BE445909A - - Google Patents

Description

       

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     NEW SYNTHETIC RESINS AND THEIR MANUFACTURING METHODS.



   The new synthetic resins which will be described are obtained by intercondensing resins derived from a urea or similar substance with an aldehyde on the one hand and a compound having at least one active methylene group or else an active mono-substituted methylene group. products thus obtained can be used as casting or molding resins, for the manufacture of agglomerates with a laminar structure, for coatings and the manufacture of adhesives, etc.



  These substances can be transformed by heat into insoluble and infusible aminoplastics. We will successively describe the cases where the constituent with an active methylene group is a beta ketonic ester, a malonic or malonic ester monosubstituted on the CH2 group, finally a malonic amide, diamide, nitrile, or dinitrile, or else the monosubstituted derivatives. of these amides and nitriles *

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   1 - USE OF ESTERS:

  KETONIC BETA
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 The formula of a beta ketone ester is nooca2000Rt, R and R 'denoting hydrocarbon radicals, such as acitylaoetic esters, in particular alkyl, aryl, alco, laryl8 or dtaralocylest les 8J11inopla.tes , based on an amino or amide compound, for example those derived from urea and formaldehyde have been known for a long time and usually must be plasticized prior to their use, for example in the production of molding compositions, if one wants to obtain the maximum commercial utility
 EMI2.2
 cialet For this purpose, different esters and other organic substances were useda The first plasticizersa were volatile substances,

   which may be released during hot die casting. Other times the plasticizer tended to sublimate or vaporize upon leaving the finished parts during their use, causing stresses, cracks or surface defects. In general, these plasticizers did not intervene in the reaction and could be extracted from the molded articles since it was chemically impossible for them to condense with the aminoplasts or their constituents, integrating into the resinous molecule. On the other hand, the incorporation of a latent or active deprivation catalyst is known to facilitate the transformation of the resin into an insoluble and infusible vane. This method has not always proved to be entirely satisfactory.
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  According to the invention, the internal plastitioatton of the aminoplasts is carried out thanks to a reaction between the following constituents: 10 -) an amino or amidated compound, for example aminotriazinea, in particular aBméllne, "melamine, or even urea, thiourea or mixtures of these substances.



     2 '-) an aliphatic aldehyde, preferably formaldehyde,
3 '-) a beta ketone ester.



   Such compositions can be transformed into soluble and meltable condensation products, but which can be transformed by heat, in particular at the usual molding temperatures, into insoluble and infusible materials. Aminoplasts
 EMI2.4
 These are both internally plasticized (self-planted) and potentially reactive (self-catalyzed) at the same time and require no additional plasticizer, catalyst or other setting reagent to obtain useful castings. These aminoplasts can be said to "set spontaneously", the resin molecule associating radicals borrowed from each of the starting constituents when it passes into the insoluble and infusible state.

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   Usually, the reaction of an acetlylacetic ester with formaldehyde results in an oily phase which separates from the bulk. If a condensation catalyst is incorporated, the reaction becomes almost instantaneous. It could not be predicted that the interoondensation of a beta ketone ester with an aliphatic aldehyde and an amine or amide compound would provide uniform, homogeneous resinous products. heat-curable, and self-plasticized (in the resin molecule itself). The resinous syrups and molding compositions obtained can be stored for a long time without deterioration. On the contrary, the already known aminoplasts, containing active catalysts, mineral or organic acids, do not remain stable over time.

   The new compositions set rapidly by heat, optionally under pressure, they fill the molds well during compression and make it possible to obtain quickly and economically parts of various shapes, even very complicated ones. The final hard products @ have good light stability, a pleasant surface, they are very water resistant and meet the requirements of hardness, toughness, etc. required by their use.



   Another advantage of the invention is that by choosing ketone esters containing at least 6 carbon atoms in the ester radical, for example hexyl, heptyl, oootyl, decyl, docecyl acetylacetates, etc. .... these esters provide the resin with self-plasticization, the property of lubricating the mold, self-catalytic hardening and water resistance, whether the resin is used by molding, by rolling, or as a adhesive, as coating, etc.



   The choice of the aldehyde depends above all on economic considerations and on the properties desired in the final product. In general, formaldehyde or compounds which generate formaldehyde, such as paraformaldehyde, examethylene tetramine, etc., are preferred. also employ the other aliphatic aldehydes, saturated or not, aromatic, etc., or else mixtures of any several of these aldehydes, or else of one of these aldehydes with a compound generating formaldehyde. In general, the longer chain the aliphatic aldehyde, the slower the setting of the resinous product, resulting in a softer end product.



   The amino compounds or amides which can be used are, for example, urea, thioureas, diethylene triurea, methylated, acetylated, benzoylated, allylated, 2-chlorallylated, ethylidelated, methylolated, methylenated, phenylthiourea, N, N- ureas. diethylurea, eta ..; substances of the nature of urea t

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 EMI4.1
 guanidine, dioyandiamide, guanviurd, guanylthiourea, biguanidine, aminoguanidine, aminotriasins (melamine, alimelin, etc.), creatinine, guanolin, etc., or mixtures of such compounds. All these products will be indiscriminately designated under the name of "ur4ic substances".
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  In the general formula of the beta ketone esters RCOCET-OOOB ', R and x! denote similar or different radicals belonging to the series of alkyls, aryls, alkylaryls, aralkyls, alkenes, cycloalkyls, etc. * in particular the methyl, ethyl, propyl, butyl, isobutyl, amyl,
 EMI4.3
 hexyl, ootyl, dayl, allyl, methallyl, benzyl, toluylee phenethyl, etc.



  The compounds to be interconnected are mixed and the reaction carried out at room temperature or higher, in the presence or absence of an acid or alkali catalyst, preferably alkaline * For this purpose, alkali or alkaline earth hydroxides, alkali carbonates, can be incorporated. aliphatic or aromatic tertiary amines, etc.

   Practice has shown the advantage
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 to choose a basic compound from the ammonia class, possibly aqueous, primary and secondary amines, all substances taking part in, or facilitating the formation of methylol derivatives between the aldehyde, for example formaldehyde, and the other constituents of the resin , providing methylolurea, On the other hand, tertiary amines appear incapable of
 EMI4.5
 andintercondenate with the other constituents.

   As examples of primary and secondary amines, there will be mentioned the mono and diala5ylaminea, for example the mono- and di-methylated, ethylated, propylated, isopropylated, butylated, 8m; 114es, etc., or else the mono - and di-arylamines, for example mono- and di-phenylamines, mono- and di-benzylamines, etc., or else alcoholic amines such as mono- and di-etlumolamines, etc. **
In order to carry out the initial reaction between constituents, all the reagents can first be mixed in the presence or absence of substances ad-
 EMI4.6
 ditional catalysts, fillers, natural or synthetic resinous substances, solvents, dilutives, etc. ** The ketone ester can also be added to a partially condensed product of a urea and an aliphatic aldehyde,

   and then continue the condensation between all the components. Conversely, one can condense the ketone ester and an aliphatic aldehyde on the one hand, the vane
 EMI4.7
 urfic tance and the aliphatic aldehyde on the other hand, then mix these substances for the interooniensert One can also condense or partially condense the oetone ester with an excess * of aliphatic aldehyde, add a

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 EMI5.1
 urea and inter-react with the constituents. Various alternative embodiments may still be employed, according to methods known to all skilled in the art.

   The intercondeusation can be carried out under various conditions of duration, temperature and pressure, the temperature possibly being between ambient and that of reflux., Under reduced pressure, atmospheric, or higher.



   The Intermediate condensation products thus obtained set by heat, either isolated or mixed with the usual fillers, pigments, accelerators, dyes, lubricants, etc.. These resinous masses, modified or not, can in any case be transformed, without catalyst and at high temperatures, into insoluble and infusible substances.



   The Intermediate condensation products can be concentrated or diluted by adding or removing volatile solvents which make it possible to prepare varnishes, the viscosity and concentration of which can be adjusted as desired by standard technique. These solutions are applicable as paints,
 EMI5.2
 varnishes, lacquers, enamels, a ° h4ia, or in the production of laminar articles, etc. The liquid inter-condensate can also be used as a casting resin. Laminar products having the structure of a gel can be edged and granulated to give clear, heat-hardening resins.
In the examples below, the proportions given are by weight.



  Example 1- The following mixture is heated under reflux for 30 minutes t
 EMI5.3
 urea - 137.0t aqueous ammonia at enTe $ 28 - 14.4; aqueous formaldehyde at approx.



  37.1% - 384.0; caustic soda in 24 parts of water - 0.096; Ethyl aetylacetate - 13 # 2o After heating, the pH of the resinous syrup has fallen to 4985 The intercondensed product obtained is clear, without a trace of precipitate despite its acid reaction (resinous syrup No. 1). In the absence of the ketone ester an ordinary aminoplastic resin under such acidic conditions would precipitate into an amorphous white powder, little or no use for molding or making laminar agglomerates.



   The syrup does not jelly and does not precipitate after standing for several days at room temperature. It sets in heat and is especially suitable for molding. In the absence of the ketone ester, the above composition gives a less plastic and non-heat curable substance.



   All of the resinous syrup No. 1 is mixed with 161.0 floche

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 alfa and 1,2 zinc stearate (lubricant for the mold). We thus obtain
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 composition n * 1 which dries 3 hours at 50, grinds and molds at 130 ', under pressure of 140 kg / 0 # 2 for three minutes; thus obtaining uniform, hard parts free from blowholes and which perfectly match the shape of the mold.



   The setting of this composition and those described below can be accelerated, if desired, by addition of acidic substances or by inter-condensation with setting reagents, and prior to mixing with the feed. These acid setting catalysts can also be chosen from
 EMI6.2
 mi those having a lantente actionb Examples 2, 3 and 4 indicate compositions of this kind. example 2 -
The mixture of t urea - 57.0 is heated under reflux for 20 minutes;
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 aqueous ammonia at approx. z - 6.0; formaldehyde to eny. 37.1% - 161.0; caustic soda in 10 parts of water - 0.04; Ethyl acetylacetate - 5.56 After heating, 0.2 citric acid is added. It is mixed with 70 parts of alfa flask and 0.4 of zinc stearate.

   We dry two and a half hours at 70 and
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 molded for two minutes at 120 * under 140 ° 1E8 / cm2. The molding plasticity is excellent, much better than that of similar compositions, but free of acetylacetic ester. The parts have set throughout the entire mass and are free of blisters * The result is analogous by replacing citric acid with the same weight of phthalic anhydride or hydrochloric acid *
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 ftem'D1e 3 -
The mixture is heated under reflux for 30 minutes: urea - 57.0; approx. 28% aqueous ammonia - 6.0; approx. 37.1% aqueous formaldehyde -160.01
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 caustic soda in 10 parts of water - 0.04;

   Ethyl acetylacetate - 5.5 * Resin syrups were prepared according to this formula but by intercontending them separately with each of the following reagents, so as to obtain aminoplasts which set spontaneously faster than by the use of Itacetylaoetate. ethyl alone. t
 EMI6.7
 
<tb> reagent <SEP> from <SEP> socket <SEP> parts <SEP> additional <SEP> duration
<tb> under <SEP> reflux,
<tb>
 
 EMI6.8
 monoahloraaetamide .................. 10.0 10 minutes dichloroacetamide .................... 8.0 3E1 " triahioraaetamide ....., ............. 1.0 8 attroui4e ......................... .. z brought back to reflux glycine 2 "" chlorac4ty1urfe .....................

   $ 1 0 10 minutes

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 EMI7.1
 taking reagent --dured @ supp1.! Il8D.taire under reflux ethylene diamine mOnOcUorhydrate 0 # 5 brought back to reflux amlndb6tamide hydrochloride ...... 1.0 "" diethanolamine hydrochloride .... 1.0 "" amino hydrochloride 6% oni% rile, 0.3 chloractonitrile ................. 8, o 13 minutes gamma-chlorobutyronitrile 4.0 10 ohloral 4.0 10 chloroacetone .., ......... "........

   1.0 10 "symmetrical alpha dichloroacetone .., 0.3 10" parchlorophenylphenacycle bromide 200 10 "phenoyol chloride 1.0 10"
 EMI7.2
 The above various intercondensation products were mixed with 70 parts of alfa and 14 zinc stearate fluff, dry and z-treated, in the usual manner. Cast for two minutes at 130 ° s under 140 Icg / om and l. 'one obtains in all cases parts having set well and without cracks.



    Example 4 -
To three resinous syrups prepared according to Example 3, each of the following latent catalysts is respectively added t
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<tb> catalyst <SEP> latent <SEP> parts <SEP> additional <SEP> duration
<tb>
 
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 .¯, .. ¯ ..,. ¯¯ .... ¯¯, ¯¯., ¯ ------- under reflux. glycine ethyl ester hydrochloride,. "....., ...., .....,." 0.4 brought back to reflux sodium chloracetate ............ 1.0 none diethylobloraeftmide 1.0 none
The syrups obtained were mixed with 70 parts of alfa floche and 0.4 of zinc stearate, dry, treated in the usual way, fine * -
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 Lely molded for two minutes at IWO under 140 ke / ci $ 2, giving pieces which have set well and similar to those of example 3.



  Example 5
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 The mixture is mixed and heated for 15 minutes under melanin reflux - 120j ammonia aqmmee at 28f. we. - 6.0; $ 37 1% reg aqueous formaldehyde -28o, Oi caustic soda in 20 parts of water - 0.16t of ethyl acetylacetate - 6, bo The syrup * obtained is mixed with 133 parts of alfa fluff and 0.8 of zinc stuer rate * it is dried at 67 * 0 for two and a half hours, grinds and molds for three minutes at 130 '' under 140% 1em # n The molded place has taken well, no blowholes, but is slightly gummy when hot.

   This plastic consistency is advantageous for injection molded parts in threaded dies. For other applications it is desirable to have harder molded products, which is achieved by the methods of Examples 6 and 76.

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 E7IE 6 -
To six resinous syrups according to Example 5, the following setting catalysts were added, so as to obtain spontaneously setting and accelerated hardening aminoplasts.
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<tb> catalyst <SEP> from <SEP> take <SEP> parts <SEP> additional <SEP> duration
<tb>
 
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 ------------------- ------- under reflux ohloraoetam1de ..................... ......

   2.0 10 minutes ohloral hydrate ....................... 4.0 a nitrourde .............. .................. 0.4 "wisteria ........................... ....... 0.4 tt "monochlorhydra% e% hyleno ** iiomine ...... 1.0" diethanolamine hydrochloride ........... 1.0 brought back to reflux
The interoondensation products obtained are added with 133 parts of alfa floche, and 0.8 of zinc stearate, dry, ground, cast two
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 minutes at 130, under 140 irgom The parts obtained are quite rigid when they are unmolded while still hot.

   
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 MOMPY 7
Equal amounts of resinous syrups prepared according to the formula of Example 5, but without additional heating under reflux, were added.
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 born respectively from two parts of diethylchloraoetamide (as latent catalyst) or from 0.6 parts of citric acid (active catalyst). The preparation up to molding is completed as in Example 6 and the molded parts are similar.
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  SBELEL6-- The mixture of melamine - 31.5 is heated under reflux for 15 minutes; thiourde - 57.0; aqueous ammonia at enT. 28, 6.0; 37.1% enTe aqueous formaldehyde - 190.0; caustic soda in 20 parts of water - 0.12; ethyl acetylacetate - 4.0, Then add 0.7r1f, hydrochloride of the ethyl ester of glycine, For the molding, 94 parts of alfa floche and 0.6 of sine spleen are incorporated * It is dried for 3 hours at 60 ° C., it is ground and molded for 4 minutes at 130 under 140 kg / cm 2. The parts come out hot without deformation. They are hard and have taken well.



    EXAMPLE 9 -
The mixture of urea - 45 is heated for 15 minutes under reflux; melamine
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 31.8; approx. 37.1% - 190.0 aqueous formaldehyde; aqueous ammonia, ony. $ 28 - 6.0; caustic soda in three parts of water - 0.12; ethyl acetylacetate - 2.5, To the syrup obtained, part of the hydrochloride of the ethyl ester of glycine is added, it is dried for four hours at 60, crushed and molded at 130 for

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 three minutes under 140 kg / cm2.

   The parts are similar to those in example 8, but lighter in color *
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 MMIPLE 10 -
The same treatment as for Example 9 is carried out and the marl quantity of the same catalyst is added. The original mixture is dicyandiamide - 63.0;
 EMI9.2
 melamine - 31.5; aqueous formaldehyde at approx. 3'X, 1240t0; aqueous ammonia at approx. 38% - 6.0; caustic soda in 5 parts of water - 0.2; aoitylaedtate t- t1,> <yle 5.0 * The resinous syrup is processed, as in example 8, and produced from moldgea After drying for 5 hours at 60% grinding and molding for 5 minutes at 135 * under 140 k8 / am2, the very plastic composition when molded, provides moldable parts that are still hot, because they have set well and are very hard.



   The ratios between the constituents can be varied in a similar way.
 EMI9.3
 sable, but it is better to exceed 1 mol. of aliphatic aldehyde per mol. of total urea plus ketone ester. In general, at least 1.5 mol is employed. aliphatic aldehyde, especially formaldehyde, often 1.75 to 5 or 6 moles and more per mole of the total urea and ketone ester; it is for the proportion of 2 to 3 months of aldehyde that the most satisfactory results are obtained, in particular for the cost price of the unit.



   The proportion of the ketone ester can also be considerably varied, but most often 1 to 35 months of this ester is sufficient for 100 mols of urea substance. In general, 25 months per hundred mols of ketone ester are not exceeded. The most advantageous compositions for molding with
 EMI9.4
 charges arise from the intercondensation in the soluble and fusible state of one mol of single or complex urea substance, with at least 1.5 mol, and preferably 1.75 to 2 months of aliphatic aldehyde (preferably formaldehyde) and around
 EMI9.5
 0 * 25 mol of ketone ester, in particular acetylacetic acid ester. The use of higher levels of ketone ester should be rejected for most applications because the molded parts are then more difficult to obtain with the required hardness;

   but it is on the contrary useful if the product must permanently retain a high plasticity. If, for example, ketone esters are used
 EMI9.6
 At considerable molecular weight, for example octa4eoyl acetylacitate, the ketone portion of the resinous molecule is greater by weight than the urea portion. As a result, the resin retains a waxy consistency, which may be detrimental to certain applications, in particular those requiring high resistance to the action of organic solvents, #

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From the above, the molar ratio of the ketone ester to the other constituents depends both on the characteristics of this ester and on the
 EMI10.1
 properties sought in relation to setting, plasticity,

   etc., curable or hardened rinses, and final molded compositions derived therefrom,
The basic resins described can be modified in a wide variety of ways by incorporating before, during or after the primary condensation of the mo-
 EMI10.2
 difiers such as mono- or polyhydric alcohols, amides, polyamides, amines, polyamines, aminophenols, summer, or alternatively high molecular weight blades, such as lignin, materials derived from hydrolysis of wood, proteins and their condensation products with aldehydes, condensation products of furfuraldehyde, aldehydes with phenols or anilines, saturated or unsaturated alkyd resins, cellulose derivatives soluble in water 'water, gums and natural resins,

   synthetic polymers
 EMI10.3
 vinyl compounds, long chain / polymers, such as superpolyomides, aulfonamide and aldehyde resins, etc.



    Relative to the use of the usual ingredients: fillers, pigments,
 EMI10.4
 opacifier, mold lubricants, etc., conventional techniques can be used for the preparation of molding compositions. The modifiers can be incorporated according to known techniques, then the compositions can be dried cold or hot, making these mixtures more dense by working in a machine.
 EMI10.5
 la: them 1! 8ndbury, or else by rolling, oalandrage, etc., all followed by grinding and sieving to the required dimensions. Preferably, between L00 and Leo- are molded under a pressure of 7p to 300 kgom2. Applications of these molded compositions include firewalls, water-repellent parts, impregnation of electrical coils, etc.
 EMI10.6
 



  II - USE OF ESTERS b5AD0I3IJES.



  It is possible to use either the monoesters of malonic acid according to the general formula EDOOea2 or the RtQa0t700R dlesters. In these formulas R and Rif denote bydrooarbon radicals, alooyl, aryl, etc. .., as in the mode of application described above. During condensation, the malonic ester chemically combines with the resin molecule and can no longer be extracted by vaporization or by dissolution.



   Any composition comprising * at least: 1. an amino or amide compound, 2 an aliphatic aldehyde, 3 a malonic ester, even if it is not hard
 EMI10.7
 heat-resistant by becoming insoluble and infusible, can be made

 <Desc / Clms Page number 11>

 such by incorporating in it a latent or active setting catalyst, or else by intercondensing with at least a fourth reagent which provides this property, for example chloracetamide, aminoacetamide hydrochloride, ohloroetylurea, nitrourea, etc. thus ultimately obtains amine-plastic materials that set spontaneously *
The reaction of formaldehyde on a malonic ester,

   for example dimethyl or diethyl malonates, carried out according to the usual technique, provides an oily phase which separates from the mass; in the presence of the usual aminoplast catalysts. the reaction is almost. instant. But it could not be predicted that the intercondensation of a malonic ester with an aliphatic aldehyde and an amide or amine compound would provide uniform, homogeneous resinous substances, potentially susceptible to heat setting and intramolecular plasticized, ie plasticizer being integrated into the molecule.



   As another advantage of the invention, it will be indicated that the esters chosen, in particular the malonic monoesters of alkyls containing 6 and rather at least 8 carbon atoms, or else the malonic diesters whose alkyl chains contain at least 4 carbon atoms. carbon each, impart to the mixed resinous products described self-plasticizing, water-repellent and self-lubricating properties of the molds which make them valuable for molding, the manufacture of laminar or adhesive products, etc.



   The choice of aldehyde depends more on economic considerations than on the properties sought in the finished product. Generally, fora maldehyde or a formaldehyde generating product is preferred, but one or more aldehydes, preferably aliphatic, may be employed; as an amino or amide compound, any one of the urea substances defined above is used, or mixtures of such substances.



   The general preparation conditions are those described above with regard to the condensation temperature, the use of the acidic or alkaline catalyst, preferably for ammonia; primary or secondary amines and the combination of a weaker catalyst, such as ammonia, and a stronger catalyst, in small quantities, such as sodium hydroxide,
The technique to be followed involves any of the variants which have been carried out either simultaneous intercondensation of all the constituents in the presence or absence of fillers, solvents, diluents, etc., or the separate condensation of the aldehyde with the 'one and / or the other of the reactants, then the mixture of the partially condensed products,

   to perform the final intercondensation

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 The temperatures, time and pressures at which these reactions are carried out are chosen as in the previous case.



   The products thus obtained result from partial condensation and can be modified by incorporating a setting catalyst into them or by inter-condensation with a reagent capable of catalyzing setting. These reagents or cata-
 EMI12.1
 lyaeuraheont Not useful when one of the raw materials is a monoester of malonic acid.



   To use these intermediate products, we can mix them with fillers and other ingredients, such as those already listed, or even dissolve them so as to obtain varnishes, lacquers, paints, adhesives and etc., we can finally use them liquids, as casting resins
 EMI12.2
 1I: TIWPT. "F. 11 -
A mixture of t urea - 57.0 is heated for 30 minutes under reflux; aqueous ammonia at approx. 28% - 7.6; approx. 37.1% aqueous formaldehyde - 161.0; caustic soda 0.04, in 10 parts of water, diethyl malonate - 8.0. Then added 0.02 of hydrochloric acid (active catalyst) in 5 parts of water, then 70 parts of floche * dtalfa and 0.04 of zinc stearate are incorporated.

   After s-
 EMI12.3
 6 hours chage at 5o, grinding, sieving and molding for 3 minutes at 1306 under 140 kg / cm2, a molded part is obtained which has set well, shiny, of pleasant color and hot release. The plasticity was very good during the compression. Hydrochloric acid can be replaced with an equal weight of citric acid or phthalic anhydride and similar parts can be obtained.



  EXAMPLE 12 -
A series of mixtures having the starting composition of example 11 is heated for 30 minutes under reflux. Each of these preparations is then interoondenseed with one of the following compounds, so as to obtain spontaneously setting aminoplasts.
 EMI12.4
 
<tb> Catalyst <SEP> of <SEP> socket <SEP> parts <SEP> Additional <SEP> duration
<tb> under <SEP> reflux,
<tb>
 
 EMI12.5
 Chloracdtonitrils ......................... 2.0 10 minutes Gasma-ohioro'butyronitrile .............. ... 5.0 85 Monochloracitamide ........................ 1.0 10 Diahloraoetamide 2.0 17 Triohioraoetamide ........ ................. 1.0 16 Aminoketamide hydrochloride 1.0 brought to reflux ethylone diamine gonooblohydrate ....... 9.5 5 minutes Konoehydrochloride diethaaolamine ........ 1.0 5 Nitrourea .................................

   0 $ 3 brought back to reflux ah101 "aa6, rlule ........................... 110 10 minutes Ohloracetyl hydantoate ....... ......... 1.0 8 "Glyameh ................................... 3.0 brought back to reflux

 <Desc / Clms Page number 13>

 
 EMI13.1
 Aminoaoeton hydrochloride 1tr11e ............ 0, B brought back to reflux
 EMI13.2
 
<tb> Hydrate <SEP> of <SEP> ohloral <SEP> ......................... <SEP> 4.0 <SEP> 15 <SEP> minutes
<tb>
 
 EMI13.3
 Qh7.orecetone ........:

  ...................... 1.0 10 "Diebloracetone symmetrical .................. 0.3 10 "Para-ehlorophenylphenacyl bromide ...... 10 10"
 EMI13.4
 
<tb> <SEP> Phenacyl <SEP> <SEP> ...................... <SEP> 1.0 <SEP> 10 <SEP> "
<tb>
 
The resinous syrups obtained are loaded with alfa floche, lubricated with zinc stearate and then treated as usual for the molding of
 EMI13.5
 3 to 6 minutes at 130-t under 140 kg / om2. All the pieces obtained had taken well, were light in color and very shiny.



    'EXAMPLE 13 -
 EMI13.6
 To the resinous syrup obtained according to Example 11, 0.5 part of glycine ethyl ester hydrochloride was added as a latent catalyst. Was heated for two more minutes under reflux and then incorporated into the liquid 70 parts of alfa flask and 0.4 of zinc stearate. After drying, grinding and molding, we obtain well-set pieces, very little colored, having perfectly matched the shape of the mold. The latent catalyst can be replaced by sodium chloracetate
 EMI13.7
 or by diethylobloracetamidet EXAMPLE 14 -
Same formula as in Example 11, except substitution of 54 to 57 parts of urea and 6 of diisopropyl malonate for 8 of diethyl malonate.

   After heating for 30 minutes under reflux, one part of chloracetamide is added and heated for a further 10 minutes. 75 parts of alfa fluff and 0.4 of zinc stearate are added to the liquid resin. After drying and grinding, a very plastic composition is obtained which is molded under the usual conditions, and which gives well-set pieces having a good appearance. We can replace the
 EMI13.8
 chloroacetamide by any of the reagents listed in Example 12.



    EXAMPLE 15 -
By heating each mixture for 15 minutes under reflux, two charges each having the following composition: melamine - 113, 2; ammonia
 EMI13.9
 aqueous at 28 - 6.0; aqueous formaldehyde at enta 3, Z, e - 2% Cg caustic soda - 0912 in 10 parts of water; malonate diétiy7, daA - 2116 * To one of the preparations, two parts of phthalic anhydride were added and to the other 0.6 of citric acid. Each syrup was loaded with 133 parts of alfa floche and
 EMI13.10
 out6 of zinc stearate. Dry for 18 minutes at 67 ', grind and mold for 3 minutes at 130 under 140 kg / cm2. The two compositions are very plastic and give
 EMI13.11
 excellent parts suitable for hot demoulding without deformation.

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   Instead of the active catalysts mentioned above, the resinous syrup can be transformed into a spontaneous setting product by incorporating a catalyst.
 EMI14.1
 latent, such as sodium chloroacetate, diethylchloroacetamide, etc., ** a molding composition comprising two parts of sodium chloroacetate, heated for about 65 hours at 67 hours, retained its characteristic plasticity and moldability which can be observed if the 'the malonic ester is removed from the composition, EXAMPLE 16 -
A series of resinous syrups conforming to the formula of
 EMI14.2
 Example 15, then they were intercondensed with one of the following reagents, to obtain resins which set spontaneously:

   
 EMI14.3
 
<tb> catalyst <SEP> from <SEP> take <SEP> parts <SEP> Additional <SEP> duration
<tb>
 
 EMI14.4
 ######## ------- under reflux¯¯¯¯¯¯¯ Trichloracdtamide 2 $ 0 5 minutes
 EMI14.5
 
<tb> Hydrate <SEP> of <SEP> chloral <SEP> ....................... <SEP> 4.0 <SEP> 5 <SEP > "
<tb>
<tb> Nitrou'és <SEP> ................................ <SEP> 0.4 <SEP> reduced <SEP> to <SEP> reflux
<tb>
<tb> Glycine <SEP> .................................. <SEP> 0.4 <SEP> "<SEP>"
<tb>
<tb> <SEP> diethanolamine hydrochloride <SEP> ........... <SEP> 2, to <SEP> "<SEP>"
<tb>
 
 EMI14.6
 Chloroacetylurf ........................... 2.3 "" Chloroacetylurf ................ .......... 2,3 "" Symmetrical dichloroacetu ................

   2.3 "Phenacyl chloride 2.3" Aminoacetamide hydrochloride 2.3 ""
The liquid resins prepared, loaded as in the examples above and molded, are very plastic and give tough parts and very good appearance.



  EXAMPLE 17 ..
 EMI14.7
 



  A mixture of t ur4e - 45.0 is heated under reflux for 20 minutes; melanin - 31.5; aqueous formaldehyde at approx. 39.1f, $ - 190; aqueous ammonia at approx. Sa% - 6.0; caustic soda -0.12 in three parts of water; diethyl malonate -8.0. In the resinous syrup, part of the hydrochloride of the ethyl ester of glycine, 94 of floche alfa, 0.5 of zinc stearate are incorporated. It is dried for 17 hours in air, without raising the temperature, then for one hour 45 min, at 70. The molding for two minutes at 130 under 140 kg / cm 2 gives excellent parts.



  EXAMPLE 18 -
The following composition was treated as in Example 17: melamine-
 EMI14.8
 31; 5; thiourea .. 57.0 Oj aqueous formaldehyde at approx. 37.1% - 190.0; aqueous ammonia & enT.2t1f. - 6.0; caustic soda in three parts of water - 0.18; Diethyl marlonate - 7.0. The parts 11 .. molded .. are very hard, well taken and

 <Desc / Clms Page number 15>

 have an excellent appearance.



   Here are the general rules to be followed for the proportions between reagents 1 in general at least 1 mol of aliphatic aldehyde per mol in total of urea substance and of malonic ester. Good results are obtained for a proportion of at least 1.5 mol, in general 1.75 to 5 or 6 mol and more aliphatic aldehyde, in particular formaldehyde, per mol of urea plus ester * At the point From the cost point of view, 0 'is with 2 or 3 mols of aldehyde that the most satisfactory results are obtained.



   The proportion of the malonic ester should be selected from one to 35 mols per hundred mols of urea substance, generally at most about 25 mols per cent. An excess of malonic ester does not improve the placteness and lowers the hardness of the molded product. This can be given a waxy consistency by choosing the malonic esters of higher alcohols, for example di-octadecyl malonate.

   On the other hand, these products are less hard and have poor resistance to organic solvents *
Like mixed resins derived from ketone esters, those derived from malonic esters are modifiable by many substances t mono- and polyhydric alcohols, mono- and polyamides, amines and polyamines, amine phenols, substances with large molecules such as lignin and products derived from wood, proteins, condensation products of aldehydes with each other or with proteins, phenols, amines, sulfonamides, etc *. alkyd resins and resins, natural or synthetic, polyvinyl compounds, super-polyamides, etc *.,
The practical use of these resins also includes dyes, pigments, opacifiers, lubricants,

   mineral or organic fillers, etc ,,,, conventional in the molded materials industry. The preparation is carried out by the same mechanical means described with regard to resins based on beta ketone esters.



  III - USE OF COMPONENTS WITH A RADICAL METHYLENE LINKED TO TWO GROUPS ON,
According to this variant, the substance to be condensed with a urea material and an aliphatic aldehyde corresponds to the general formula XCH2Y, the atoms X and Y denoting any one of the functional groups nitrile, amide or thiamide, limited to the following: CN , CONH2, CSHN2, CONHR and CSNHR.



  In the latter symbol, R represents any univalent radical, alkyl, aryl, aralaoyl, alkaryl, acyl, naphthyl, nitro, halogen, aceto, acetox

 <Desc / Clms Page number 16>

 carbalkoxy, etc. These radicals can also be alicyclic or heterocyclic series. To abbreviate the language, these XCH2Y substances will be called "malonic compounds".



   We are aware of the difficulties encountered in the preparation of syrupy resins derived from amino or amide compounds and from Mliphatic aldehydes. The premature precipitation of the resin generally does not allow the regularity which is essential in manufacture. The various ingredients added to remedy this have not always overcome these difficulties, or have lowered the quality of the resins after curing.



   The invention makes it possible, on the contrary, to obtain clear resins, or homogeneous dispersions having a low tendency to pass from the liquid state to that of gel during storage. After molding or making up of laboratory articles, the new resins give significantly better and much more uniform results than those known.



   Another advantage of the compositions described is their self-plasticizing nature (intramoleoular plasticization); they require a very small addition of plasticizer only to satisfy exceptional molding conditions. It is further believed that the presence of a polymerizable double bond in the malonic diamide or in the equivalent substances allows to obtain white or barely colored resins and to stabilize the color.



  In fact, this double bond can fix oxygen by eliminating the oxidation products which tend to darken the color.



   As in the previous cases, it is possible to carry out interoondensation in acidic, alkaline or neutral media. For this purpose, it is possible to use inorganic or organic bases, salts with an alkaline, inorganic or organic reaction, if it is desired to operate in an alkaline medium. In the contrary case, mineral or organic acids or acid salts are used. Mixtures of alkaline reacting substances or of acid reacting substances can be used, as the case may be.



   To carry out the condensation, one can mix all the constituents and cause the reaction, or else start a partial reaction between the aliphatic aldehyde and a substance that, and / or between the same aldehyde and the malonic compound, to end with the intercondensation. Each partial condensation can be carried out in an acidic, neutral or alkaline medium, optionally in the presence of fillers, solvents, additives and additives. The methods have been described above.

   The usual proportions include 0.75 to

 <Desc / Clms Page number 17>

 6 mols of aliphatic aldehyde, preferably from 1 to 4 mols, per mol of malonic compound. This results in a methylol or methylene derivative which can subsequently be condensed with a urea substance, or else with a methylol derivative of such a substance (obtained by its reaction with an aliphatic aldehyde). This methylol derivative should generally be prepared using 0.75 to 6 mols of aldehyde, preferably 1 to 4 mols, per mol of urea substance.

   As a result, it usually takes 0.75-6 months of aliphatic aldehyde, and for best results 1.5-2.5 mols of aldehyde per mole total ureic substance plus malonic compound *. For economic reasons, in particular, it is finally advisable not to exceed practically one mol of malonic compound per mol of urea substance and, preferably, to keep below 0.6 mol, practically between 0.05 and Ci, 5 mol of malonic compound per mol of urea matter,
Regarding the conditions of temperature, duration, pressure to achieve interoondensation, we refer to what has already been indicated, the modalities being the same * However,

   it is advantageous to start the reaction in an alkaline medium and to end it in an acid medium
Soluble and fusible resinous substances are thus obtained, but which can be hardened by heat, optionally under pressure, by becoming insoluble and infusible. It is possible to incorporate in these resinous syrups setting catalysts having a direct or latent action, the addition of these catalysts being made in the syrups prepared. However, by introducing certain compounds capable of interoondensation, resins which set spontaneously by heat are obtained which do not require a setting catalyst.



   In their uncured form, the resins obtained can be clear liquid, colorless, soluble in water, or else be in the form of milky dispersions * These substances can be concentrated or diluted and give, for example, compositions for coatings whose viscosity and concentration can be adjusted at will. Such liquids serve as varnishes, adhesives, etc. They can be mixed with fillers, dyes, lubricants, etc. to transform them into compositions for molding, EXAMPLE 19-
Aqueous formaldehyde at approx. 37.2% - 161; urea - 54; malonic diamide-10.2; caustic soda - 0.2 in 5 parts of water; ohloroacetylurea - 3.45.

   The first three reagents are mixed in the order given, then after dissolution, caustic soda is added and heated for 30 minutes under reflux. We then add

 <Desc / Clms Page number 18>

 the last reagent and heating is continued for another 12 minutes, The chbra-cetylurea condenses with the intercondensation product of urea, formaldehyde and malonic diamide, resulting in a syrup that can set without catalyst ad hoc. The molding is carried out after addition of 74.8 parts of alfa fluff and 0.58 of zinc stearate, then drying for 85 minutes around 55. The parts molded in 3 minutes at 135, under 280 kg / cm2, match the shape of the mussels, are tenacious and their surface pleasant.



  EXAMPLE 20 -
Same formula as for Example 19, except replacement of the chloroetylurea by a latent catalyst, dietbylchloracetamide, which is added to the interoondensation product of the first reactive tris * Heating is continued for 10 minutes under reflux and mold following Example 19, obtaining similar results * EXAMPLE 21-
Formaldehyde, urea and malonic diamide according to Example 19, phthalic anhydride - 5. The four components are mixed in the order shown.



  Boil and let cool; the syrup sets quickly, becoming insoluble and infusible.



    EXAMPLE 22-
Same formula as for the previous example, except 1.2 10% acetic acid instead of 5 phthalic anhydride. Same technique as for example 21.



  Heating for 6 minutes under reflux. The syrupy resin sets rapidly at 120-150, becoming insoluble and infusible.



  EXAMPLE 23-
In the following order, t approximately 37.2% aqueous formaldehyde is mixed. 1611 urea-54; malonic diamide - 7.95; hydrochloric acid - 0.018 dissolved in 5 parts of water. The resinous syrup obtained rapidly becomes insoluble and infusible between 120 and 150 approximately. EXAMPLE 24 - The constituents are mixed in the order indicated below: urea-54, aqueous ammonia at approx. 28%. - 7.6, approx. 37.2% aqueous formaldehyde -161, caustic soda in 1.5 parts of water - 0.06, malonic diamide - 10.2.

   The mixture is heated for 30 minutes under reflux, then 0.042 of hydrochloric acid dissolved in

 <Desc / Clms Page number 19>

 11.7 parts of water * Heating is continued for 10 minutes under reflux * For the molding, 71.3 parts of alfa flask, 0.59 of zinc stearate are incorporated.



  Dried 90 minutes at around 55, The parts set in 3 minutes at 130 under 280 kg / cm2; their surface is beautiful and follows the details of the mold well.



  EXAMPLE 25 - Berne composition as for Example 24; except that the hydrochloric acid is replaced by 5.85 parts of 10% acetic solution. The first 4 components are mixed in the order indicated, then the malonic diamide is added and heated under reflux for 30 minutes, After incorporation of the acetic acid; the mixture is heated for a further 10 minutes under reflux and the molding composition is prepared as in Example 24, except for substitution of wood taurine for the alfd flock. Dried 3 1/4 hours around 55. and we mold around 135. The parts obtained are tenacious, have a good surface and the molding composition is indeed plastic.



  EXAMPLE 26 -
Same formula and same method as for Example 25, but the acetic acid is omitted. For the casting, triturates with 71.3 parts of alfa floche and 0.59 of zinc stearate. Dried 90 minutes at 55 minutes, then 3.51 parts of phthalic anhydride are added in a ball mill to catalyze the setting.



  The mold is molded for 3 minutes at 130 at 280 kg / cm2, and pieces are obtained which are firmly set, tenacious and of good appearance.



    EXAMPLE 27 -
Except acetic acid, same composition as in Example 25. The first four ingredients are mixed in the order indicated, then, when the solution is clear, the malonic diamide is added and heated for 30 minutes under reflux. 3.51 parts of monochloracetamide are then incorporated. The mixture is heated for a further 12 minutes under reflux, resulting in a syrupy resin which can be hardened without the addition of catalysts. The same ingredients as in Example 26 are added thereto, except phthalic anhydride. Dried 90 minutes around 55, molded according to Example 19 and parts similar to those of this example are obtained.



    EXAMPLE 28 - Urea - 54 is mixed in the order indicated; aqueous ammonia at approx. 28% - 15; aqueous formaldehyde at approx. 37.2% - 161; malonic diamide - 10.2, APRAS heating for 30 minutes under reflux, 71 parts of floche are incorporated

 <Desc / Clms Page number 20>

 alfa and 0.6 zinc stearate. The mixture is dried for 3 hours 25 minutes at around 55 and after molding at 130 at 280 kg / cm 2, parts are obtained which fill the mold well, have a good surface and have set in the whole mass.



    EXAMPLE 29 -
The resinous syrup is prepared as in Example 28, then 6 parts of 10% acetic acid solution are added and a further 5 minutes under reflux are heated. The molding compositions were prepared as in Example 28, reducing the heating to one hour 41 minutes at 55. The molding was carried out according to Example 28 but the setting speed was greater. The castings have the oars properties.



  EXAMPLE 30 -
3.6 of chloracetamide are added to the resinous syrup prepared according to Example 28, and the mixture is heated for a further 5 minutes under reflux. The fillers and lubricants are incorporated as for Example 28, dry 2 hours 7 minutes, mold at 130 under 280 kg / cm2, and obtain tough parts, having set well, with good surface and resistant to humidity. , heat and fading.

   The syrup and the molding compositions derived therefrom set more rapidly under heat than the corresponding products of Example 29, EXAMPLE 31 -
The following are mixed in the following order: urea - 54, hexamethylene tet ratine 7, 37.8% aqueous formaldehyde - 151; malonic diamide - 10.2, After heating for 30 minutes under reflux, incorporation of 77.9 parts of alfa flask and 0.56 of zinc stearate and drying for 1 hour 35 minutes at 55, a good hardening plastic composition is obtained. uniformly in three minutes at 280 kg / cm2. The parts are hard, dense, and suitable for a wide variety of uses.



  EXAMPLE 32 -
To the syrup prepared according to Example 31, 0.04 hydrochloric acid, dissolved in 11.1 parts of water, is added. The molding composition was prepared as in Example 31, dried 1 hour 55 minutes at 55, and molded as in the previous example. The only effect of the acid inoorportation is to accelerate the setting, but the castings have the same general properties *

 <Desc / Clms Page number 21>

    'EXAMPLE 33 -
To the resinous syrup of Example 31, 5.6 parts of 10% acetic acid are added. The molding composition is prepared as in Example 31. It is dried for 2 hours 5 minutes; after molding, the parts are similar to those of Example 31.



    EXAMPLE 34 -
To the resin of Example 31, 3.33 parts of phthalic anhydride are added, then the filler and lubricant according to Example 31 are incorporated and dried for 95 minutes at 55. The castings are very similar to those in Example 31, EXAMPLE 35 -
In the syrup obtained according to Example 31, 3.33 parts of chloracetamide, 77.9 of alfa fluff, 0.56 of zinc stearate are incorporated. Then heated 232 minutes at 55 to intercondens the chloracetamide, at the same time as the water is evaporated. Casting at 135 under 280 kg / cm2 provides parts exceptionally resistant to heat, humidity and fading.



  The composition is very plastic. The parts have excellent mechanical resistance, their surface is free of irregularities. These molding compositions are more stable over time than similar compositions with latent or active catalyst * They harden quickly and uniformly by heat * EXAMPLE 36 -
The procedure is as for Example 35, except substitution of the chloracetylurea for the chloracetamide.

   The molding composition is prepared as in this example, dried for 4 hours and molded at 130, obtaining parts similar to those of Example 35, EXAMPLE 37 -
Mix in order of aqueous formaldehyde at approx. 37.2% - 161; urea - 54; -1.4 hexamethylene tetramine; malonic diamide - la, 2, caustic water - 0.6 in 1.5 parts of water. It is heated to boiling under reflux for 40 minutes, then 34 drops of 10% acetic acid are added. After heating for 10 minutes under reflux, the plastic molding composition is obtained by incorporating 75.6 parts of alfa fluff and 0.57 of zinc stearate * Dried 3 and a half hours at 55 *, and mold 6 minutes at 135 under 280 kg / cm2.

   The parts are stubborn and beautiful in appearance.

 <Desc / Clms Page number 22>

 



  EXAMPLE 38 -
Work is carried out according to Example 37, without removing the acetic acid. 75.6 parts of alfa floche, 0.57 of zinc stearate and 1.14 of dispersed phthalic anhydride are incorporated into the liquid resin. in aloool. Dry 340 minutes at 55. The molded parts have the same general properties as those of Example 37.



    EXAMPLE 39 - Example 37 is followed by replacing acetic acid with 0.04 parts of hydrochloric acid in 11.4 parts of water. The mixture is heated under reflux for a further 10 minutes. The molded parts are prepared according to Example 37 (drying 4 hours) and have the same general properties.



    EXAMPLE 40 -
Except for acetic acid, the syrupy resin is prepared according to Example 37 with heating for 40 minutes under reflux. 1.14 parts of chloroacetylureas, 75.6 of alfa flask, 0.57 of zinc stearate are then added. Heated 13 and a half hours at 55 to intercondens the chloroacetylurea with the other constituents. The mass is dried. The molded parts as in Example 37 are resistant to heat, humidity and discoloration. They have a good appearance, they set in the whole mass and are tenacious. The composition is very plastic.



    EXAMPLE 41 -
The resinous syrup is prepared as in Example 37, removing the acetic acid (reflux 40 minutes); sodium chloroacetate is incorporated as a latent catalyst, and heating is continued for 10 minutes. The molding composition further comprises 75.6 parts of alfa flock and 0.57 of zinc stearate. Drying 5 hours at 55 *, molding 5 minutes at 130 under 260 kg / cm2. The parts have the general properties described in Example 37.



    EXAMPLE 42 -
Example 41 is followed, but the sodium chloroacetate is replaced by 46 drops of diethylchloroacetamide as latent catalyst. Heating under reflux 40 minutes before, 10 minutes after addition of the catalyst. Molding composition as in Example 41. Drying 3 3/4 hours; molding at 135.



    Property * of parts similar to those in example 37.

 <Desc / Clms Page number 23>

 



    EXAMPLE 43 -
One mixes in the following ocher t urea - 54: aqueous ammonia at 28% approx. -7.5; 37.2% formaldehyde approx. - 161; caustic soda in 1.5 parts of water - 0.06; malonic diamide - la; 2 * After 30 minutes under reflux, 0.92 of monochloracetamide dissolved in a little water is added, and eight sheets of special quality paper for laminar articles are impregnated with this resinous syrup *
 EMI23.1
 It is air-dried to facilitate handling, then 65 minutes at 65 i The inter-condensation of ethyl acetamide then continues * The dried leaves are superimposed and they are laminated together by heating them for 30 minutes at 130 * under 105 kg cm2 These sheets are then compressed between unheated trays.

   It is left to cool before removing from the press * The leaves are well agglomerated, the surface is beautiful and the product is extremely resistant to water, It does not tend to disintegrate after the action of boiling water for 5 minutes, A
 EMI23.2
 Similar product, incorporating 1.38 of monochloracitamide, had the same general properties.



   As in β-ketone ester resins, one can use
 EMI23.3
 some aliphatic aldehydes or mixtures of these aldehydes or aldehyde-generating substances, optionally mixed with formal- 4hyde ot "1f.Dre8 aliphatic aldehydes. The urea mentioned in the above examples can be replaced by any urea substances, in particular those enumerated above. Similarly, instead of malonic diamide, it is possible to use
 EMI23.4
 the malonic compounds having the general formulas a Be m.cr.aa2ocr.1 # B. and BOSy. # 2. #.

   In these formulas, Y represents an oxygen or sulfur atom with a double bond and R a univalent radical such as those indicated above.
 EMI23.5
 In this series, we find the following non-limiting examples! s cyanaedtamide, malonic monothiodiamide, malonic dithiodiamide, malonic diamides substituted once on each of the nitrogen atoms by a phenyl group, totyl,
 EMI23.6
 benzyl. p-hydromhenyl, p-monophenyl, etc. One can obviously associate two or more malonic compounds which intervene each one with its particular properties, or else two or more urea substances, by
 EMI23.7
 example urea and thiourea, thiourea and allylurea, urea and melamine, thiourea and guaaldine, summer *.

   Finally, it is possible to use one or more aldehyde with one or more malonic compounds and one or more urea substances.



   As shown in the previous examples, potentially reactive resins can incorporate a setting catalyst into their molecule.
 EMI23.8
 latent or active. for example diethylch10racetamide (latent catalyst).

 <Desc / Clms Page number 24>

 



  This substance belongs to the class of amides derived from secondary amines and halogenated in alpha, in beta or at the same time in alpha and beta. The incorporation of halogenated reagents of this kind has already been described.



   As for the beta ketone ester resins described above, modifying substances can be incorporated therein, in particular of high molecular weight, having or not having resinous characteristics, alcohols or polyaloools, amides or polyamides, amines or polyamines, aminophenols, ete6o *
When additional plasticization is necessary, in particular in the special cases indicated above, known plasticizers can be used, such as alkyl phthalates, phosphoric esters of phenols, etc.



   With regard to the use of fillers, dyes, lubricants for molds, substances conventional in the molded materials industry are employed. The charges are of all known species. The incorporation of these substances is carried out according to the usual techniques in the plastics industry.



   Finally, the applications are those of synthetic resins, for example as flame retardants, water repellents, artificial textiles and fabrics, optionally impregnated with a suitable finish. The parts that can be manufactured are, for example, Paris articles, boxes, household utensils, decorative parts, paints, varnishes, lacquers, enamels, articles suitable for all electrical uses, for example arc extinguisher tubes, enamelled wires, agglomerated mica flakes, laminar insulators, coils impregnated with these insulating resins, etc ...


    

Claims (1)

ABSTRACT 1 - Resinous compositions resulting from the interoondensation of the following constituents a) - An aliphatic aldehyde and / or a material generating such an aldehyde. b) - A substance of the nature of urea. c) - A substance containing an active methylene (CH2) group, or an active monosbustituted methylene (CHR) group. In these formulas, R denotes an atom or a univalent radical. Two or more substances from each of the above three categories can be used together. 2 - general application biodes comprising as substances with an active methylene group the use of 1 <Desc / Clms Page number 25> EMI25.1 a) - A beta ketone ester, the type of which is ethyl acetylacetate; p) A malonic diester whose type is diethyl malonate b1) - A malonic monoester whose type is ethyl acid malonate; a) - A malonic diamide or dithiodiamide or malonic amide and thioamide; c1) - Malonic dinitrile; c2) - A substance both nitrile and amide or malonic thioamide. 3 .- To the main constituents can be added constituents EMI25.2 secondary intercondansable with the former and whose presence in the resinous mold gives it spontaneous setting properties at high temperature $ for example monochloracetamidel ohloraoetylurea, chlora-edtonitrile, symmetrical dichloraoetone, glycine, nitrourea , etc * ,, 4 .- General modalities of preparation concerning! t a) - The preparation of the resinous substance in two phases, leading to a syrupy intermediate substance which can be stored cold for a long time without appreciable modification of its properties (first phase). but being able to set hot, possibly under pressure, this setting constituting the second step; b) - The setting can be catalyzed by the incorporation of a substance with direct action, for example an acid, or with latent action, for example sodium chloroetate; @) - The preparation of the syrupy resin is carried out under atmospheric pressure or under higher or lower pressure, preferably under atmospheric pressure at the boiling point under reflux; EMI25.3 d) - The intercondensation reaction is catalyzed by the use of an alkaline medium or an acidic medium, preferably alkaline, with the simultaneous use of a weak base such as ammonia or organic bases (primary amines preferably) and a strong base, for example cauatic soda, the final setting can be catalyzed, on the contrary, by a substance with an acid reaction, for example acetic acid or hydrochloric acid, or else by an anhydride, such as phthalic anhydride. EMI25.4 e) - The intercondensation is carried out according to one of the methods below. ej - All the constituents to be condensed, as well as the catalysts, are mixed, and the intercondensation is continued to the desired point. eg) - Part of the aldehyde is intercondensed separately with the urea component, then the other components are added and the inter- EMI25.5 condensation, eg) - One starts with the separate condensation of the component containing an active methylene group, with part of the aldehyde, then one ends by adding the other components and continuing the reaction. e4) - Part of the aldehyde is condensed separately with the constituent medium EMI25.6 tbylenic, another part of the aldehyde with the uraemic constituent, then the products obtained are mixed, the condensation of which has been stopped to the desired degree, and the interoondensation is carried out. eg) - When the cross-fertilization product additionally comprises a substance which must function as an internal latent catalyst and incorporated into the mo- EMI25.7 the resinous ecule, this latent catalyst can be intercondensed with the other constituents *, according to any one of the variants (E1), (e2), (e3), or (e4). <Desc / Clms Page number 26> f) - When the condensation reaches the desired degree, the molding substances, fillers, lubricants, possibly plasticizers, etc. are incorporated. The mixture is worked to homogenize it, it is dried at room temperature or relatively low, it is crushed and molded at a temperature above 100, preferably under a pressure of 80 to 500 kg / om2, g. usually between 125 and 300 kg / cm2. g) - The proportion of aldehyde is generally between 0.75 and 10 months of aldehyde per mol of the total urea substance plus substance containing an active methylene group, preferably from 1 to 6 months of aldehyde. h) - The molar proportion of the substance (s) with an active methylene group relative to the urea substance (s) is at most 100%, and preferably less than about 35%. The usual proportions are of the order of approximately 5 to 25%. i) - To the basic constituents of paragraph 1-) we can add organic modifiers having at least one reactive group per molecule. 5, - New industrial products consisting of t a) - resinous syrups prepared according to the invention. b) compositions for plasters, coatings, adhesives, in particular varnishes, paints, lacquers, enamels based on these soluble and fusible resins. c) - Iwa molding compositions containing these resins in the soluble and meltable state, but dehydrated and also containing the usual fillers, dyes, pigmenta, lubricants, plasticizers, etc.. d) - The molded parts prepared by means of these compositions, or by the resins in the pure state but having set in the heat. e) - Agglomerated laminar compositions based on paper, fabric, asbestos sheets, mica flakes, etc. and on an agglomerating agent consisting entirely or mainly of the resins described. 6 .- Application of the resins described in the preparation of new insulators for electrical engineering, and in particular of aro fire extinguisher tubes.