Patent Publication Number: US-4370424-A

Title: Plastic and foam plastic and method for making them

Description:
This is a continuation of application Ser. No. 065,039, filed Aug. 9, 1979 now abandoned. 
    
    
     The present invention relates to new plastics and foam plastics and to methods for making the same. 
     Urea-formaldehyde-resin foam plastics (UF foam plastics), methods for making them and fields of application for the same are known from the literature and patents. 
     To make UF foam materials, a water-soluble tenside and a UF resin (UF condensation product) are required. The constitution of UF resins has still not been fully investigated. 
     Suitable tenside mixtures contain, besides the actual tenside in diluted solution, a hardener and a chemical substance to prevent mildewing in the final UF foam plastic, e.g. resorcinol. Compositions have been described in the literature. 
     As hardeners, preferably inorganic acids, particularly phosphoric acid, are used. As tenside, e.g. diisobutyl naphthalene sulfonic sodium, a water-soluble, anionic tenside, called DIBNS-Na, can be used. 40 ml of a commercial tenside mixture as suited for making foamed plastics consist of, for example, 13.83 g DIBNS-Na, 4.40 g resorcinol and 11.80 g of 85%-phosphoric acid in the form of a yellowish, highly viscous paste with ca. 24 to 30% water content (pH 10 to 12) or in the form of a dry substance as a light, hygroscopic powder (pH 7 to 11). 
     For making UF foam plastics, the tensides in the foam solution are strongly diluted with water. The ready-for-spraying solutions have a solid content of between 2 and 5%. 
     Earlier it was assumed that the tenside served only as a carrier for the UF resin (Plastverarbeiter 9 (1958) 453); later, however, it was believed that it might also react ionically with the reactive groups of the UF resin (Plastverarbeiter 27 (1976) 235). 
     The addition of other chemical substances to the basic solutions in order to improve the physical and chemical properties of the finished UF foam plastic has also long been known (Kunststoffe 47 (1957) 256). 
     Among many suggestions in the literature, amidosulfonic acid was proposed as a hardener and not as a tenside (Bachmann und Bertz, Aminoplast, VEB-Verlag fur Grundstoff-Industrie, Leipzig 1969). 
     UF foam plastic, e.g. as thermal insulation material in two-sheet masonry, may frequently give off pungent formaldehyde fumes when drying out. Extensive tests were made for the purpose of finding ways to bind this free formaldehyde in any form whatsoever. 
     It was surprisingly found that under certain conditions compounds containing sulfonic groups and aldehydes in the presence of a hydroxy compound reacted quantitatively with one another, and that a new plastic material was formed thereby. 
     The method according to the invention for making this plastic is characterized in that: 
     (a) one or several compounds containing sulfonic groups in the presence of: 
     (b) a mono-, di- or polyhydroxy compound or mixtures thereof and 
     (c) possibly one or several inorganic or organic acids provided, when (a) is present in form of a salt, (c) must be present, 
     in the form of a concentrated aqueous solution with a water content of about 25 to 30%, as well as 
     (d) possibly other, customary additives and 
     (e) possibly other synthetic and natural resins are reacted with 
     (f) one or several saturated or unsaturated aldehydes or mixtures thereof or a compound which is able to form an aldehyde in acid medium, 
     under stirring, with or without addition of heat. 
     This was surprising particularly for the reason that though tenside mixtures that contained sulfonic acid and e.g. resorcinol as hydroxy compound had been used for many years in strongly diluted form in a foaming agent in the preparation of UF foam plastics no substantial reaction between the tenside and excess formaldehyde in the UF plastic had ever been observed. 
     It was further surprisingly found that according to the invention foam materials could be produced by foaming of only monomers according to the aforementioned components (a), (b), (f) and possibly (c), without requiring the presence of a finished resin product in the starting materials. Only after everything has been foamed is a resin formed from the monomers. The monomeric components (a), (b) and (c) as used for the preparation of the resin according to the invention are introduced into the resin tank in practically undiluted form, i.e. with a water content of 20 to 30%, and preferably 24%, and the same mixture, but in strongly diluted form as tenside together with the aldehyde into the pressure tank for the foaming agent solution, and then everything together foamed up. 
     The method according to the invention for making foam plastics is characterized in that: 
     (a) one or several compounds containing sulfonic groups in the presence of: 
     (b) a mono-, di- or polyhydroxy compound or mixtures thereof and 
     (c) possibly one or several inorganic or organic acids provided, when (a) is present in the form of a salt, (c) must be present, 
     in the form of a concentrated aqueous solution with a water content of 20 to 30%, as well as: 
     (d) possibly other, customary additives and 
     (e) possibly other synthetic and natural resins are foamed with 
     (f) one or several saturated or unsaturated aldehydes or mixtures thereof or a compound which is able to form an aldehyde in acid medium, 
     under addition of a tenside in a dilution as usually used for foam production of component (f) in a conventional foam making installation. 
     Numerous reactions between formaldehyde, other aldehydes, chemical compounds of an inorganic and organic nature are known; and also the production of synthetic resins. The most widely known are urea-, phenol-, resorcinol-, cresol- and xylol-formaldehyde resins. Further compounds were also prepared: 
     Huston and Eving prepared xylol-formaldehyde oligomeric aromates with formaldehyde in the presence of acids (Amer. Chem. Soc. (1915) 2394). 
     Formaldehyde-sulfuric acid is formed by the reaction of sulfur dioxide and formaldehyde (Reinking, Denehl and Labhard (Ber., 38 (1905) 1075). 
     Kalber obtained methylene-bis-derivatives from beta-naphthyl sulfonic acid and formaldehyde in aqueous solution (U.S. Pat. No. 2,056,924). 
     Phenol-formaldehyde-novolac (1 mol) can be sulfonated with hydrosulfuric acid (0.45 mol); also ligninsulfonic acids react with phenol-formaldehyde condensates (British Plastics (1949) 641). 
     Cohn describes a detection of formaldehyde up to 0.00005 mg by placing a layer of the same volume of a 0.1%-resorcinol solution over the solution to be analyzed and then adding slowly 2 ml of conc. sulfuric acid; in the presence of formaldehyde a violet-red zone will result (Chem.Ztg., 45 (1921) 997). 
     Ellis obtained slightly polyvalent phenolic resin products by reaction with formaldehyde, which are hard to isolate in the intermediate stage (&#34;The Chemistry of Synthetic Resins&#34;, 277-395, Reinhold Publishing Corp., 1935, New York). 
     Fuler prepared methylol derivatives of hydroquinone with formaldehyde (Chem. Centr. (1941) I, 128-9) and CARO prepared methylene-bis-pyrogallol, the latter with formaldehyde in the presence of hydrochloric acid, at room temperature (Ber. 25 (1892) 941). 
     The new plastics not only yield foam plastics which give off practically no pungent formaldehyde or only for a relatively short period, but also have vis-a-vis UF plastics and UF foam plastics strongly improved stability to acids, alkalis and organic solvents, good temperature and flame resistance, as well as good mechanical and electrical properties. They, furthermore, can be produced at room temperature with simple stirring which results in low costs and energy savings. 
     The plastics according to the invention can be used in the production of fibers, injection moldings and thermal insulators. 
     The foam plastics made from these plastics find use as insulating and thermal insulating materials, in plastoponics, as oil absorbents, wound dressings, flower pinning materials, and in powder form as fillers, filter materials and pharmaceutical powders. 
     As compounds containing sulfonic groups there may be used sulfonic acids, sulfinic acids and sulfamidic acids and their salts either alone or mixed together. 
     Examples are arylalkyl sulfonates like alkyl benzene sulfonates and alkyl naphthalene sulfonates, which are used as important interface surface-active materials. 
     Naphtholsulfonic acids, naphthylaminesulfonic acids and aminonaphtholsulfonic acids and their sodium salts are known as readily available basic or intermediate products in dye manufacture. Anthraquinonesulfonic acid and its sodium salts are likewise intermediates in dye synthesis. A list of these compounds is given in &#34;Rompps ChemieLexikon&#34;, 7.Ed., P. 2259. 
     Naphthalenesulfonic acids are known as mono-, di-, tri- and tetrasulfonic acids. 
     Heterocyclic sulfonic acids can be produced, for example, from acridine and acridone by means of chlorosulfonic acid. 
     Sulfamic acids are, for example, amidosulfuric acid, amidosulfonic acid or compounds to be denoted as sulfamidic acids. 
     A number of sulfonic acids that can be used according to the invention are given as follows: phenolsulfonic acids, alkylsulfuric acid and alkylsulfuric salts, alkylsulfonic chlorides, alkylsulfonic esters, alkylsulfonic acid and alkylsulfonic salts, paraaminobenzenesulfonic acids, aminonaphtholsulfonic acids, aminosulfonic acids, anilinsulfonic acids, anthraquinonesulfonic acids, arylsulfonic acids and their amides and chlorides, ethanesulfonic acid, ethylsulfuric acid, benzenedisulfonic acids, benzenesulfamic acid and benzenesulfinic acid, benzcatechinsulfonic acid, bromobenzenesulfonic acid, bromocamphorsulfonic acid, chlorosulfonic ester, diaminoanthraquinonedisulfinic acid, nitrobenzolsulfonic acid, nitronaphthalenesulfonic acid, nitroso-beta-naphthol-6-sulfonic acid, phenoldisulfonic acid, phenolsulfonic acid, phenylhydrazinesulfonic acid, phenylhydrazinesulfonic sodium, pyridinesulfonic acid, thiophenesulfonic acid, vinyl-sulfonic sodium salts, dinitro-oxynaphthalene-sulfonic acid, halogensulfonic acid, hydrazinesulfonic salts, indigosulfonic acid and indigodisulfonic acid, isododecylbenzenesulfonic sodium, perfluorosulfonic acid, bathocuproindisulfonic sodium salt and disodium salt, dimethylbenzenesulfonic acid, morpholino-ethanesulfonic acid, naphthoquinonesulfonic acid and salts and rarer sulfonic acids such as ferrospectral (III (II-pyrinyl)-V, VI-bis (IV-phenylsulfonic acid)-1,2,4-triacine-disodium salt). 
     Particularly preferred are aryl and alkylaryl sulfonic acids and their salts, and particularly diisobutylnaphthalenesulfonic sodium. 
     They can be used with success in both aqueous and nonaqueous solutions in relatively concentrated form. 
     Aldehydes to be used according to the invention are both saturated and unsaturated aliphatic and aromatic aldehydes as well as compounds that are able to form aldehydes in acid medium. 
     Suitable examples for aldehydes are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, glutardialdehyde, pelargonaldehyde, furfurylaldehyde, crotonaldehyde, tiglicaldehyde, sorbicaldehyde, stearinaldehyde, malonaldehyde, myristicinaldehyde and pyridinaldehyde as well as glyoxal and mixtures thereof. An example of a compound which is able to form an aldehyde in acid medium is hexamethylenetetramine. They can be used in amounts of about 0.5 to 12 mol per mol sulfonic group-containing compound. Usually, the same are used in their commercially obtainable concentrations which may differ from one aldehyde to another. Especially preferred is a 35%-aqueous formaldehyde solution. 
     Phenols are particularly suited as hydroxy compounds. These phenols can be mono- or polyvalent, substituted or not substituted phenols such as phenol, resorcinol, brenzcatechin, hydroquinone and their tautomeric carbonyl forms; trihydroxybenzenes such as pyrogallol, hydroxyhydroquinone, polyhydroxybenzenes in their three possible forms (1,2,3,4-, 1,2,3,5- and 1,2,4,5-tetrahydroxybenzene); dihydroxytoluene, salicylic acid and gallic acid as well as mixtures thereof. They can be used in amounts of 0.1 to 5 mol per mol of compound containing sulfonic groups. Especially preferred is resorcinol. 
     When using compounds containing sulfonic groups in the free acid form the use of organic or inorganic acids as hardeners is not absolutely necessary, but has proved to be of a great advantage. When, on the other hand, the compounds containing sulfonic groups are used in the form of their salts then the use of an acid is necessary. 
     Acids suited according to the invention can be practically all inorganic and organic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid and acetic acid. Especially preferred are phosphoric and sulfuric acids. 
     Usually, the acids are used in their commercial concentrations; however, the same can also be used in more diluted form. 
     The amounts to be used can be up to about 10 mol, relative to one mol of the compounds containing sulfonic groups. 
     The solutions of the starting compounds should be concentrated and contain only enough water or non-aqueous solvent to keep the products dissolved. 20 to 30% water have proved to be of particular advantage. 
     Other, usually used additions according to the invention are: fillers, dyestuffs, pigments, alcohols, inorganic or organic fibers, buffer substances, indicators, catalysts, regulators, emulsifiers, plasticizers, stabilizers, displacement reagents, deuterated compounds, metalloorganic compounds, metals and metal salts, alcoholates, phenolates, acetyl acetonates, solvents, hydrides, amides, heteroelement compounds, products for regulating the polymerization, polyaddition and polycondensation, radicals and radical initiators, cationic and anionic initiators, enzymes, vitamins, hormones, steroids, biochemicals, additives, flame retardants, cross-linking agents, expanding agents, UV stabilizers, antistatic conductive polymers or substances. 
     The same can be used alone or in mixture with one another, and in amounts up to about 50 mol per mol of compound containing sulfonic groups. 
     Also other known synthetic or natural resins or mixtures thereof can further be used before or during the condensation process. The said resins can be soluble or insoluble in water. Suitable resins are for example: resins based on aminoplasts, phenoplasts, desmodur, alpha-omega-urea resins or mixtures thereof, UF, PUR, PF resins, as well as styrene polymers, elastomer-modified copolymers, polyamides, polymethacrylates, polycarbonates, polytetrafluoroethylene and copolymers, basic substances for making polyacetals, aromatic polyethers, polyalkylene terephthalates, unsaturated polyester resins, silicone polymers, melamine resins and epoxide resins. The same can be used in amounts of up to 80 wt.-%. 
     The formation of the synthetic resins according to the invention takes place in most cases at room temperature without addition of heat, the temperatures rising at times up to 80° C. through exothermic reactions, depending on the kind of starting materials and additions used. With the more diluted solutions, however, external heating may be required or individual components may be preheated to a predetermined temperature so as to affect reaction times. To retard the reaction, individual substances or the entire solution may be cooled to 0° C. or diluted solutions may be used. The latter method is preferred where a particular mixture tends to explosionlike reactions. Usually, the reaction is effected at atmospheric pressure under simple stirring. However, the reaction can likewise be effected in vacuum or under pressure. 
     By varying the mole ratios of the starting materials within the aforementioned ranges, products with differing physical properties can be obtained such as sediments, precipitates, oligomers, lavalike products, slightly hardened products, viscous solutions, fibers or quantitatively hardened resins. The synthetic resins according to the invention can be hardened by radiation. 
     The transparent substances are of small crystalline structure, while the non-transparent substances are of an amorphous nature. 
     For a preliminary condensation, a small portion of the aldehyde to be used can be added to the reaction mixture, and the remainder added at some later time. 
     As already mentioned, foamed plastics can be produced from the plastics according to the invention, viz. soft (molded and bulk) foam, semirigid, rigid, structural and in situ foamed plastics. 
     Two processes are known in the manufacture of UF foam plastics. Besides the process described hereinbelow, so-called resin foaming is known. A resin and tenside in powder form are mixed together, dissolved in water before use, and the hardener added after the foaming. 
     The foams can be produced in situ or stationary, in pressure tanks or with pumps, or parts of the solutions from pressure tanks or conveyed by pumps can be fed to a foam spray gun (foam apparatus). Any desired pressure and any gas or compressed air as suited for foaming can be used. 
     All apparatuses described in the literature and patent literature can be used for the process according to the invention. It is of no consequence whether the solutions or solid additions are conveyed at an acute angle or at right angles, in parallel flow or in counterflow operation. What is important is that the reaction components are thoroughly mixed so that the necessary chemical reactions are initiated and a foam is produced. 
     It is also possible to produce foams from small handy spray cans in a one- or multichamber system. 
     A foam plastic could industrially be produced by using a tenside in place of a UF resin condensate and as foaming agent a similar tenside slightly diluted with water to which formaldehyde had already been added. Tenside concentrates foam very poorly or not at all. To achieve a foaming action, the concentrated tenside must be diluted with water. The degree of foaming can be readily and rationally determined from the foam spray gun in the Baumann-Graf apparatus. (Chemiker Zeitung, Chem. App. 90 (1966) 449). 
     A concentrated tenside can also be diluted with another sulfonic acid as a dilute or saturated aqueous solution. As a result, the reaction time of resin formation can be shortened. 
    
    
     The examples that follow serve for a further explanation of the invention. 
     EXAMPLE 1 
     400 ml of an aqueous mixture of 138.3 g DIBNS-Na, 44 g resorcinol and 118 g of 85% -phosphoric acid with a water content of about 24% were mixed with 40 ml of 35%-formaldehyde and stirred with a glass rod, the temperature rising thereat from 22° C. to 42° C. The dark-brown solution changed its color and first turned light-brown. It then became solid after a few seconds, spontaneously turning red during that time. 
     A sample of this synthetic resin of 480 g was dried in an oven at 105° C. for one hour. Following that, the sample weighed 431.5 g. After two years of storing at room temperature, the weight dropped to 320 g. After five years, the weight was still the same. The weight loss of 33.33% roughly corresponds to the amount of water of the starting solution. The substance did not change over the entire period. 
     EXAMPLE 2 
     10 g of the resin from Example 1 were pulverized, mixed with 100 ml of a 10%-sodium hydroxide solution, and stirred for 15 hours; the mixture was then filtered. 
     A slightly brownish, needle-shaped substance precipitated from the filtrate which was washed with methanol, acidified with sulfuric acid, and shaken out with ether. After evaporation of the ether, no residue remained. 
     The precipitate of the resin treated with sodium hydroxide solution gave a yield of 94% after drying at 115° C. This shows that the reactants had combined almost quantitatively. 
     EXAMPLE 3 
     10 g DIBNS-Na were acidified with sulfuric acid and shaken out with ether. The diisobutylnaphthalenesulfonic acid went over to the ether and remained after evaporation of the ether. Since, in contrast to the above, no diisobutylnaphthalene sulfonic sodium was found to exist in Example 2 it shows that the sulfonic acid in Example 2 is incorporated in the molecule. 
     EXAMPLES 4 through 23 
     In the examples that follow, differing amounts in formaldehyde were tested. 
     
                       TABLE I                                                     
______________________________________                                    
Differing amounts of formaldehyde added to a 40 ml basic solution         
(BS) consisting of: 13.83 g diisobutylnaphthalene sulfonic sodium         
4.40 g resorcin, 11.80 g (85%-) phosphoric acid in aqueous solution       
(water content ca. 24%) - In all examples,                                
the formaldehyde was added with stirring                                  
Exam- 35%-     Starting        Reaction                                   
ple   formalde-                                                           
               tempera- Max.   time    Color                              
No.   hyde, ml ture, °C.                                           
                        temp. °C.                                  
                               sec.    state                              
______________________________________                                    
4     1        28       30     no                                         
                               noticeable                                 
                               reaction                                   
5     2        28       45     striation                                  
6     3        28       40     striation                                  
7     4        24.5     55.5   48      pink, solid                        
8     5        24.5     57     48      pink, solid                        
9     6        24.5     57     48      pink, solid                        
10    7        24.5     59.5   48      pink, solid                        
11    8        24.5     58     48      pink, solid                        
12    9        27.5     59.5   30      pink, solid                        
13    10       27.5     56     48      pink, solid                        
14    11       23.5     52     45      pink, solid                        
15    12       23.5     50.5   45      pink, solid                        
16    13       23.5     51     60      pink, solid                        
17    14       23.5     49     75      pink, solid                        
18    15       23.5     48     75      pink, solid                        
19    16       23.5     49     75      pink, solid                        
20    17       23.5     48     90      pink, solid                        
21    18       24       50     90      pink, solid                        
22    20       24       48     95      pink, solid                        
23    25       24       48     120     pink, solid                        
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         ______________________________________                                    
Weight of resins from the reactions using differing                       
amounts of formaldehyde                                                   
       Weight 12 days                                                     
                   30 days       8 months                                 
Example                                                                   
       after reaction                                                     
                   after reaction                                         
                                 after reaction                           
______________________________________                                    
4      40.77       cannot be weighed                                      
5      41.85       &#34;                                                      
6      42.93       &#34;                                                      
7      44.01       40.10         38.15                                    
8      45.09       40.30         31.90                                    
9      46.17       40.40         32.20                                    
10     47.25       42.24         33.55                                    
11     48.33       41.72         32.53                                    
12     49.41       40.00         32.25                                    
13     50.49       41.12         32.48                                    
14     51.57       41.91         32.45                                    
15     52.65       42.25         33.24                                    
16     53.75       42.81         33.65                                    
17     54.81       42.21         33.00                                    
18     55.89       44.26         33.18                                    
19                 43.88         32.90                                    
20                 44.20         33.20                                    
21                 43.86         33.08                                    
22                 not measured  33.10                                    
23                 &#34;             33.88                                    
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     In the following examples, various starting materials, molar ratios, temperatures and addition of other compounds as well as the production of foam materials were demonstrated. 
     EXAMPLE 24 
     1 mol diisobutylnaphthalene sulfonic sodium +0.6 mol resorcinol +2.4 mols phosphoric acid were mixed in concentrated aqueous solution with 0.7 mol hexamethylene tetramine and heated with stirring. At 50° C., at sticky, light-brown, coherent substance was obtained which, after filtering, did not dissolve in water, sulfuric acid, toluene and hydrochloric acid. It turned yellow in ethanol, red in soda lye. The substance could again be precipitated from the soda lye with hydrochloric acid. In nitric acid the substance turned yellow, and was soluble in n-butanol and dimethylformamide. Also from these solutions, the substance could be recovered with hydrochloric acid. Phosphoric acid hardened the solid substance still further. 
     EXAMPLE 25 
     1 mol diisobutylnaphthalene sulfonic sodium +0.6 mol resorcinol, 2.6 mols phosphoric acid and 1.6 mols urea were mixed in concentrated aqueous solution with 2.11 mols formaldehyde. 
     At 50° C., under stirring, a coherent lavalike resin precipitated, a few milliliters of a greenish solution remained. The solid substance was insoluble in cold soda lye and dimethylformamide. In hot soda lye, it turned bloodred, in dimethylformamide ocher. 
     The greenish solution did not react with soda lye, hydrochloric acid, n-butanol, cyclohexane and furfural. 
     EXAMPLE 26 
     1 mol diisobutylnaphthalene sulfonic sodium was dissolved in water and mixed with 0.6 mol resorcin, 2.4 mols phosphoric acid, 1.6 mols urea and 1.1 mols oxalic acid and heated. At 45° C., 0.7 mol hexamethylene tetramine was added. A lavalike resin as in Example 25 formed; however, the remaining solution was yellow-brown. It was dried in an oven. At 105° C., its volume increased about three-fold. 
     The filtered resin was boiled in soda lye, and after cooling, precipitated with hydrochloric acid, filtered and washed out. One part of the purified substance was mixed with a solution of soda lye and copper sulfate, a second part was mixed with a solution of ammonium hydroxide and iron-III-chloride. The corresponding salts were obtained in good yield. 
     EXAMPLE 27 
     1 mol diisobutylnaphthalene sulfonic sodium was dissolved in 5 mols water and heated to 60° C. This solution was then mixed with 20.5 mol resorcinol and 2 mols formaldehyde. No reaction took place; only after addition of 4 mols phosphoric acid did a red colored substance result. 
     This example demonstrates that an acid, phosphoric acid in this case, must be added to split off the sodium in the sulfonic acid so that a reaction can take place. The acid is required as an activator as well as a curing catalyst. 
     EXAMPLE 28 
     1 mol diisobutylnaphthalene sulfonic sodium was dissolved in 5 mols water and 2 mols formaldehyde and 4 mols phosphoric acid added thereto. The mixture was then heated to 60° C. Here too, no reaction took place. Only upon the addition of 0.5 mols resorcinol did a red resin form. 
     It can be inferred from this example that a hydroxy compound, resorcinol in this case, is required as the crosslinker of the reaction. 
     EXAMPLE 29 
     1 mol diisobutylnaphthalene-disulfonic acid was mixed with 10 mol water, 2.14 mol formaldehyde, 1.23 mols resorcin and 4.58 mols phosphoric acid. On heating, the solution reacted, and a precipitate formed. The latter was filtered off and washed with water until the aqueous solution was neutral. The precipitate was rubberlike and of a dark-brown color. It could not be pressed out on a clay plate. The large volume disintergrated after standing in air for 19 days. 
     EXAMPLE 30 
     1 mol diisobutylnaphthalenesulfonic sodium was mixed with 0.6 mol resorcinol and 2.4 mols phosphoric acid in 13 mols water and 0.6 mol formaldehyde added thereto. 
     The initially brown solution became lighter at 35° C., and thickened at 48° C., but was still stirrable at 80° C. It could not be filtered after cooling, but could be pressed on a clay plate. It did not change when drying at 105° C. 
     EXAMPLE 31 
     0.9 mol diisobutylnaphthalene sulfonic sodium, 1.8 mols resorcinol, 0.9 mol hydrochinone, 0.03 mol tin chloride as catalyst, and 8.5 mols phosphoric acid were dissolved in 50 mols water and mixed with 4.8 mols formaldehyde. On heating, a resin precipitated at 50° C. 
     EXAMPLE 31a 
     Foam production: 
     1 l of a commercial tenside consisting of 0.34 g DIBNS-Na, 0.11 g resorcinol and 0.295 g 85%-phosphoric acid in about 24% aqueous solution was introduced into the resin tank of an apparatus used for UF foam plastic production. 1 l of the same tenside which was diluted with 250 cc water and to which 80 cc 35% formaldehyde had been added was introduced into the pressure tank for the foaming agent solution. The whole was then foamed with nozzles used for UF foam plastic production, viz. a 2 mm resin nozzle and 1.5 mm foam nozzle, and with compressed air at 4.5 bars. From the hose connected with the spray gun a slightly yellowish foam emerged which did not collapse. Within 8 minutes, the temperature in the foam rose from 23.5° to 32.5° C. At the start of the reaction, the foam turned reddish. In the course of the reaction, the color turned a deep red. The resultant foam was flexible and resilient, could be dried at 120° C. without any change and under color intensification. Its weight per cubic meter was about 40 kg. 
     The foam was of open pore structure, individual cells being occasionally covered over with resin films, as they appear in a 30 kg UF foam. The foam was hydrophilic. 
     
         ______________________________________                                    
Solution tests  after 24 hours boiled                                     
______________________________________                                    
1.   95%-sulfuric acid                                                    
                    dissolved      --                                     
(1a) 40%-sulfuric acid                                                    
                    no change      no change                              
2.   37%-fuming hydro-                                                    
     chloric acid   no change      no change                              
3.   85%-phosphoric acid                                                  
                    no change      color                                  
                                   intensifi-                             
                                   cation                                 
4.   65%-nitric acid                                                      
                    dissolved      --                                     
(4a) 25%-nitric acid                                                      
                    dissolved      --                                     
5.   96%-acetic acid                                                      
                    no change      no change                              
6.   Absolute alcohol                                                     
                    no change; substance                                  
                                   no change                              
                    turns yellow                                          
7.   Acetone        no change      no change                              
                    substance turns                                       
                    yellow                                                
8.   Dimethylformamide                                                    
                    no change      no change                              
9.   Dioxane        no change      no change                              
                    substance turns yellow                                
10.  Paraffin oil   no change      no change                              
(10a)                                                                     
     Motor oil      no destruction --                                     
11.  20%-soda lye   no change      no change                              
12.  Water          no change      no change                              
                    (the pH value both                                    
                    before and after                                      
                    boiling was 2.5)                                      
______________________________________                                    
 
    
     The melting point of the foam is about 200° C. The foam chars in the flame at about 300° C. without dripping. 
     
                                           TABLE II                                
__________________________________________________________________________
In all examples the aldehyde was added under stirring                     
__________________________________________________________________________
                       Starting                                           
                              Max.   Reaction                             
                       temperature                                        
                              temperature                                 
                                     time                                 
No.                                                                       
   BS                                                                     
     Aldehyde   Hardener                                                  
                       °C.                                         
                              °C.                                  
                                     sec.                                 
__________________________________________________________________________
31b                                                                       
   BS                                                                     
     4 ml formaldehyde                                                    
                4 ml H.sub.3 PO.sub.4                                     
                       30     50     48                                   
32   2 ml formaldehyde                                                    
                2 ml H.sub.3 PO.sub.4                                     
                       20     60                                          
33 BS                                                                     
     6 ml formaldehyde 24     40     40                                   
34   6 ml formaldehyde                                                    
35 BS                                                                     
     5 ml furfurylaldehyde                                                
     (95%)                                                                
36   4 ml formaldehyde 23     70     48                                   
37   6 ml formaldehyde 23     30                                          
38   7 ml formaldehyde 23     29                                          
39   7 ml formaldehyde 22.5   36                                          
40 BS                                                                     
     7 ml formaldehyde 22.5   75                                          
41 BS                                                                     
     7 ml formaldehyde 22.5   75                                          
42 BS                                                                     
     9 ml acetaldehyde                                                    
43 BS                                                                     
     9 ml propionaldehyde                                                 
44 BS                                                                     
     9 ml butyraldehyde                                                   
45 BS                                                                     
     7 ml formaldehyde 23     75                                          
46 BS                                                                     
     7 ml valeraldehyde                                                   
47 BS                                                                     
     7 ml formaldehyde 24     42                                          
__________________________________________________________________________
   Sulfonic acid and/or hydroxy compound                                  
No.                                                                       
   in aqueous solution                                                    
                      Other substances                                    
                                 Remarks                                  
__________________________________________________________________________
31b                              pink, solid                              
32 3.4 anthraquinone-2-sulfonic                                           
   sodium + 1 g resorcinol       red, solid                               
33                    2 ml iron-II-chloride                               
                      solution   red, solid                               
34 5 g p-toluenesulfonic acid                                             
   + 1 g resorcinol              pink                                     
35                               black, solid                             
36 10 g p-toluenesulfonic acid                                            
   + 4.8 g resorcinol            red, solid                               
37 10 g diisobutylnaphthalene-di-                                         
                      10 ml iron-III-chloride                             
                                 brown, solid                             
   sulfonic sodium +                                                      
   3.5 g resorcinol                                                       
38 20 g as in 37 + 1.4 g resorcinol                                       
                      1.4 g tannic acid                                   
                                 brown, solid                             
39 15 g benzenesulfonic acid +                                            
   1.4 g resorcinol              light red, solid                         
40 1.4 g pyrocatechol            red, soft                                
41 1.4 g phloroglucinol          red, soft                                
42                               greasy brown                             
                                 substance, which                         
                                 becomes solid                            
                                 after some time                          
43                               brown substance,                         
                                 hardens with                             
                                 prolonged ex-                            
                                 posure                                   
44                               brown substance,                         
                                 hardens with                             
                                 prolonged ex-                            
                                 posure                                   
45 1.4 g hydroquinone            brown, soft                              
46                               brown substance,                         
                                 hardens with                             
                                 prolonged ex-                            
                                 posure                                   
47 20 g diisobutylnaphthalene-   brown, solid                             
   disulfonic disodium                                                    
   + 4.2 g resorcinol                                                     
__________________________________________________________________________
 
    
     
                                           TABLE III                               
__________________________________________________________________________
                      Starting                                            
                           Max. temp.                                     
                                 Reaction                                 
No.                                                                       
   BS                                                                     
     Aldehyde  Hardener                                                   
                      temp. °C.                                    
                           °C.                                     
                                 time sec.                                
__________________________________________________________________________
48   7 ml formaldehyde                                                    
                      23.5 52                                             
49   7 ml formaldehyde                                                    
               40 ml 98%-                                                 
               sulfuric acid                                              
50 BS                                                                     
     8 ml formaldehyde                                                    
                      18   45    120                                      
51 BS                                                                     
     7 ml formaldehyde                                                    
                      20   40    240                                      
52 BS                                                                     
     4 ml formaldehyde                                                    
                      20   43     80                                      
53 BS                                                                     
     4 ml formaldehyde                                                    
                      18   38                                             
54 BS                                                                     
     4 ml formaldehyde                                                    
                      24         120                                      
55 BS                 24   41    110                                      
__________________________________________________________________________
   Sulfonic acid and/or hydroxy-                                          
No.                                                                       
   compound in aqueous solution                                           
                    Other substances                                      
                                Remarks                                   
__________________________________________________________________________
48 as in example 37 + 5.4 g resorcinol                                    
                                brown, solid                              
49 + 5 g resorcinol             red, solid                                
50 + 2.8 g resorcinol           red, solid                                
51 3 g sulfanilic acid + 2 g resorcinol                                   
                                brown, soft                               
52                  1.4 g ammonium chloro-                                
                    cuprate II  red, solid                                
53 1 g sulfanilic acid          red, semirigid                            
54                  40 ml water red, solid                                
55                  40 ml water red, solid                                
__________________________________________________________________________
 
    
     
                                           TABLE IV                                
__________________________________________________________________________
                           Starting temp.                                 
                                   Max. Reaction time                     
No.                                                                       
   BS                                                                     
     Aldehyde    Hardener  °C.                                     
                                   temp. °C.                       
                                        seconds                           
__________________________________________________________________________
56 BS                                                                     
     7 ml formaldehyde     22      30   30                                
57 BS                                                                     
     4 ml formaldehyde     18      27   127                               
58 BS                                                                     
     4 ml formaldehyde     20      38   240                               
59 BS                                                                     
     4 ml formaldehyde     20      41   300                               
60 BS                                                                     
     7 ml pyridinaldehyde  18      40   60                                
61 BS                                                                     
     4 ml pyridinaldehyde  18      40   80                                
62   2 ml formaldehyde                                                    
                 18.7 ml phosphoric                                       
                           26      35   45                                
                 acid                                                     
63   7 ml formaldehyde                                                    
                 11.8 ml phosphoric                                       
                           26      38   220                               
                 acid                                                     
64   7 ml glutardialdehyde                                                
                 6 ml phosphoric                                          
                           26      40   70                                
     (25%-)      acid                                                     
65   7 ml formaldehyde                                                    
                 11.8 ml phosphoric                                       
                           28      41   68                                
                 acid                                                     
66   7 ml formaldehyde                                                    
                 11.8 ml phosphoric                                       
                           28      40   60                                
                 acid                                                     
67 BS                                                                     
     7 ml pelargonaldehyde 21      35   80                                
68 BS                                                                     
     3.5 ml formaldehyde +                                                
     3.5 ml pelargonaldehyde                                              
                           21      40   80                                
__________________________________________________________________________
   Sulfonic acid and/or hydroxy                                           
No.                                                                       
   compound in aqueous solution                                           
                       Other substances                                   
                                     Remarks                              
__________________________________________________________________________
56 Mixture of diisobutylnaphthalene                                       
                       1.4 g tannic acid                                  
                                     black, solid                         
   di-and-trisulfonic acid +                                              
   1.4 g resorcinol                                                       
57                     1 g tannic acid + 4 ml water                       
                                     brown, solid                         
58                     3 ml ethanol  brown, solid                         
59                     1 g 2-amino-diphenyl-                              
                                     yellow substance,                    
                       amine in 8 ml ethanol                              
                                     solid, after 1 hour                  
                                     recoloration                         
60                                   soft, hardens after                  
                                     12 hours                             
61                                   red, solid                           
62 40 ml of a solution of 282.19 g ben-                                   
   zenedisulfonic (1,3)-disodium in  milky, solid                         
   500 ml water and 3.52 resorcinol  pink, solid                          
63 as example 62                     pink, solid                          
64 40 ml saturated aqueous solution of                                    
                                     turns pink and                       
   diisobutylnaphthalenesulfonic-Na +                                     
                                     solid at 60° C.               
   3 g resorcin                                                           
65 as example 64 and 3 g orcinol     yellow substance,                    
                                     solid                                
66 13.8 g dodecylbenzenesulfonic sodium +                                 
   3 g resorcinol      18 ml water   light pink, solid                    
67                                   light brown, draws                   
                                     threads                              
68                                   red, solid                           
__________________________________________________________________________
 
    
     
                                           TABLE V                                 
__________________________________________________________________________
                                Reaction                                  
                     Starting                                             
                          Max. temp.                                      
                                time                                      
No.                                                                       
   BS                                                                     
     Aldehyde   Hardener                                                  
                     temp. °C.                                     
                          °C.                                      
                                seconds                                   
__________________________________________________________________________
69 BS                                                                     
     7 ml propionaldehyde                                                 
                     22   40    60                                        
70 BS                                                                     
     4 ml propionaldehyde                                                 
                     22   40    65                                        
71 BS                                                                     
     7 ml butyraldehyde                                                   
                     22   40    60                                        
72 BS                                                                     
     4 ml butyraldehyde                                                   
                     22   40    60                                        
73 BS                                                                     
     4 ml valeraldehyde                                                   
                     22   40    60                                        
74 BS                                                                     
     14 ml formaldehyde                                                   
                     22   44    50                                        
75 BS                                                                     
     7 ml formaldehyde                                                    
     + 7 ml butyraldehyde                                                 
                     20   44    55                                        
__________________________________________________________________________
   Sulfonic acid and/or hydroxy                                           
No.                                                                       
   compound in aqueous solution                                           
                  Other substances                                        
                           Remarks                                        
__________________________________________________________________________
69                         darkbrown, soft                                
70                         red, solid                                     
71                         darkbrown, soft                                
72                         brown, solid                                   
73                         brown, solid                                   
74 + 4 ml of a saturated   raspberry colored,                             
   p-toluene sulfonic acid solid                                          
75 as Example 74           deep red (jellylike)                           
                           solid                                          
__________________________________________________________________________
 
    
     
                                           TABLE VI                                
__________________________________________________________________________
                            Starting temp.                                
                                    Max. Reaction time                    
No.                                                                       
   BS  Aldehyde  Hardener   °C.                                    
                                    temp. °C.                      
                                         seconds                          
__________________________________________________________________________
76     7 ml formaldehyde                                                  
                 11.8 g phos-                                             
                            22      40   67                               
                 phoric acid                                              
77 44 ml                                                                  
       5 ml formaldehyde                                                  
                 --         28      29   65                               
   BS                                                                     
78     5 ml formaldehyde                                                  
                 5 ml sulfuric acid                                       
79     1.5 g para-                                                        
                 5 ml sulfuric acid                                       
       formaldehyde                                                       
80     7 ml formaldehyde                                                  
                 2.5 ml phosphoric                                        
                 and 0.4 ml sulfuric                                      
                 acid                                                     
81     1 ml formaldehyde                                                  
                 1 ml phosphoric acid                                     
                            22      35                                    
82 BS  7 ml formaldehyde    18      39   245                              
83     6 ml formaldehyde                                                  
__________________________________________________________________________
   Sulfonic acid and/or                                                   
No.                                                                       
   hydroxy compound                                                       
                   Other substances                                       
                                Remarks                                   
__________________________________________________________________________
76 13.8 g commercial dodecyl-   Lightred substance.                       
   benzenesulfonic acid-        quantitatively solid                      
   Na and 3 g                                                             
   resorcinol in 18 ml water                                              
77                 3 ml monostyrene                                       
                                light brown, solid                        
                   2 ml ethanol substance                                 
78 13 g indigocarmine with 3 g  semisoft beige sub-                       
   resorcinol in 20 ml water    stance                                    
79 3 g solid DIBNS powder and   oligomers are formed                      
   1 g resorcinol dissolved in                                            
   20 ml glacial acetic acid                                              
80 40 ml of a saturated solution                                          
                                no immediate reaction,                    
   of DIBNS powder and 5 g sali-                                          
                                after hours the sub-                      
   cylic acid                   stance becomes quanti-                    
                                tatively solid. It is                     
                                of a green color.                         
                                At 120° C., it turns into          
                                a dirty yellow                            
81 0.5 g o-sulfanilic acid is dissolved                                   
                                Solution turns red                        
   in water and mixed with 0.4 g re-                                      
                                and becomes solid                         
   sorcinol                                                               
82                 3 g ammonium phosphate                                 
                                A ball of threads is                      
                                formed under continuous                   
                                stirring. Color: light-                   
                                red. Yield 24 g                           
83 40 ml diisobutylnaphthalene- No immediate reaction.                    
   disulfonic acid concentrate  If after 8 hours a fur-                   
   are mixed with 1.4 g resorcinol                                        
                                ther 1.4 g resorcinol are                 
                                added a fibrous sub-                      
                                stance is obtained after                  
                                15 min. stirring which does               
                                not change at 105° C., it is       
                                dark brown, turns red in soda             
__________________________________________________________________________
                                lye                                       
 
    
     
                                           TABLE VII                               
__________________________________________________________________________
                       Starting temp.                                     
                               Max. temp.                                 
                                      Reaction time                       
No.                                                                       
   Aldehyde  Hardener  °C.                                         
                               °C.                                 
                                      sec.                                
__________________________________________________________________________
84 5 ml formaldehyde                                                      
             5 ml phosphoric   70°                                 
             acid                                                         
85 4 ml formaldehyde                                                      
86 7 ml formaldehyde                                                      
             3 ml phosphoric                                              
             acid                                                         
87 2 ml formaldehyde                                                      
             10 ml 95%-sulfuric                                           
             acid                                                         
88 7 ml formaldehyde                                                      
             4 ml phosphoric                                              
             acid                                                         
89 1 ml formaldehyde                                                      
             1 ml phosphoric                                              
             acid                                                         
90 7 ml formaldehyde                                                      
             2 ml sulfuric                                                
             acid                                                         
__________________________________________________________________________
   Sulfonic acid and/or                                                   
No.                                                                       
   hydroxy compound   Other substances                                    
                               Remarks                                    
__________________________________________________________________________
84 10 g anthraquinone-2-       Hardener and formaldehyde                  
   sulfonic sodium salt        are added together at the                  
   in 100 ml water + 4 g       end, then heated. At about                 
   resorcinol                  90° C. explosionlike solidifi-      
                               cation takes place.                        
85 40 ml diisobutylnaphthalene-                                           
                               upon stirring, a substance                 
   disulfonic acid + 14 g resorcinol                                      
                               in form of a ball of threads               
                               is formed                                  
86 30 g sulfanilic acid + 2.8 g                                           
                               A red resin is formed                      
   resorcinol in aqueous solution                                         
87 2.8 g resorcinol            oligomers are formed under                 
                               red coloration                             
88 30 g benzenedisulfonic acid-                                           
                               oligomers                                  
   (1,3) disodium salt +                                                  
   1.4 g resorcinol                                                       
89 5 g Na-salt of 4&#39;-(dimethyl-                                           
                               oligomers are formed                       
   amino)-azobenzene-4-sulfonic                                           
   acid dissolved in boiling water                                        
   + 0.5 g resorcinol                                                     
90 40 ml diisobutyl-disulfonic disodium salt                              
                               at 80-85° C. oligomers are          
   + 1 g of phenol             formed which harden further                
                               after cooling                              
__________________________________________________________________________
 
    
     
                                           TABLE VIII                              
__________________________________________________________________________
                         Starting temp.                                   
                                 Max. temp.                               
                                       Reaction                           
No.                                                                       
   BS                                                                     
     Aldehyde   Hardener °C.                                       
                                 °C.                               
                                       time sec.                          
__________________________________________________________________________
91   7 ml formaldehyde                                                    
                1 ml phos-                                                
                phoric acid                                               
92                                                                        
93   1.5 ml formaldehyde                                                  
94   10 ml formaldehyde                                                   
                2 ml phosphoric                                           
                         20      40                                       
                acid                                                      
95   10 ml formaldehyde  22      48    60                                 
96   7 ml formaldehyde   26.5    62                                       
97   0.35 ml formaldehyde                                                 
                3 ml sulfuric acid                                        
98   0.7 ml formaldehyde                                                  
__________________________________________________________________________
   Sulfonic acid and/or                                                   
No.                                                                       
   hydroxy compound  Other substances                                     
                              Remarks                                     
__________________________________________________________________________
91 40 ml 5%-DIBNS-            Reaction takes place upon                   
   solution + 2.8 g resorcinol                                            
                              heating, at 90° the solution         
                              becomes quantitatively solid                
92 as 91, but 4.2 g resorcinol                                            
                              same result as example 91                   
93 20 ml of a saturated toluene-                                          
                              The temperature rises from                  
   sulfonic acid solution +   17 to 54° C. The solution            
   9.93 g resorcinol          turns wine yellow. With                     
                              addition of 5 ml phosphoric                 
                              acid, a resin is formed.                    
94 40 ml of the solution from example 93                                  
                              A solid raspberry resin is                  
                              formed. About 20 ml liquid                  
                              could be decanted which was                 
                              slightly yellow, but solidi-                
                              fied with further addition                  
                              of formaldehyde                             
95 20 ml of a suspension of congo red in                                  
                              The blue color of the solu-                 
   95%-sulfuric acid are mixed with 6 g                                   
                              tion changes to brown red                   
   resorcinol and diluted to 60 ml                                        
                              and becomes solid. Color                    
                              does not change although                    
                              pH value is still acid.                     
96 as Example 95, only 5 g resorcinol                                     
                              The solution becomes solid                  
                              under brownred coloration                   
97 2 g benzenesulfinic sodium With careful heating, a                     
   + 0.15 resorcinol          pink resin is quantitatively                
                              formed                                      
98 as Example 97              On heating, the mixture                     
                              reacts explosionlike.                       
                              The solid substance is hurled               
                              3 m away from reaction flask                
__________________________________________________________________________
 
    
     
                                           TABLE IX                                
__________________________________________________________________________
                                       Reaction                           
                             Starting                                     
                                  Max. time                               
No.  Aldehyde  Hardener      temp. °C.                             
                                  temp. °C.                        
                                       seconds                            
__________________________________________________________________________
 99  7 ml formaldehyde                                                    
               10 ml sulfuric acid                                        
100  7 ml formaldehyde                                                    
               10 ml 35%-hydrochloric acid                                
101  7 ml formaldehyde                                                    
               10 ml phosphoric acid                                      
102                                                                       
   BS                                                                     
     5 ml formaldehyde       22.8 43.3 60                                 
103  9 ml formaldehyde                                                    
               3 ml phosphoric acid and                                   
               1 ml sulfuric acid                                         
104  5 ml formaldehyde                                                    
               10 ml phosphoric acid                                      
                             30   40   60                                 
105  5 ml formaldehyde       32   48   240                                
__________________________________________________________________________
   Sulfonic acid and/or                                                   
No.                                                                       
   hydroxy compound  Other substances                                     
                              Remarks                                     
__________________________________________________________________________
 99                                                                       
   40 ml of a conc. solution  solution turns red, a deep-                 
   of an alkanesulfonic acid- red precipitate is formed                   
   sodium salt with 1.75 g resorcinol                                     
100                                                                       
   as Example 99              solution behaves as in                      
                              Example 99                                  
101                                                                       
   as Example 99              the mixture reacts imme-                    
                              diately and becomes quanti-                 
                              tatively solid                              
102                                                                       
   40 ml without resorcinol + a solid substance is formed                 
   1.0 g 3,5-dihydroxytoluene                                             
103                                                                       
   40 ml of a saturated       the solution solidifies                     
   DIBNS solution + 5 salicylic acid                                      
                              after several hours stan-                   
                              ding quantitatively. The                    
                              resin is of a green color.                  
                              After drying at 120° C. a            
                              yellowish discoloration                     
                              takes place.                                
104                                                                       
   13.8 g dodecylbenzenesulfonic                                          
                              resin, light pink, solution                 
   sodium + 5 g resorcinol in quantitatively solid                        
   saturated aqueous solution                                             
105                                                                       
   40 ml of a solution from 0.4                                           
                              freshly prepared solution.                  
   mol DIBNS and 0.27 mol re- Solution becomes viscous-                   
   sorcinol and 0.83 mol phosphoric acid                                  
                              hard, red and transparent                   
__________________________________________________________________________
 
    
     
                                           TABLE X                                 
__________________________________________________________________________
                     Starting temp.                                       
                             Max. temp.                                   
                                    Reaction time                         
No.                                                                       
   BS                                                                     
     Aldehyde  Hardener                                                   
                     °C.                                           
                             °C.                                   
                                    seconds                               
__________________________________________________________________________
106  5 ml formaldehyde                                                    
                     25      43     90                                    
107                                                                       
   BS                                                                     
     5 ml formaldehyde                                                    
                     27      46     45                                    
108                                                                       
   BS                                                                     
     5 ml formaldehyde                                                    
                     26      30     110                                   
109                                                                       
   BS                                                                     
     5 ml formaldehyde                                                    
                     26      53     120                                   
111                                                                       
   BS                                                                     
     7 ml formaldehyde                                                    
                     23      46     75                                    
110                                                                       
   BS                                                                     
     5 ml formaldehyde                                                    
                     24      76     180                                   
112                                                                       
   BS                                                                     
     14 ml formaldehyde                                                   
                     23      44     73                                    
113                                                                       
   BS                                                                     
     7 ml formaldehyde                                                    
__________________________________________________________________________
   Sulfonic acid and/or                                                   
No.                                                                       
   hydroxy compound                                                       
             Other substances                                             
                            Remarks                                       
__________________________________________________________________________
106                                                                       
   as Example 105           substance solidifies quanti-                  
                            tatively. Test lasted 18 days.                
                            According to mixture from                     
                            Example 105                                   
107                                                                       
   40 ml     20 ml urea-formaldehyde-resin                                
                            The UF resin was added at the                 
             condensate     start of the reaction when the                
                            solution became cloudy after                  
                            45&#34;. The resin mixture is                     
                            amorphous and hard as rock,                   
                            almost no shrinkage after expo-               
                            sure for several weeks.                       
108                                                                       
   40 ml     10 ml phenolic resin (bakelite                               
                            With the addition of resin, the               
             H 981)         solution clears up again. After               
                            2 minutes, a raspberry red                    
                            resin is formed quantitatively.               
109                                                                       
   40 ml     10 ml bakelite-resin (AF2580)                                
                            resin is amorphous, red and                   
                            hard.                                         
111                                                                       
   40 ml     10 ml desmodur 44 V                                          
                            substance is hard and solid.                  
110                                                                       
   40 ml     10 ml furfurylalcohol                                        
                            a green, slightly rubberlike                  
                            resin is formed                               
112                                                                       
   100 ml    20 ml desmodur 44 V + 3 ml                                   
                            solid, but gritty resin is                    
             PU 1109        formed                                        
113                                                                       
   25 ml     10 ml desmodur 44 V +                                        
                            a foam is formed. 5-fold                      
             1 ml glycerin  foaming.                                      
             1 ml desmor 726 B                                            
             2 ml frigen                                                  
__________________________________________________________________________
 
    
     
                                           TABLE XI                                
__________________________________________________________________________
                           Starting                                       
                                Max.                                      
                                    Reaction                              
                           temp.                                          
                                temp.                                     
                                    time                                  
No.                                                                       
   GL Aldehyde    Hardener °C.                                     
                                °C.                                
                                    seconds                               
__________________________________________________________________________
114   2.33 mols formaldehyde                                              
                  4 mols phos-                                            
                           27   46  135                                   
                  phoric acid                                             
115   4 mols formaldehyde                                                 
                  4 mols phos-                                            
                           27   39  95                                    
                  phoric acid                                             
116   2.33 mols formaldehyde                                              
                  none     25.5 36  300                                   
117   4 mols formaldehyde                                                 
                  2 mols phosphoric                                       
                           26   40  65                                    
                  acid                                                    
118   4 mols formaldehyde                                                 
                  2 mols phosphoric                                       
                           27   39  80                                    
                  acid                                                    
119   4 mols formaldehyde                                                 
                  none     25   33  540                                   
120   5 mols formaldehyde                                                 
                  5 mols phos-                                            
                           31   52  90                                    
                  phoric acid                                             
121   3 mols formaldehyde                                                 
                  6 mols phos-                                            
                           31   45.5                                      
                                    80                                    
                  phoric acid                                             
__________________________________________________________________________
   Sulfonic acid and/or                                                   
                   Other                                                  
No.                                                                       
   hydroxy compound                                                       
                   substances                                             
                           Remarks                                        
__________________________________________________________________________
114                                                                       
   1 mol paratoluenesulfonic acid                                         
                           quantitatively solid resin                     
   + 1 mol resorcinol in aqueous                                          
   conc. solution                                                         
115                                                                       
   as Example 114          quantitatively solid resin                     
116                                                                       
   as Example 114          as examples 114 a. 115                         
117                                                                       
   as Example 114, only 0.45 mol                                          
                           as example 116                                 
   resorcinol                                                             
118                                                                       
   as Example 117          as example 116                                 
119                                                                       
   as Example 117          after 14.5 min, solid resin                    
                           is formed                                      
120                                                                       
   1 mol naphthalenetrisulfonic                                           
                   UF resin                                               
                           components do not solidify.                    
   trisodium salt + 3 mol resorcinol                                      
                           If UF is added after 3 days                    
                           (1 part UF resin per 3 parts                   
                           of solution), the mixture                      
                           solidifies only after 15                       
                           minutes in spite of ph 1 (one)                 
                           The rapid reaction of UF                       
                           resin can thus be delayed.                     
121                                                                       
   as Example 120  0.8 mol butanol                                        
                           2 resin types are precipi-                     
                           tated. A coherent, fiber-                      
                           like compound is soluble                       
                           in NaOH and precipitates                       
                           again with hydrochloric                        
                           acid. It is yellow.                            
__________________________________________________________________________
 
    
     
                                           TABLE XII                               
__________________________________________________________________________
                        Starting                                          
                             Max. Reaction time                           
No.                                                                       
   BS                                                                     
     Aldehyde  Hardener temp. °C.                                  
                             temp. °C.                             
                                  seconds                                 
__________________________________________________________________________
122  2 mol formaldehyde                                                   
               0.4 mol sulfuric                                           
                        27   46.5 17                                      
               acid                                                       
123  4 ml formaldehyde                                                    
               2.5 ml sulfuric                                            
                        28   41   25                                      
               acid                                                       
124  4 ml formaldehyde                                                    
               2.5 ml fuming                                              
                        23   35   55                                      
               hydrochloric acid                                          
125  4 ml formaldehyde                                                    
               2.5 ml 65%-                                                
                        24.5 40   45                                      
               nitric acid                                                
126  4 ml formaldehyde                                                    
               2.3 g oxalic acid                                          
                        22   23   60                                      
127                                                                       
   BS                   21.2 37.3 185                                     
128                                                                       
   BS                   21.4 33.6 140                                     
__________________________________________________________________________
   Sulfonic acid and/or                                                   
No.                                                                       
   hydroxy compound                                                       
                 Other substances                                         
                          Remarks                                         
__________________________________________________________________________
122                                                                       
   as Example 120, only 1 mol                                             
                          a red colored resin imme-                       
   resorcinol             diately precipitates                            
                          quantitatively                                  
123                                                                       
   3.1 g naphthalenetrisulfonic                                           
                          resin is formed immediately                     
   trisodium + 0.9 g resorcinol                                           
                          quantitatively                                  
124                                                                       
   as Example 123         as example 123                                  
125                                                                       
   as 123                 as example 123                                  
126                                                                       
   as 123                 with addition of oxalic acid                    
                          sodium oxalate precipitates.                    
                          With addition of 3 ml acetic                    
                          acid the solution quantitatively                
                          solidifies within 15 min.                       
127                                                                       
   20 ml + (15 ml BS +    a resin is formed                               
   5 ml water + 5 ml                                                      
   formaldehyde)                                                          
128                                                                       
   40 ml + (10 ml BS +    a resin is formed. (The BS                      
   5 ml formaldehyde)     of this example is 3 weeks                      
                          older than the BS of                            
                          example 127).                                   
__________________________________________________________________________
 
    
     
                                           TABLE XIII                              
__________________________________________________________________________
                      Starting temp.                                      
                              Max. temp.                                  
                                    Reaction time                         
No.                                                                       
   BS                                                                     
     Aldehyde   Hardener                                                  
                      °C.                                          
                              °C.                                  
                                    seconds                               
__________________________________________________________________________
129                                                                       
   BS                 21.4    37     80                                   
130                                                                       
   BS                                                                     
     3 ml formaldehyde                                                    
                      24.4    53.6  300                                   
131                                                                       
   BS                                                                     
     4 ml formaldehyde                                                    
                      24.5    37    480                                   
132                                                                       
   BS                                                                     
     4 ml crotonaldehyde                                                  
                3 cc H.sub.2 SO.sub.4                                     
                      24.5    40     50                                   
133                                                                       
   BS                                                                     
     5 ml crotonaldehyde                                                  
                      24.5    41    240                                   
     1 ml formaldehyde                                                    
134                                                                       
   BS                                                                     
     7 ml glyoxalaldehyde                                                 
                3 cc H.sub.2 SO.sub.4                                     
                      24.5    40     40                                   
135                                                                       
   BS                                                                     
     2 ml glyoxalaldehyde                                                 
                      22.0           5 hours                              
136                                                                       
   BS                                                                     
     4 ml formaldehyde                                                    
                      21.0    42     50                                   
__________________________________________________________________________
   Sulfonic acid and/or                                                   
No.                                                                       
   hydroxy compound                                                       
              Other substances                                            
                          Remarks                                         
__________________________________________________________________________
129                                                                       
   as Example 128         as example 128 (the solution of                 
                          this example is 4 months old).                  
                          There is a clearly recognizable                 
                          color difference between the                    
                          formed resins of examples 128                   
                          and 129.                                        
130                                                                       
   40 ml, but without                                                     
              little ethanol                                              
                          the solution becomes viscous at                 
   resorcinol + 5.62 g                                                    
              10 ml furfuryl                                              
                          48.2. The substance is soluble                  
   gallic acid dissolved                                                  
              alcohol     in NaOH and precipitates again                  
   in hot water           with hydrochloric acid. After                   
                          prolonged standing, the substance               
                          hardens further from above. The                 
                          amorphous substance turns into a                
                          clear lightbrown compound. After                
                          14 days, the fully hardened resin               
                          is no longer soluble in NaOH. It                
                          changes its color lengthwise, it                
                          turns red. The amorphous sub-                   
                          stance still soluble in NaOH no                 
                          longer precipitates with addition               
                          of hydrochloric acid                            
131                                                                       
   40 ml                                                                  
132                                                                       
   40 ml                                                                  
133                                                                       
   40 ml                  lightbrown, semirigid monomers                  
134                                                                       
   40 ml                                                                  
135                                                                       
   40 ml                  separation of a green liquid,                   
                          the formed resin is solid with                  
                          a brown color                                   
136                                                                       
   40 ml      polystyrene pellets                                         
                          the pellets are firmly incorpo-                 
              (15 g/l)    rated in the resin formed                       
__________________________________________________________________________
 
    
     It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.