200 cP), made from 30 parts by weight of maleic anhydride, 9 parts by weight of phthalic anhydride, 23 parts by weight of propylene glycol and 12 parts by weight of propylene glycol

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Dipropylene glycol and mixed with 36 parts by weight of styrene are stirred with 1.5 parts by weight of stearylamine and then with 100 parts by weight of quartz flour. After 24 hours storage at 50 ⁰ C a small breiförmiger set that can be very easy to stir again, followed by back receives the nature of the original dispersion is on the ground. If the same experiment is carried out without stearylamine, a hard sediment that cannot be stirred in is obtained after storage for 24 hours.

Example 6 ;

100 parts by weight of a commercially available polyether polyol, made from trimethylolpropane and propylene oxide in a molar ratio of 1: 6 with an OH content of 13% (viscosity at 25 ° C. = 620 cP), which is usually used as a curing agent for isocyanates, is 2.5 Tine by weight of stearyl alcohol and 120 tine by weight of quartz flour are mixed together. After standing at 50 ^° C. for 24 hours, no settling certificates can be detected. The parallel experiment without an anti-settling agent leads to a strong sediment that can no longer be stirred.

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Claims (2)

Claims: 2361 1. Anti-settling agents for solid, insoluble additives
in curable liquid casting resin mixtures or the components of the casting resin mixtures, characterized in that 1-octadecane or l-cis-9-octadecene derivatives are used as anti-settling agents. 2. Procedure to prevent or reduce the
Settling of solid, insoluble additives in hardenable liquid hardenable casting resin mixtures or their
Components, characterized in that one in the casting resin mixture or in the components of the casting resin mixture before, during or after the addition of the solid insoluble
Additives 0.1 - 5% by weight, based on the mixture or
Component of the casting resin, a 1-octadecane or 1-cis-9-0ctadecene derivative stirred. Le A 15341 - 13 - 0 9 8 2 6/1032