CA1167593A - Production of plastics and foamed plastics - Google Patents

Abstract

Abstract of the Disclosure Plastics are produced by reacting at least one compound containing sulfonic acid groups with at least one aldehyde in the presence of a hydroxy compound in an acidic concentrated aqueous solution having a water content of about 20 to 30% by weight. If a tenside is present the reactants will form a foam. the preferred sulfonic acid-containing compound is the sodium salt of diisobutyl-naphthalene sulfonic acid, the preferred hydroxy compound is a phenol, vix. resorcinol, and the preferred aldehyde is formaldehyde which may be formed in situ from hexa-methylenetetramine, paraformaldehyde, trioxane, or the like.

Description

1 ~7593 ~he present invention relates to new plastics and foam plastics and to methods for makin~ the same.

Urea-ormaldehyde-resin foam plastics (UF foam plastics~, methods for making them and fields of application for the same axe }~nown from the literature and patents.

To ma}e UF foam materials, a water-soluble tenside and a UF resin (UF condensation product) are re~uired. The constitution of UF resins has still not been fully in-vestigated.

Suita~le tenside mixtures contain~ besides the actual ten-side in diluted solution, a hardener and a chemical sub-stance to prevent mildewin~ in the final UF foam plastic, e.~. resorcinol. Compositions have ~een-described in the literature.

~s hardeners, preferably inor~anic acids, particularly phosphoric acid, are used. As tenside, e.~. diisobut~l naphthalene sulfonic sodium, a water-soluble, anionic tenside, called DIBI~IS-Ma, can be used. 40 ml of a commercial tenside mixture as suited for ma]ing foamed plastics consist of, for exam~le, 13.83 g DIBNS-Na, 4.40 ~ resorcin~ and 11.80 g of 85%-phosphoric acid inthe orm of a yellowish, highly viscous paste with ca. 24 to 30 ~
w~ter content (pll 10 to 12) or in the form of a dry substance as a light, hygroscopic powder (pH 7 to 11).

For ma]cing I~F foam plastics, the tensides in the foam solution are strongly diluted with water. qhe ready~for-spraying solutions have a solid content of between 2 ancl 5 %.

Earlier it was assumed that the tenside ~erved only as a carrier ~r the UF resin ~Plastverarbeiter 9 (1958) 453);
later, however, it was believed that it might also react ionically with the reactive ~roups of the UF resin (~last-verarbeiter 27 (1976) 235).

1'he addition of other chemical substances to the baslc solutions in order to improve the physical and chemical properties of the finished UF foam plastic has also long been ~nown (l~unststoffe 47 (1957) 256).

~mong many su~gestions in the literature, amidosulfonic acid was proposed as ~ hardener and not as a ten~ida (Bachmann und Bertz, ~mino~last, V~B~Verlag f~r Grundstoff-Industrie, Leipæig 1969).

UF foam plastic, e.g. as thermal insulation ~aterial in two-sheet masonry,may fre~uently give off pun~ent formaldehyde fumes when dryi.ng out. Extensive tests were made for the pur-pose of finding ways to bind this free formaldehyde in any form whatsoever.

~ ~75~3 It was surprisingly found that under certain conditions compounds containing sulfonic groups and aldehydes in the presence of a hydroxy compound reacted quantitively with one another, and that a new plastic material was formed thereby.
According to the present invention; there is provided a method for making a plastic comprlsing reacting at least one compound containing sulfonic acid groups (a), with at least one aldehyde (b) or a compound which in acid medium is able to form an aldehyde (c), wherein (a) and (c) are present in the form of an acidic concentrated aqueous solution having a water content of about 20 to 30% by weight.
The invention may also be defined as a method for making a plastic foam comprising reacting at least one compound sulfonic acid groups (a), with at least one aldehyde (b) or a compound which in acid medium is able to form an aldehyde in the presence of a hydroxy compound (c) and a tenside (d) wherein (a) and (c) are present in the form of an acidic concentrated aqueous solution having a water content of about 20 to 30% by weight and (d) is present in the form of an aqueous solution sufficiently diluted to have a foam formed, and permitting the reactants to foam and harden.
~ hus, the method according to the invention for making this p.~astic is generally 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 ~ ~7~93 (c) possibly one or several inorganic or organic acids providedl 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 20 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 ~r~3 - 3a -in strongly diluted form inafoaming agent in the prepara-tion of UF foam plastics no substantial reac-tion between the tenside and excess Eormaldehyde in the UF plastic had ever been observed.

It was further surprisingly found that according to the inventiorl foam materials could be produced by foaming of only monomers according to the aforementioned components (a), (h), (f) and possibly (c), without requiring the presence o a finished resin product in the starting materials~ Only after everything has keen foamed is a resin formed from the monomers. The monomeric compo~
nents (a), (b) and tc) 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) ~ossibly 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 concentratecl aqueous solution with a water content of 20 to 30 %, as ~.7ell as (d) ~ossibly other, cu5tomary additives and (e) possi'nly otl~er synthetic and natural resins are foamed with (f) one or several saturated or unsaturated aldehydes or mixtures thereof or a compound ~7hich is able to form an aldehyde in acid medium, under addition of a tenside in a dilution as usually used for foam production of com~onent (f) in a conventional foam making installation.

~jumerous reactions between formaldehyde, other aldehydes, chemical compounds of an inorganic and orqanic 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:

E~USTON and EVI~G prepared xylol-formaldehyde oligomeric aromates with formaldehyde in the presence of acids (.~mer.Chem. Soc. ~1915) 2394)~

Formaldehyde-sulfuric acid is formed by the reaction of sulfur dioxide and formaldehycle (R~INKING, D~N~L and ~BE~RD (Ber., 38 (lqO5) 1075).

KALP,ER obtained methylene--bis-derivatives from beta na~hthyl sulfonic acid and formaldehyde in aqueous solution(US P. 2 056 924) ~ ~7~

Phenol-formaldehyde-novolac (1 mol) can ~e sulfonated with hydrosulfuxic acid (0.45 mol); also lianinsulfonic acids react with phenol-formaldehyde condensates (British P]~stics (1949) ~

C0~ describes a detection of formaldehyde up to 0.00005 mg hy 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.Zt~., 45 (1921) 997).

FLLIS obtained sli~htly polyvalent phenolic resin pro-ducts hy reaction with formaldehyde, which are hard to-isolate in the intermediate stage ("The Chemistry of Syn-thetic Resins", 277-395, Reinhold Pu~lishing Corp., 1935, New York).

PULk'R prepared methylol derivatives of hydroquinone with formaldehyde (Chem. Centr. (1941) I, 128-9) and CAR0 pre-pared methylene-bis-pyrogallol, the latter with formal-dehyde in the presence of hydrochloric acid, at room temperature (P,er. 25 (1892) 941)o lhe 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 tenperature and flame resistance, as well as good ~echa-nical and electrical properties rThey, fur-thermore,-can be produced at room tem2erature with simple stirrin~ ~hich re.sults in low co.sts and enerqy savinqs.

Tllc plastics according to the invention can ~e used in the production of fibers, i.njection moldinas and thermal insulators.

l'he foam ?lastics made from these plastics find use as insulatinq and thermal insula-ting materials, in ~lasto~
ponics, as oil absorbents, wound dressings, flower pinning materials, and in po~7der form as fillers, filter materials and pharmaceutical powders.

~s compoun~s containing sulfoni.c groups there may be used sulfonic acids, sulfinic acids ancl sulfamidic acids and their salts either alone or mixed together.

Examples are arylalkyl sulfonates like alkyl benzene sulfo-nates and alkyl naphthalene sulfonates, which are used as im~ortant interface surface-active materials.

Na~htholsul.fonic acids, naphthylaminesulfonic acids and ami.nonaph-tholsulfonic acids and their sodium salts are known as reaâily available basic or intermediate products in dye manufacture. Anthraquinonesulfonic acid and its sodiurn salts are likewise intermed.iates in dye synthesis.

list of these compounds is ~iven in "~ornpps Chemie-LeY~ikon", 7.Ed., P. 2259.

~ ~75~

Naphtllalenesulfonic acids are known as mono-, di~, tri-and tetrasulfonic acids.

heterocyclic sulfonic acids can be produced, for examnle, from acridine and acridone by means of chlorosulfonic acid.

~.ulfamic acids are, for example, amidosulfuric acid, amido-sulfonic aci.d or compounds to be denoted as sulfamidic acids.

A numher of sulfonic acids that can he used according to the invention are given as follows: phenolsulonic acids, alkylsulfuric acid and alkylsulfuric salts, alkylsulforlic ch]orides, alkylsulfonic esters, alkylsulfonic acid and alkylsulfonic salts, paraaminobenzenesulfonic aci~, amino~
narhtholsulfonic acids, aminosulfonic acids, anilinsulfonic acids, anthraquinonesulfonic acids, arylsulfonic acids and their amides and chlorides, ethanesulfonic acid, ethyl-sulfuric acid, benzenedisulfonic. acids, benzenesulfamic acid and benzenesul ~ ic acid, benzcatechinsulfonic acid, hro~o-benzenesulfonic acid, bromocamphorsulfonic acid, chloro-sulfonic ester, diaminoanthraquinonedisulfinic acid, nitrobenzolsulfonic acid, nitronaphthalenesulonic acid, nitroso-heta-naphthol-6-sulfonic acid, phenoldisulfonic acid, phenolsulfonic acid, phenylhydrazinesulfonic acid, phenylhydrazinesulfonic sodium, pyridinesulfonic acid~
thiophenesulfonic acid~ vinyl-sulfonic sodium salts, dinitro-oxyna~hthalene-sulfonic acid, halogensulfonic acid, hydrazinesulfonic salts, indigosulfonic acid and 9 ~

indigodisul~onic acid, isododecylbenzenesul~onic sodium, perfluorosulfonic acid, bathocuproindisulfonic sodium salt and dlsodium salt, dimeth~lbenzenesul~onic acid, morpholino-ethanesulfonic acid, naphthoquinonesulfonic acid and salts and rarer sulfon;c acids such as ferro-spectral (III (Il-pyrinyl)-~ bis ~IV-phenylsulfonic acid)-1,2,4-triacine-disodium salt).
Particularly preferred are aryl and alkylaryl sulfonic acids and their salts, and particularly di-lQ isobutylnaphthalenesulfonic sodium.
They can be used with success in both aqueous and non-aqueous solutions in relati~ely concentrated form.
Aldehydes to be used according to the invention are both saturated and unsaturated aliphatic and aromatic alde-hydes as ~ell as compounds that are able to form alde-hydes in acid med~um~
Suitable examples for aldehydes are formaldehyde, acetaldeh~de, pr~pionaldehyde, butyraldehyde, valeraldehyde, glutardialdehyde, pelargonaldehyde, furfurylaldehyde, crotonaldehyde, tlglicaldehyde, sorbicaldehyde, stearin-aldeh~de, malonaldehyde, myristicinaldehyde and pyridin-aldehyde 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 ab~ut 0.5 to 12 mol per mol sulfonic group-containing compound. Usually, the same are used in their commercially obtainable concentrations which may differ _ 9 _ from one aldehy~e to another. Especial]y preferred is a 35~-a~ueous formaldehyde solution.

Phenols are particularly suited as hydroxy compounds These phenols can be mono or polyvalent, substituted or not substituted ~henols such as phenol, resorcinol, renzcatechin, hydroquinone and their tautomeric carbo-nyl forms- trihydroxybenzenes such as pyrogallol, hydroxy-hydroquinone, polyhyclroxybenzenes in their three possible forms (1,2,3,4-, 1,2,3,5- and 1,2,4,5-tetrahydroxy~enæene);
dihydro ~ oluene , 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. ~specially preferred is resorcinol.

Wnen usin~ compounds containing sulfonic groups in the free acid form the use of organic or inorganic acids as hardeners is not absolutely necessary, ~ut has proved to ~e of a ~reat 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.

~cids sulted accordin~ 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.

sually, the acids are used in their commercial concen-trations; however, the same can also be used in more dilu~ed ~orm.

- -10- ~

7!~3 The amounts to be used can be up to about 10 mol, rela-tive to one mol of the compounds con-tainin~ sulfonic ~roups.

The solutions of the starting compounds should be concen-trated and contain only enough water or non-aqueous sol~
vent to keep the products dissolved. 20 to 30 6 water have proved to ~e of particular advantage.

Other, usually used additions according to the invention are: fillers, dyestuffs, pigments, alcohols, inorganic or organic fibers, buffer substances, indicators, cata-lysts t regulators, emulsifiers, plasticizers, stabilizers, displacement reagents, deuterated compounds, me~allo-or~anic compounds, metals and metal salts, alcoholates, phenolates, acetyl acetonates, solvents, hvdrides, amides, heteroelement compounds, products for re~ulatin~ the poly-merization, polyaddition and polycondensation, radicals and radical initiators, cationic and anionic initiators, enzymes, vitamins, hormones, steroids, biochemicals, addi-tives, flame retardants, cross-linking agents, expanding a~ents, UV stabilizexs, antistatic conductive polymers or substances.

~'he same can be used alone or in mixture with ~ne another, and in amounts up to about 50 mol per mol of compound con tainin~ sulfonic groups.

Also other known synthetic or natural resins or mixtures thereof can further be used before or during the condensation ~ ~6~93 process. The said resins can be soluble or insoluble in water. ~uitable resins are for example: resins based on aminoplasts, phenoplasts, desmodur, alpha~omega-urea resins or mi~-tures thereof, UF, PUR, PF resins, as well as styrene polymers, elastomer-modiEied copolymers, poly-amides, polymethacrylates, pol~carbonates, polytetra-fluoroethylene and copolymers, basic substances for makiny polyacetals, aromatic polyethers, polyalkylene terephtha~ates, unsaturated polyester reslns, 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 accordin~ to the invention takes place in most cases at room tem~erature without addition of heat, the temperatures rising at times up to 80C through exothermi~ reactions, depending on the klnd of starting materials and additions used. ~ith the more diluted solutions~ however, external heating may be re~uired 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 0C or diluted solu-tions 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. ~owever, the reaction can like-~ise be effected in vacuum or under pressure.

~ 1~7'~93 ~y varying the mole ratios of the starting materials within the aforementioned ranges, products with differing physical properties can ~e obtained such as sediments, precipitates, oliqomers, lavalike products, sli~htly hardened products, viscous solutions, fibers or quantitatively hardened resins.
I~he synthetic resins according to the invention can be hardened by radiation.
The transparent substances are of small crystalline struc-ture, while the non-transparent substances are of an amor-phous nature.

For a preliminary condensation, a small portion of the aldehyde to be used can be added to the reaction mixture, ancl the remainder added at some later time.

~s already mentioned, foamed plastics can be produced from the plas~ics according to the invention, viz.
soft (molded ancl bulk) foam, semirigid, rigid-, struc~ural and in situ foamed plastics.

~rwo 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 ~um~s, or parts of the solutions from pressure tanks or conveyed by pumps can be fed to -13~

~ ~e7~3 a foam spra~ gun ~foam apparatus~. Any desired pressure and any gas or compr~ssed air as suited for foaming can be used.

All apparatuses described in the literature and patent literature can be used for the process accordin~ to the invention. It i5 of no consequence whether tne solutions or solid adclitions are conveyed at an acute angle or at ri~ht angles, in paral]el flow or in counterflow operation.
~hat is important is that the reaction components are thoroughly mixed so that the necessary chemical reactions are initiated and a foam is produced.

It i~ also possible to produce oams from small handy spray cans in a one~ or multichamber system.

,h foam plastic could industrially be produced by using a tenside in place of a ~F resin condensate and as foaming agent a similar tenside sli~htly diluted with water to which formaldehyde had already been added. Tenside con-centrates foam very poorly or not at all. 1'o achieve a foam;ng action, the concentrated tenside must be diluted with water. The degree of foaming can be readi~y and rationally determined Erom the foam spray gun in the BAUr~NN-GI~ a~paratus. (Chemiker Zeitun~, Chem. ~pp. 90 ~1966) 449).

concentrated tenside can also be diluted with another sulfonic acid ~s a dilute or saturated aqueous solution.
~s a result, the reaction time of resin formation can be shortened.
' -14~

~ ~7~

The examples th~t follow serve for a further ex~lanation of the invention.

~xample 1 400 ml of an a~ueou~ mixture of 138.3 q DIBNS-Na, 44 g resorcinol and 118 ~ of 85~-phosphoric acid with a water con-tent of about 24% were mixed wlth 40 ml of 35%-formaldehyde and stirred with a glass rod, the temperature rising thereat from 22C to 42C. The dark-brown solu-tion changed lts color and first turned light-brown. It then became solid after a few seconds, spontaneously turning red during that time.

sample of this synthetic resin of 480 g was dried in an oven at 105C for one hour. Following that, the sample weiqhed 431.5 g. After two years of storing at room tem-perature, the weight dropped to 320 g. After five years, the weight was still the same. The weight loss of 33.33~
rouqhly corresronds to the amount of water of the starting solution. The suhstance did not chan~e over the en-tire ~eriod.

I~xample 2 . _ ___ l() g of the resin from Example 1 were pulverized, mixed witll 100 ml of a 10%-sodium hydroxide solution, and stirred for 15 hours; the mixture was then filtered.

sliahtly ~rownisll, needle-shaped substance precipitated from the filtrate which was washed with methanol, acidified with sulfuric acid, and shaken out witll ether. ~fter evaporation of the ether, no residue remaineci.

~he precipitate of the resin treated wlth sodium hydroxide solution gave a yield of 94 % after dryin~ a-t 115C. This sihows that the reactants had combined almost quantitatively.

Example 3 _._ _ _ _ 10 ~ ~IB~IS-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 diiso-butvlnaphthalene sulfonic sodiu~ was found to exist in Example 2 it shows that the sulfonic acid in Example 2 is ~ncQ~p~ted in the molecule.

~xamples 4 through 23 __ _ __ _ _ . _ __ _ _ _ In the examples that follow, differinq amounts in formal-aehyde ~7ere teste~.

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-17~
~.
.~, .~, '~7eiaht of resins frorn the reactions using differing amounts of ~or~aldehyde ~xample~ei~ht 12 days 30 days 8 months after reaction after reaction after reaction 4 40.77 cannot be wei~hed 41.85 ~ "
6 42.93 " "
7 44.01 40.10 38.15 8 45.09 40.30 31.90 9 4~.17 40.40 32.20 47.25 42.24 33.S5 11 48.33 41.72 32.53 12 49.41 40.00 32.25 13 50~99 41.12 32.48 14 51.57 41.91 32.~5 52.65 42.25 33.24 16 53.75 42.81 33.65 ]7 ~4.81 42.21 33.00 18 55.89 44.26 33.18 19 43.88 32.90 44.20 33.20 21 43.86 33.08 22 not measured 33.10 23 " " 33.88 ~ ~57~3 In the follo~in~ examples, various startin~ materials, molar ratios, temperatures and addition of other com-~ounds as ~ell as the production of foam materials were demonstrated.

Ixample 24 1 mol diisobutylnaphthalene sulEonic sodium ~ 0.6 mol resorcinol + 2.4 mo~ phosphoric acid were mixed in con-centrated aqueous solution ~ith 0.7 mol he~ametllylene tetramine and heated with stirring. At 50C, a 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 solu~le in n-butanol and dimethylformamide. ~lso from these solutions, the substance could be recovered with hydro-chloric-acid. Phosphoric acid hdrdened the solid sub-stance still further.

~xam~le 25 1 mol diiso~ut~lnaphthalene sulfonic sodium + 0.6 mol resor~nol, 2.6 molsphosphoric acid and 1.6 mo~ urea were mixed in concentrated aqueous solution with 2.11 mols formal~ehyde.

At 50C, under stirrin~, a coherent lavali]~e resin pre-cipita-ted, a e~J milliliters of a ~reenish solution remained.

The solicl substance was insoluble in cold soda lye and dimethylforramide. In hot soda lye, i-t turned bloodred, in dimethylformamide ocher.
l'he greenish solution did not react with soda lye, hydrochloric acid, n-butanol, cyclohexane and furfural.

rlxam~le 26 1 mol diiso~utylnaphthalene sulfonic sodium was dissolved in water and mixed with 0.6 mol resorcin, 2.4 mols phos-phoric acid, 1.6 mo~ urea and 1.1 mo~ oxalic acid and hea-ted. ~t 45C, 0.7 mol hexamethylene tetramine was added. A lavalike resin as in ~xample 25 formed; how-ever, the remaining solution was yellow-brown. It was dried in an oven. At 105C, 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 ~urified suhstance 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.

~xample 27 _ . _ 1 mol diisobutylna~'nthalene sulfonic sodium was dissolved in 5 mo~ water and heated to 60C. This solution was then mixed with 20.5 mol resorcinol and 2 mols formaldehyde. No ;7~
reaction too} ~lace; only after addition of a mo~ phos-~horic acid did a red colored substance result.

~his exam~le demonstrates -that an acid, phosphoric acid in this case, must be adcled to split off the sodium in the sulfonic acid so that a reaction can take ~lace, The ac~d is ~equired as an actiYator as well as a curin~
cat~lyst.

~;xam le 28 1 mol diisobutylnaphthalene sulfonic sodium was dissolved in 5 mo~ water and 2 mo~ formaldehyde and 4 mo~ phos-plloric acid added thereto. The mixture was then heated to 60C. ~ere too, no reaction took place. Only Upon the addition of O.5 mo~ resorcin~did a red resin form.

It can be inferred from this example that a hydroxy com-pound,resorcinol in this case, is required as the cross-linker of the reaction.

Example 29 1 mol diisobutylna~hthalene-disulfonic acid was mixed with 10 mol water, 2.14 mol formaldehyde, 1.23 moh resorcin and 4.58 mo~ phosphoric acid. On heating, the solution reacted, and a precipitate formed. The latter was filtered off and washed with water until the aqueous solu-tion 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 dislntegratedafter standing in air for 19 days.

-2~-~ ~7~93 Lxample 30 1 mol diisobutylnaphthal~nesulfonic sodium was mixed with 0.6 mol resorciTx~ and 2.4 mo~ phosphoric acid in 13 mols water and 0.6 mol formaldehyde added thereto.
The initially brown solution became lighter at 35C, and thic]cened at 48C, but was still stirrable at 80C. It could not be filtered after cooling, but could be pressed on a clay plate. It did not change when drying at 105C.

Example 31 0.9 mol diisobut~lnaphthalene sulonic sodium, 1.8 mo~
resoreinol, 0.9 mol hydrochinone, 0.03 mol tin chloride as catalyst,and 8.5 mols phosphoric acid were dissolved in 50 mols wate~ and mixed with 4.8 mo~ formaldehyde. On heating, a resin precipitated at 50C.

~`xample 31a Foam production-1 1 of a coT~mercial tenside consisting o~ O.34 a DIBNS-Na, 0.11 g r~sorcinDl and 0.295 g 85%~ osphoric acid in about 24%
aqueous solution was introduced into the resin tank of an apparatus used for UF foam plastic production. 1 1 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 foamin~ agent solution.
The whole was then foamed with nozzles used for VF foam ~ ~7~3 ?lastic production, viz. a 2mm resin nozzle and 1.5 mm Eoam nozzle, and with compressecl air a-t 4~5 hars.
~rom the hose connected with the spray aun a slightly yellowish foam emerged which did not collapse. Within 8 minutes, -the temperature in the foam rose from 23.5 to 32.5C. ~t the start o the rcacti.on, the foam turned reddish. In the course of the reaction, the color turned a deep red. The resultant foam was flex-ible and resilient, could be dried at 120C ~7ithout any char,ge and under color intensification. Its weight ~er cubic meter was about 40 kg.
mhe 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 hydro-philic.

5 ~ ~

Solution tests after 24 hours boiled 1. 95%-sulfuric acid dissolved ---la) 40%-sulfuric acid no change no change 2. 37%-fuming hydrochloric acid no change no change

3. 85%-phosphoric acid no changecolor intensification

4. 65%-nitric acid dissolved ---4a) 25%-nitric acid dissolved ---

5. 96%-acetic acid no change no change

6. Absolute alcohol " "; substance no change turns yellow

7. Acetone no change substance turns yellow no change

8. Dimethylformamide no change no change

9. Dioxane no change no change substance turns yellow

10. Paraffin oil no change no change lOa) Motor oil no destruction ---

11. 20%-soda lye no change no change

12. Water no change no change (the p~l value both before and after boiling was 2.5) The melting point of the foam is about 200C. The foam chars in the flame at about 300C without dripping.

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~7~3 It will be appreciated tha~ the instant specification and examples are set forth by way of ill.ustration and not limitation, and that various modiflcations and changes may be made withotlt departing from ~he spirit and ~cope of the present invention.

Claims (14)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method for making a plastic comprising reacting at least one compound containing sulfonic acid groups (a), with at least one aldehyde (b) or a compound which in acid medium is able to form an aldehyde (c), wherein (a) and (c) are present in the form of an acidic concentrated aqueous solution having a water content of about 20 to 30% by weight.

2. A method for making a plastic foam comprising reacting at least one compound containing sulfonic acid groups (a), with at least one aldehyde (b) or a compound which in acid medium is able to form an aldehyde in the presence of a hydroxy compound (c) and a tenside (d) wherein (a) and (c) are present in the form of an acidic concentrated aqueous solution having a water content of about 20 to 30% by weight and (d) is present in the form of an aqueous solution sufficiently diluted to have a foam formed, and per-mitting the reactants to foam and harden.

3. A method according to claim 1 or 2, wherein the compound contain-ing sulfonic acid groups is added in the form of a salt along with an acid.

4. A method according to claim 1 or 2, wherein the aldehyde is formed in situ by addition of a material which forms the aldehyde under the prevail-ing conditions.

5. A method according to claim 1 or 2, wherein per mol of sulfonic acid-containing compound there are present about 0.1 to 5mols of hydroxy compound, about 0.5 to 12 mols of aldehyde, and 0 to about 10 mols of an acid.

6. A method according to claim 1 or 2, wherein the sulfonic acid-containing compound is a sulfonic acid, a sulfinic acid, a sulfamidic acid or a salt thereof.

7. A method according to claim 1 or 2, wherein the sulfonic acid-containing compound is an aryl- or alkylarylsul-fonic acid or a salt thereof.

8. A method according to claim 1 or 2, wherein the hydroxy compound is a phenol.

9. A method according to claim 1 or 2, wherein the hydroxy compound is resorcinol.

10. A method according to claim 1 or 2, wherein the aldehyde is a saturated aliphatic aldehyde with up to about 9 carbon atoms.

11. A method according to claim 1 or 2, wherein the aldehyde is formaldehyde.

12. A method according to claim 1 or 2, wherein the solution is acidic by virtue of the presence of at least one of phosphoric acid, sulfuric acid or acetic acid.

13. A method according to claim 1 or 2, wherein per mol of sulfonic acid-containing compound there are present about 0.1 to 5 mols of hydroxy compound, about 0.5 to 12 mols of aldehyde, 0 to about 10 mols of an acid, and up to about 80 weight % based on total materials other than water of a resin selected from the group consisting of UF, PUR, PF resins, styrene polymers, elastomer-modified copolymers, polyamides, polymethacrylates, poly-carbonates, polytetrafluoroethylene and copolymers, basic substances for mak-ing polyacetals, aromatic polyethers, polyalkylene terephthalates, unsaturated polyester resins, silicone polymers, melamine resins and epoxide resins.

14. A method according to claim 1 or 2, wherein per mol of sulfonic acid-containing compound there are present up to about 50 mols of at least one additive selected from the group consisting of fillers, dyestuffs, pig-ments alcohols, inorganic or organic fibers, buffer substances, indicators, catalysts, regulators, emulsifiers, plasticizers, stabilizers, displacement reagents, deuterated compounds, metalorganic compounds, metals and metal salts, alcoholates, phenolates, acetyl acetonates, solvents, hydrides, amides, hetero-element 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, and antistatic conductive polymers.