Plastic and foam plastic and method for making them

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 ("The Chemistry of Synthetic Resins", 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 "Rompps ChemieLexikon", 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 sodium4.40 g resorcin, 11.80 g (85%-) phosphoric acid in aqueous solution(water content ca. 24%) - In all examples,the formaldehyde was added with stirringExam- 35%-     Starting        Reactionple   formalde-          tempera- Max.   time    ColorNo.   hyde, ml ture, °C.                   temp. °C.                          sec.    state______________________________________4     1        28       30     no                          noticeable                          reaction5     2        28       45     striation6     3        28       40     striation7     4        24.5     55.5   48      pink, solid8     5        24.5     57     48      pink, solid9     6        24.5     57     48      pink, solid10    7        24.5     59.5   48      pink, solid11    8        24.5     58     48      pink, solid12    9        27.5     59.5   30      pink, solid13    10       27.5     56     48      pink, solid14    11       23.5     52     45      pink, solid15    12       23.5     50.5   45      pink, solid16    13       23.5     51     60      pink, solid17    14       23.5     49     75      pink, solid18    15       23.5     48     75      pink, solid19    16       23.5     49     75      pink, solid20    17       23.5     48     90      pink, solid21    18       24       50     90      pink, solid22    20       24       48     95      pink, solid23    25       24       48     120     pink, solid______________________________________

______________________________________Weight of resins from the reactions using differingamounts of formaldehyde  Weight 12 days              30 days       8 monthsExample  after reaction              after reaction                            after reaction______________________________________4      40.77       cannot be weighed5      41.85       "6      42.93       "7      44.01       40.10         38.158      45.09       40.30         31.909      46.17       40.40         32.2010     47.25       42.24         33.5511     48.33       41.72         32.5312     49.41       40.00         32.2513     50.49       41.12         32.4814     51.57       41.91         32.4515     52.65       42.25         33.2416     53.75       42.81         33.6517     54.81       42.21         33.0018     55.89       44.26         33.1819                 43.88         32.9020                 44.20         33.2021                 43.86         33.0822                 not measured  33.1023                 "             33.88______________________________________

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 change2.   37%-fuming hydro-chloric acid   no change      no change3.   85%-phosphoric acid               no change      color                              intensifi-                              cation4.   65%-nitric acid               dissolved      --(4a) 25%-nitric acid               dissolved      --5.   96%-acetic acid               no change      no change6.   Absolute alcohol               no change; substance                              no change               turns yellow7.   Acetone        no change      no change               substance turns               yellow8.   Dimethylformamide               no change      no change9.   Dioxane        no change      no change               substance turns yellow10.  Paraffin oil   no change      no change(10a)Motor oil      no destruction --11.  20%-soda lye   no change      no change12.  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                                timeNo.   BSAldehyde   Hardener                  °C.                         °C.                                sec.__________________________________________________________________________31b   BS4 ml formaldehyde           4 ml H3 PO4                  30     50     4832   2 ml formaldehyde           2 ml H3 PO4                  20     6033 BS6 ml formaldehyde 24     40     4034   6 ml formaldehyde35 BS5 ml furfurylaldehyde(95%)36   4 ml formaldehyde 23     70     4837   6 ml formaldehyde 23     3038   7 ml formaldehyde 23     2939   7 ml formaldehyde 22.5   3640 BS7 ml formaldehyde 22.5   7541 BS7 ml formaldehyde 22.5   7542 BS9 ml acetaldehyde43 BS9 ml propionaldehyde44 BS9 ml butyraldehyde45 BS7 ml formaldehyde 23     7546 BS7 ml valeraldehyde47 BS7 ml formaldehyde 24     42__________________________________________________________________________   Sulfonic acid and/or hydroxy compoundNo.   in aqueous solution                 Other substances                            Remarks__________________________________________________________________________31b                              pink, solid32 3.4 anthraquinone-2-sulfonic   sodium + 1 g resorcinol       red, solid33                    2 ml iron-II-chloride                 solution   red, solid34 5 g p-toluenesulfonic acid   + 1 g resorcinol              pink35                               black, solid36 10 g p-toluenesulfonic acid   + 4.8 g resorcinol            red, solid37 10 g diisobutylnaphthalene-di-                 10 ml iron-III-chloride                            brown, solid   sulfonic sodium +   3.5 g resorcinol38 20 g as in 37 + 1.4 g resorcinol                 1.4 g tannic acid                            brown, solid39 15 g benzenesulfonic acid +   1.4 g resorcinol              light red, solid40 1.4 g pyrocatechol            red, soft41 1.4 g phloroglucinol          red, soft42                               greasy brown                            substance, which                            becomes solid                            after some time43                               brown substance,                            hardens with                            prolonged ex-                            posure44                               brown substance,                            hardens with                            prolonged ex-                            posure45 1.4 g hydroquinone            brown, soft46                               brown substance,                            hardens with                            prolonged ex-                            posure47 20 g diisobutylnaphthalene-   brown, solid   disulfonic disodium   + 4.2 g resorcinol__________________________________________________________________________

                                  TABLE III__________________________________________________________________________                 Starting                      Max. temp.                            ReactionNo.   BSAldehyde  Hardener                 temp. °C.                      °C.                            time sec.__________________________________________________________________________48   7 ml formaldehyde                 23.5 5249   7 ml formaldehyde          40 ml 98%-          sulfuric acid50 BS8 ml formaldehyde                 18   45    12051 BS7 ml formaldehyde                 20   40    24052 BS4 ml formaldehyde                 20   43     8053 BS4 ml formaldehyde                 18   3854 BS4 ml formaldehyde                 24         12055 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, solid49 + 5 g resorcinol             red, solid50 + 2.8 g resorcinol           red, solid51 3 g sulfanilic acid + 2 g resorcinol                           brown, soft52                  1.4 g ammonium chloro-               cuprate II  red, solid53 1 g sulfanilic acid          red, semirigid54                  40 ml water red, solid55                  40 ml water red, solid__________________________________________________________________________

                                  TABLE IV__________________________________________________________________________                      Starting temp.                              Max. Reaction timeNo.   BSAldehyde    Hardener  °C.                              temp. °C.                                   seconds__________________________________________________________________________56 BS7 ml formaldehyde     22      30   3057 BS4 ml formaldehyde     18      27   12758 BS4 ml formaldehyde     20      38   24059 BS4 ml formaldehyde     20      41   30060 BS7 ml pyridinaldehyde  18      40   6061 BS4 ml pyridinaldehyde  18      40   8062   2 ml formaldehyde            18.7 ml phosphoric                      26      35   45            acid63   7 ml formaldehyde            11.8 ml phosphoric                      26      38   220            acid64   7 ml glutardialdehyde            6 ml phosphoric                      26      40   70(25%-)      acid65   7 ml formaldehyde            11.8 ml phosphoric                      28      41   68            acid66   7 ml formaldehyde            11.8 ml phosphoric                      28      40   60            acid67 BS7 ml pelargonaldehyde 21      35   8068 BS3.5 ml formaldehyde +3.5 ml pelargonaldehyde                      21      40   80__________________________________________________________________________   Sulfonic acid and/or hydroxyNo.   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 resorcinol57                     1 g tannic acid + 4 ml water                                brown, solid58                     3 ml ethanol  brown, solid59                     1 g 2-amino-diphenyl-                                yellow substance,                  amine in 8 ml ethanol                                solid, after 1 hour                                recoloration60                                   soft, hardens after                                12 hours61                                   red, solid62 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, solid63 as example 62                     pink, solid64 40 ml saturated aqueous solution of                                turns pink and   diisobutylnaphthalenesulfonic-Na +                                solid at 60° C.   3 g resorcin65 as example 64 and 3 g orcinol     yellow substance,                                solid66 13.8 g dodecylbenzenesulfonic sodium +   3 g resorcinol      18 ml water   light pink, solid67                                   light brown, draws                                threads68                                   red, solid__________________________________________________________________________

                                  TABLE V__________________________________________________________________________                           Reaction                Starting                     Max. temp.                           timeNo.   BSAldehyde   Hardener                temp. °C.                     °C.                           seconds__________________________________________________________________________69 BS7 ml propionaldehyde                22   40    6070 BS4 ml propionaldehyde                22   40    6571 BS7 ml butyraldehyde                22   40    6072 BS4 ml butyraldehyde                22   40    6073 BS4 ml valeraldehyde                22   40    6074 BS14 ml formaldehyde                22   44    5075 BS7 ml formaldehyde+ 7 ml butyraldehyde                20   44    55__________________________________________________________________________   Sulfonic acid and/or hydroxyNo.   compound in aqueous solution             Other substances                      Remarks__________________________________________________________________________69                         darkbrown, soft70                         red, solid71                         darkbrown, soft72                         brown, solid73                         brown, solid74 + 4 ml of a saturated   raspberry colored,   p-toluene sulfonic acid solid75 as Example 74           deep red (jellylike)                      solid__________________________________________________________________________

                                  TABLE VI__________________________________________________________________________                       Starting temp.                               Max. Reaction timeNo.   BS  Aldehyde  Hardener   °C.                               temp. °C.                                    seconds__________________________________________________________________________76     7 ml formaldehyde            11.8 g phos-                       22      40   67            phoric acid77 44 ml  5 ml formaldehyde            --         28      29   65   BS78     5 ml formaldehyde            5 ml sulfuric acid79     1.5 g para-            5 ml sulfuric acid  formaldehyde80     7 ml formaldehyde            2.5 ml phosphoric            and 0.4 ml sulfuric            acid81     1 ml formaldehyde            1 ml phosphoric acid                       22      3582 BS  7 ml formaldehyde    18      39   24583     6 ml formaldehyde__________________________________________________________________________   Sulfonic acid and/orNo.   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 water77                 3 ml monostyrene                           light brown, solid              2 ml ethanol substance78 13 g indigocarmine with 3 g  semisoft beige sub-   resorcinol in 20 ml water    stance79 3 g solid DIBNS powder and   oligomers are formed   1 g resorcinol dissolved in   20 ml glacial acetic acid80 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 yellow81 0.5 g o-sulfanilic acid is dissolved                           Solution turns red   in water and mixed with 0.4 g re-                           and becomes solid   sorcinol82                 3 g ammonium phosphate                           A ball of threads is                           formed under continuous                           stirring. Color: light-                           red. Yield 24 g83 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 timeNo.   Aldehyde  Hardener  °C.                          °C.                                 sec.__________________________________________________________________________84 5 ml formaldehyde        5 ml phosphoric   70°        acid85 4 ml formaldehyde86 7 ml formaldehyde        3 ml phosphoric        acid87 2 ml formaldehyde        10 ml 95%-sulfuric        acid88 7 ml formaldehyde        4 ml phosphoric        acid89 1 ml formaldehyde        1 ml phosphoric        acid90 7 ml formaldehyde        2 ml sulfuric        acid__________________________________________________________________________   Sulfonic acid and/orNo.   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 formed86 30 g sulfanilic acid + 2.8 g                          A red resin is formed   resorcinol in aqueous solution87 2.8 g resorcinol            oligomers are formed under                          red coloration88 30 g benzenedisulfonic acid-                          oligomers   (1,3) disodium salt +   1.4 g resorcinol89 5 g Na-salt of 4'-(dimethyl-                          oligomers are formed   amino)-azobenzene-4-sulfonic   acid dissolved in boiling water   + 0.5 g resorcinol90 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.                                  ReactionNo.   BSAldehyde   Hardener °C.                            °C.                                  time sec.__________________________________________________________________________91   7 ml formaldehyde           1 ml phos-           phoric acid9293   1.5 ml formaldehyde94   10 ml formaldehyde           2 ml phosphoric                    20      40           acid95   10 ml formaldehyde  22      48    6096   7 ml formaldehyde   26.5    6297   0.35 ml formaldehyde           3 ml sulfuric acid98   0.7 ml formaldehyde__________________________________________________________________________   Sulfonic acid and/orNo.   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 solid92 as 91, but 4.2 g resorcinol                         same result as example 9193 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 formaldehyde95 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 coloration97 2 g benzenesulfinic sodium With careful heating, a   + 0.15 resorcinol          pink resin is quantitatively                         formed98 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. timeNo.  Aldehyde  Hardener      temp. °C.                             temp. °C.                                  seconds__________________________________________________________________________ 99  7 ml formaldehyde          10 ml sulfuric acid100  7 ml formaldehyde          10 ml 35%-hydrochloric acid101  7 ml formaldehyde          10 ml phosphoric acid102   BS5 ml formaldehyde       22.8 43.3 60103  9 ml formaldehyde          3 ml phosphoric acid and          1 ml sulfuric acid104  5 ml formaldehyde          10 ml phosphoric acid                        30   40   60105  5 ml formaldehyde       32   48   240__________________________________________________________________________   Sulfonic acid and/orNo.   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 resorcinol100   as Example 99              solution behaves as in                         Example 99101   as Example 99              the mixture reacts imme-                         diately and becomes quanti-                         tatively solid102   40 ml without resorcinol + a solid substance is formed   1.0 g 3,5-dihydroxytoluene103   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 solution105   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 timeNo.   BSAldehyde  Hardener                °C.                        °C.                               seconds__________________________________________________________________________106  5 ml formaldehyde                25      43     90107   BS5 ml formaldehyde                27      46     45108   BS5 ml formaldehyde                26      30     110109   BS5 ml formaldehyde                26      53     120111   BS7 ml formaldehyde                23      46     75110   BS5 ml formaldehyde                24      76     180112   BS14 ml formaldehyde                23      44     73113   BS7 ml formaldehyde__________________________________________________________________________   Sulfonic acid and/orNo.   hydroxy compound        Other substances                       Remarks__________________________________________________________________________106   as Example 105           substance solidifies quanti-                       tatively. Test lasted 18 days.                       According to mixture from                       Example 105107   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". 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 formed112   100 ml    20 ml desmodur 44 V + 3 ml                       solid, but gritty resin is        PU 1109        formed113   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.                               timeNo.   GL Aldehyde    Hardener °C.                           °C.                               seconds__________________________________________________________________________114   2.33 mols formaldehyde             4 mols phos-                      27   46  135             phoric acid115   4 mols formaldehyde             4 mols phos-                      27   39  95             phoric acid116   2.33 mols formaldehyde             none     25.5 36  300117   4 mols formaldehyde             2 mols phosphoric                      26   40  65             acid118   4 mols formaldehyde             2 mols phosphoric                      27   39  80             acid119   4 mols formaldehyde             none     25   33  540120   5 mols formaldehyde             5 mols phos-                      31   52  90             phoric acid121   3 mols formaldehyde             6 mols phos-                      31   45.5                               80             phoric acid__________________________________________________________________________   Sulfonic acid and/or              OtherNo.   hydroxy compound              substances                      Remarks__________________________________________________________________________114   1 mol paratoluenesulfonic acid                      quantitatively solid resin   + 1 mol resorcinol in aqueous   conc. solution115   as Example 114          quantitatively solid resin116   as Example 114          as examples 114 a. 115117   as Example 114, only 0.45 mol                      as example 116   resorcinol118   as Example 117          as example 116119   as Example 117          after 14.5 min, solid resin                      is formed120   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 timeNo.   BSAldehyde  Hardener temp. °C.                        temp. °C.                             seconds__________________________________________________________________________122  2 mol formaldehyde          0.4 mol sulfuric                   27   46.5 17          acid123  4 ml formaldehyde          2.5 ml sulfuric                   28   41   25          acid124  4 ml formaldehyde          2.5 ml fuming                   23   35   55          hydrochloric acid125  4 ml formaldehyde          2.5 ml 65%-                   24.5 40   45          nitric acid126  4 ml formaldehyde          2.3 g oxalic acid                   22   23   60127   BS                   21.2 37.3 185128   BS                   21.4 33.6 140__________________________________________________________________________   Sulfonic acid and/orNo.   hydroxy compound            Other substances                     Remarks__________________________________________________________________________122   as Example 120, only 1 mol                     a red colored resin imme-   resorcinol             diately precipitates                     quantitatively123   3.1 g naphthalenetrisulfonic                     resin is formed immediately   trisodium + 0.9 g resorcinol                     quantitatively124   as Example 123         as example 123125   as 123                 as example 123126   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 timeNo.   BSAldehyde   Hardener                 °C.                         °C.                               seconds__________________________________________________________________________129   BS                 21.4    37     80130   BS3 ml formaldehyde                 24.4    53.6  300131   BS4 ml formaldehyde                 24.5    37    480132   BS4 ml crotonaldehyde           3 cc H2 SO4                 24.5    40     50133   BS5 ml crotonaldehyde                 24.5    41    2401 ml formaldehyde134   BS7 ml glyoxalaldehyde           3 cc H2 SO4                 24.5    40     40135   BS2 ml glyoxalaldehyde                 22.0           5 hours136   BS4 ml formaldehyde                 21.0    42     50__________________________________________________________________________   Sulfonic acid and/orNo.   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 acid131   40 ml132   40 ml133   40 ml                  lightbrown, semirigid monomers134   40 ml135   40 ml                  separation of a green liquid,                     the formed resin is solid with                     a brown color136   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.