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Stabilized diazonium salts and process of effecting same

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US2612494A
US2612494A US5604748A US2612494A US 2612494 A US2612494 A US 2612494A US 5604748 A US5604748 A US 5604748A US 2612494 A US2612494 A US 2612494A
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sulfate
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diazonium
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Glahn William H Von
Herman A Bergstrom
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GAF Chemicals Corp
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films

Description

Patented Sept. 30, 1952 UNITED STATES PATENT orFicE STABILIZED DIAZONIUM SALTS AND PROCESS or EFFECTING SAME William H. von Glahn, Loudonville, and Herman A. Bergstrom, Albany, N. Y., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware 1 No Drawing. Application October 22, 1948,

Serial No. 56,047 Claims. c1.260 -141) 1 tin chloride, cadmium chloride, manganese chloride, sodium fluoroborate, aromatic and aliphatic sulfonic acids, sulfates and chlorides. These are known in the trade as Fast Color Salts (see Saunders, The Aromatic Diazo Compounds, p. 29, London 1936), and the complex-forming salts and acids combinedtherein with the diazo compound are herein referred to as Fast Color Salt stabilizers. In many cases the stabilized diazonium salts thus obtained have fine grain crystals which filter very poorly, due to the particle size,-and result in a large proportion of water in the filter cake. The dried product creates dusting problems during grinding and in subsequent processing steps, such as measuring, pouring' and packaging and use in the dye house. In addition to-the dusting problems arising during theprocessing of these diazonium salts, the fine 4 dust. particles so created are a work hazard in the form of possible skin irritations and other health hazards among the workers.

It has nowbeen found that improved stabilized diazonium compounds may be obtained by first reacting the diazotization product with a surface active agent, thereby effecting a partial stabilization of the diazonium compound with the, surface active agent, and then effecting the remainder of the stabilization with one of the usual Fast Color Salt stabilizers mentioned above. The surface active agents which have been found effective are those of the anionic reactive groupwherein the surface active agent contains an aliphatic hydrophobic group and an aliphatically linked hydrophilic group. Included in this group are surface active alkyl carboxylates, sulfonates, alcohol sulfates and phosphates. More specifically, there are included the following classes of surface active agents:

1. Alkali metal soaps such as sodium oleate,

CH3(CH2)'1CHZCH(CH2)1COONa and sodium stearate CH3 (CH2) uCOONa 2. sulfates of higher fatty acids such as sulfonated castor oil (triglyceride of ricinoleic acid) OSOSNfl CHKCHDsHCHzCH:CH(CHz)1C 0 O CH;

OSOaNa CHs(CH,)5 JHCH,CH:CH(CH|)1C0 0 0H OBOaN8 armcmhtncmomomcmnco0e11, s. Sulfonated higher fatty alcohols such as" the cetyl sulfonic acid and the sodium salt of f dodecyl s-ulfonic acid of USP 1,966,187.

4. Sulfated higher fatty alcohols such asfsqaij um lauryl sulfate C12H25OSO3Na 5. Phosphated higher alcohols such as the product known as W.A.35A.

(C aHu) eNasPaOm not known as Igepon T CnHaaC ONCgH4S OaNB 9. ,Acylaminoalkyl carboxylates such as :4 sodium salt of oleyl sarcosine (3H1 017E380 oncmoooNa 1o. Alkyls-ulfonamidoalkyl sulfonates such as' the product known as Emulphor STU CH3 (CH2) 13-15SO2NHCH2CH2SO3N8.

11. Alkylsulfonamido acetates such a e product known as Emulphor S'I'H i 13. Alkylphenoxyalkyl sulfates such as the sodium sulfuric ester of isooetyl phenyl monoglycolether ooiHio'soiNa The sodium sulfuric ester of dodecyl phenyl monoglycolether CizHz O CgHfOSOsNB butylphenoxy ethanol l4. Amino soaps of fatty acids such as the stearic acid soap of 2-amino-l-butanol The diazonium compounds stabilizedby the surface activeagents and the salts or acids generally ve nployedas stabilizing agents in Fast Color Salts 'F'SuchasmetaIlic chlorides, particularly the mercury, iron, zinc, cadmium, tin, antimony, platinum, gold, copper and arsenic chlorides, naphthalenefiulfonicacids such as naphtha1ene1.5

I disulfonic acid, and fiuoroboric acid are prepared by introducing a solutionsof'the surface active agent into the diazotization solution. The combihed diazo solution and surface active agent solution is then mixed withasolution'eontaining the additional stabilizing agent. The exact order of mixing the reactants is-not' material, although it is preferableto initially mix the diazonium compoundand the' surface active agent. Thus the diazo-,andfsurface active agent can be combined first-and the combined solutions added to a solution of the Fast Color Salt stabilizer (such as 2171012)? the Fast Color 'S'alt; stabilizer can be addedto the mixture'of the'diazo plus the surface active agent; the-diazo and the surface active agent-may be run into the solution of the Fast Color. Salt stabilizer simultaneously;- 'orthe' duced from the same diazonium compounds but stabilized .onlywith the usual or conventional stabilizers. This new crystal growth results in most caseseither in the formation of larger crystals which maybe-different in structure from the crystal structure of the corresponding conventionally stabilized diazonium salts or. in a change of degree of crystal aggregation, usually forming mgr-eater degree :of aggregation. In either case the product can be handled with greater ease and thecsolutionsmoreeiiiciently filtered. It is also characteristic. oft-the diazonium compounds Sta-- I I and the sodium sulfuric acid ester of .tetramethyl- 4 bilized in accordance with this invention that a greater degree of initial dryness is present in the filter cake.

The stabilization of the diazonium salts by means of the surface active agents ,of this-invention thus results in an appreciable reduction of the water content of the filtered diazo cake, as a direct result of the change in crystal pattern or v formation of larger crystals or crystal aggregates.

As compared with ordinary Fast Color Salts which are stabilized "only with the usual metallic salts, less Water is held bythe stabilized diazonium salts of this invention than is held by the Fast Color Salts, the comparative ratio being in the range of 25 to 50% for the conventionally stabilized diazonium salts to 5 to for the diazonium salts stabilized in accordance with this invention. In order to obtain these results appreciable amounts of the surface active agent are used. Preferably about 5 to 20% of the surface active agent based on the. amount of the diazo compound is employed. Afterfiltering and dry. mixing'of the filter cake it may be noted that. the dusting characteristic I of the drypowdered.

product is decreased-to a, considerable degreeand in many cases the resulting Fast ColorSalts are.

rendered completely non-dusting. ,The resistance. .ofthe resulting stabilized diazonium-salts or Fast Color Salts to decomposition during storage .is also greatly improved by the use of they surface active agents. In order to inhibit decomposition of stabilized diazonium salts during storage, it is necessary thatthey be kept as dry as possible. This isaccomplished generally by. ad-- mixingwith the stabilizedtdiazonium salts anhy drous agents, such-as the'ianhydrous sodium sul-- fate,.anhydrousmagnesium sulfate and partially dehydratedaluminum'sulfate mentioned above. These compounds combine with water'to form Water of crystallization and thus keep the di azonium saltsdry. The less water initially pres ent in the filter cakeithe smaller the amount of dehydrating agent which'must be used. In view of the large crystal structure or increased crystal" aggregate formation resulting from the partial surface activecompound stabilization of this invention, the filter cake contains only a fraction of the-water which "is present in'the same di-' azonium salt stabilized by the usual complex salt formation with such compounds as ZnClzand hence requires smaller amounts of the dehydrating agents. Also-the necessity for rigorous'oven drying is eliminated in those cases where the Fast Color'Salts stabilized with the usual stabiliz ers' retain a large amount of-waten In' such cases it is normally necessary not only to hydraulically press them, but also to pre-dry them in ovens heated to approximately 40 C. for from 12 hours to 2 days inorderto bring down the water content. Only after such rigorous drying treatment can they be dry mixed in the usual way. In'the'case' of the surface active agent stabilized diazonium compound of this invention the stabilized diazonium salt pound due to exposure to periods of time is averted.

The following examples will serve to more fully illustrate this invention. It is understood, however, that the invention is not limited'to the.

specific conditions obtaining in these examples which are intended toloe illustrative of the best will be in such aform that only-a fraction'of the water is retained. Hence'dry mixing can be effected immediatelywith the dehydratingagents-and thedangero'f' at least partial decomposition of the diazo come excessive heat for long 'rnahner to effect the products. Unless otherwise This mixture is then cooled to ,10 C. and 13.8 gr.

of 100%. sodium nitrite are added asa 33%.solu-. tion,':care beingtaken that the temperature does not 'risegfabove +10"v C. An excess nitrite test is maintained for /2 hour. Charcoal isadded andthe. diazo solution filtered. A solution .con-

taining 6.0 .gr..sodium'oleate per cc. of water is run into the diazo solution. The resulting solution is run intov a solution containing 57.6 gr. 1.5-naphthalene disulfonic acid in 100 cc. of water.

The precipitate is filtered, sucked dry, and dry mixed and standardized with sodium sulfate, aluminum sulfate and calcined magnesium sulfate.

coarser crystalline structure than theproduct ob- The product obtained from this example has a tained in a similar mannerbutwithout the addition of the sodium oleate. crystalline structurethe filter cake has a higher.

Because of this coarser degree of initial dryness, thus requiring the additiomof smaller amounts of the drying compounds usedindry mixing and lessening the tendency to dust ofithe dry particles.

i j Example 2 follov v ing mixture is slurried for 2 to 3 hours: v 76 cc. water I 50.6 cc. hydrochloric acid (21 B.) 33.6 g-r.- i-nitro-oanisidine The mixture is cooled to 10 C. and 13.8 gr.

of 100% sodium nitrite are added as a 33% solution, care being taken-that thetemperature does not rise above +10"; (3. and excess'nitrite test is maintained for half an hour. Charcoal is added and thediazo solution filtered. l6'gr. sulfonated castor oil are added to the diazo solution and a solutionof '7 gr. of ZnClz in a small amount of water is thenadded. The stabilizeddiazo is salted out with NaCl equivalent to 10% of the volume, filtered, dried, dry-mixed andstandardized with sodiumsulfate, aluminum sulfate and calcined magnesium sulfate. v

The product thus obtained has a coarser crystalline structure than the product obtained in a similar manner, but without the addition of the sulfonated castor oil.' Because of this coarser crystalline structure the filter cake has a higher degree of initial dryness, thus requiring the addi- 8 tion of smalleramounts of the drying compounds used in dry mixing and lessening the tendency to dust of the dry particles. I v s r Erample 3 32.4 gr.-2.5-dichloroaniline are slurried with 46 cc. of water and then heated to 60 C. While applying fast agitation 78 cc. hydrochloric acid (21 B.) are added over a ten minute period.

droehloric acid (21'B.). -to -10,C. and diazotized with 13.8 .gr.' NaNO-zi l as a 33% solution. The solution is "agitated for half an hour, treated with charcoal and filtered. There are then added 30 gr. of'a phosphated high-i) er fatty alcohol known as W.A.35A, said tohavejfl 1' the formula (081117) cNasPaOza, whichis dis-sowed"? in a small amount of water, and 7 gr. ZnClz also f dissolved in a small amount of water. The thus. i stabilized diazo compound is salted out with NaCl equivalent to 10% of the volume, filtered, sucked i dry, dry mixed and standardized'with sodium' The mixtureis cooled to zero degrees and 30 gr.

of iCe ar'e added. 13.8 gr. of sodium nitrite are added asa"33%"solution. The solution is then purified by treating with charcoal followed by v filtering- 5.5 gr. of the sodium salt'of dodecyl.

sulfonicgacid are then added, followed by 7 gr. ZnQh'. disso v d in a' small amount of water. The

resulting stabilized diazo issalted out with Nafil equivalent to 10% of the volume, filtered, sucked dry, dry mixed and standardize'cl'with sodium sulfate. aluminum sulfate, and calcined magnesium 1 sulfate. I

The product obtained in accordancewith this example has properties similar to'thecon ipositions of Examples'l and 2 as comparedwitlithe product f; obtained in a similar manner to that of thisg'f example by omitting the sodium salt of ,dodejcyl'i sulfonic acid. Ezrample 4 l sulting stabilized diazonium salt is salted'out with NaCl equivalent to 10% of the volume, filtered, sucked-dry, dry mixed and standardized with sodium sulfate, aluminum sulfate and calcined I The thus obtained product: has properties similar to those of the productobmagnesium sulfate.

tained in accordance with Example 3.

Example 5 i 33.6 gr. 5-nitro-o-anisidine are slurried with cc. of water. To this are added 65 cc. hy-

sulfate, aluminum sulfate, and' calcined magnesium sulfate.

of this coarser crystalline structure the filter 'cake has a higher degree of initial dryness, thus .ree 1' 'quiring asmaller amount of the drying compound used in dry mixing and lessening the tendency toiff dust of the particles. I

V Escample'd S nitrO-o-anisidine is diazotized in the same. manner as in Example 5. After filteringwtheq charcoal treated diazo solution, petroleum oilsul-e. fonate such as Twitchell Oil 3X is added in the;

amount of 10% of the calculated;amount o diazo compound or about 8 gr. vdissolvedin a small;-

amount of water. An additional 7 gr. of concentrated aqueous solution of ZnClz is added.

The precipitate is filtered, sucked dry, stand-1 ardized and dry mixed with sodium sulfate, alu-f 5 minum sulfate and calcinedmagnesium sulfate. The product thus obtained has acoarser crystal-, line structure than the product. obtained in a.- v

similar manner without the addition of thepetroleum'joil sulfonate." Because .of this coarser CIYSj talline structure, the filter cake hasa higher. de gree of initial dryness, thus requiring the. addition of smaller amounts of-the drying compounds; i used in dry mixing and lessening the tendency;

to .dust of the dry particles... it

The mixture is cooled chloric acid"in"80 cc." of water.

The mixture is cooled to C. and 13.8 gr. sodium nitrite in a" 33 solution'are added while maintaining the temperature belowj C. The resulting di'azo The staride equivalent'to 10% ofthe volume; then fil-' tered, sucked dry,- standardized. and dry. mixed v with sodium sulfate, aluminum sulfate,- and calcined magnesium sulfate.-- 7 V The-productobtained in accordance 'with this i 1 example {has acoarser crystalline structure than I the 'product'obtained in a similar manner omit ting-the additionof diamyl ester sulfosuccinate: Because: of this crystalline structure the'filtercake-"has e, higher degree-of initial dryness, thus" 1 requiring a smaller amount of the dryingcompounds used in dry mixing and lessening the tendency to dust of the particles.-

. Example 8 31 .5 r; of 5 -chloro -o'-'anisidin'e are added to l ccfiof "water and the mixture heated togetheri't'o 85" CI 27jcc. of hydrochloricacid (21 Be.) are then 'added. The resulting solution is cooled to chloric' acid are added. The solution is" again addedas ja1333% solution. The resultingsolution is purified'jby the addition of charcoal and filtered. To the filtered'solution there is added} a solution'of 5 er. of an"acylamidoalkylsulfonate 1 in 20cc1ffof water; Aconcentrated aqueous'so'luf-f tion'of"'7gr.fof"ZnCl2 islthenadded. Theresult v ing 'stabilizeddiazo' compound is then saltedout veryislowly with Na'ClEequivalent to 10% by vol nine." The' precipitate iisv filtered, sucked dry; standardizedand dry 'mixed'with sodium sulfate;

aluminum "sulfatef'and "calcined magnesium Sulfate; A product 'is obtained which"has"a'-coarser'"1 crystalline structure than that obtained lira similar manner without the-addition of the acylami: doalkylsulfonate. This coarser crystalline prod:-

uct has a higher degree of initial dryness', thus.

elim'iiiating the necessity for special drying pro-* cedures i and: requiring the; i addition 1 of "smaller. amounts of'the drying compounds used in drymixing'i The-tendencyto dust of the drypoWderis also considerably reduced;

Example 9 2813 of:ii chloro-o toluidine are added.- 115 cc. ofwater "and the solution. heated tot85t" C. 2'z'cct of 21 B. HCl. are thenradded andthe solution coole'd'to- 5 C. while adding:antaddis. tional'i27 cc." of 21.B; HCl.

again f cooled ta -5 C. after'i'whic'h 13.8 gifizo'f". sodiumln itri'te'are added'as a '33% solution; .The f The 'SO'llltiOD. is

resulting diazogcompoun'd is purifiedbythe addia tion' of charcoaland filtered. To the filtered: diaizo solution thereareadded 4 gn ofthev sodiumi': salt' 'ofoleyl sarcosine in 20 cc; of water;- A con-'- eentrated aqueous solution of 7 gr, Of 'ZIiCIQ'ar'e those obtained .as-the product ofExample thenfradded. and the stabilized: diazoncompoundt.

resulting from these additions iS"Sa,1t6d.Ol1t.'by'.fi adding slowly N aCl equivalent to 10% by volume. The precipitate is filtered, sucked dry, standardized and drymixed withisodiumsulfataialui minum sulfate and calcined magnesium sulfate The product thus obtained has characteristics similar to the product of Example 8.

Example .10

31.5 gr. l of 4-chloro-fo-anisidine; tare 'saddedttoc 115 cc. 10f wateriand. the soluti'omheatedat. 30

ing solution is cooled-to -5?'Cfandani'additionah;

27 630. 01- 21 'B. HCl are"added. Thesolutionzis again cooled to 5 0., after which 13.8. grxso-r dium' nitrite -are added 'as:'a'l33%' solution. Thee resulting diazo solution.is"= purified by the audi -I tion'iof charcoal and filtered. To the filtered-sea 'luti'on' 'thr'eare then added 1 5 gr. 'ofzi'a' vsodium salt of an alkyl sulfonamido alkyli sulfonate hav ing the general formula- CH3"(CH2) 13 1tSO2NI-ICHi'CHiSO:iNa' in a solution of20 cc. .ofs'water. A concentrated.

aqueous.-solutiontcontaining 7 gr.. ZnCl-z. is then i. added. The resulting ista'bilized'di'azonium salt-1st,

s'altediout byslowly. adding an amount of NaCl:.;. equivalent to 10% of the volume. The precipi-l 'tateis filtered,:suckeddry,' st'andardizedtand dry mixed withsodium sulfate, aluminumisulfate and 1 calcined magnesium sulfate. The productcobei tained has a coarser crystallineistructurea than;

that obtained in a similar.. manner without the addition of the sodium alkyl sulfo-namido alkyl sulfonate. This coarser crystalline =product -in the form of the filter cake has a higher degree" 7 of essential dryness, thus eliminating the necessity for special drying procedures and reducing.

the amount of drying compoundsrequirediin the dry mixing. The tendency to dust of the dry. particles'is also reduced. q

7 E m le- 33.6" gr; 5-nitro-'o'-anisidine' aretslurried with"- cc. ofw'ater. To this slurry are added 65cc. of 21 B'. HCl." The mixture is cooled to -l0'-"C. and there are then added-13.8gr. sodium nitriteas a'33 %-solution. The resulting diazotized'solution is agitated for'halfan hour, clarified by? the addition of charcoal and filtered. To-'the-filtered 'diazo solution there areadded 5 'gr. ofth'e sodium alkyl sulfonamido acetate having the for--- mula CH3 (CHsi) i R I5NI-ICHaCOONQI dissolved iii-.15 cc.. of. water. A concentrated. aqueous solution of ZnClz is then added. The

stabilized diazonium salt thu s obtainedis salted) I out by the additionof an amount of NaGl equiva .lent to 10% of the volume.. Theprecipitateis filtered, sucked dry, standardized, and dry mixed with sodium sulfate, aluminum sulfate-and cal-.-

cined magnesium sulfate. The crystalline product .thus obtained has characteristics similar to Emmpze 12 33.6 gr. Z-nitro-p-anisidine are slurriedrin r46 cc. of water. 53 color 21 BVHCI are addedto: 1 the slurry and theresulting solutionis .cooledto 5 C.,- after which 13.8 gr. sodium"nitritev aref addedas 9. 33% solution. Thisdiazotizationrsolution is then salted to saturation; clarified byr treatment with charcoal and filtered. To the fil--- .-'tered solution there are addedQgr; oi sulfate-oi mixed fatty, acid monoglycerides knowngasiArctic *Syntex M (Young and Coons Surface-Active Agents, =p. 119) dissolved-in 30 cc.ofwater. To this solution there are added 7 gr. of Zl'lClz' in concentrated aqueous solution. The thussfiabiflized diazonium salt is then salted out, filtered,

sucked dry, standardized and dry mixed with so- .dium;;sulfate;-. aluminum sulfate and calcined ;=imagn'esium'-su1fate. The product thusuobtained has a coarser crystalline structure than that obtained ina similar manner but without the addiation of: thesulfated'mixed fatty acid monoglyceride.,,:..,

' Ezcarnple 13" -f. mi'inoglycoletherdissolvedin'20. cc. of water. A

concentrated aqueous solution of 95 gr, of bad- Qhlblflde is Tth'en. added. The resulting product is salted out andfinished inthesame salted out by, the addition of an; amount of NaCl equivalent to 15% of the volume while cool- -;ing to about -C 2.. ;The precipitateis filtered,

Thefollowing mixtureisslurried for'l 51.2 gr. l -amino fi5 me thyl-mrbnzanisld 9', minutes. Thediazonium solution .is;,cl'a'r charcoal treatment followed by,.filtration.-.

' ,mannerasthe product of the preceding example.

' 'thalt exam'ple.

"It"has' similar characteristics tov the. product of E mamp leild 1 1 manner as in Example 12. To the filtered diazo solution there are added 4.5 gr. of the stearic acid soap of Z-aminobutanol followed by the addition of 7 gr. ZnCh in .aconcentrated aqueous solution. The resulting product is salted out and finishedpin'the samemanner as in the case of Example 12. Its properties are similar to those of the product of Example .12.

Example] 5 Theljf ol-lowing mixturel is slurried for '1 hr.:

24.4 gr. dianisidine 532 cc. water 63 cc.21B.HCl

"*The mixture is cooled to 5" Cfand tetrazotized in '5 3 4 hr. with 13.8 gr. sodiur'rihitrite as a'33% so'-' lution. The temperature should be held below 10 C. An excess nitrite test is maintained for min. The diazonium solution is clarified by charcoal treatment followed by filtration. 9 gr. of sodium lauryl sulfate are added and a concentrated aqueous solution of 7 gr. of ZIlClz. The stabilized diazo is salted out with an amount of NaCl equivalent to 10% .of the volume, filtered, sucked dry, and dry mixed and standardized by the addition of sodium sulfate, aluminum sulfate and calcined magnesium sulfate. The crystalline product thus obtained is similar in characteristics to the product of Example 10.

Example 16 The following mixture is slurried for 1 hr.:

42.8 gr. 4'-methoXy-4-aminodiphenylamine I 555 cc. water 107.5 cc. 21 B. I-ICI solution, then purified by charcoal treatment and -mt'ro -'p-anisidine-is diazotized in the same tion of anjaqueo'usj 's'uspension tli filter cakev of thel'corresponding arom -um salt combine'd as a com e so ly:

filtered. 7.5 gr. diamyl ester of sodium sulfosucout with ,NaCl equivalent to -.10% or, filtered, sucked dry. and .dry

. he product has'jch acteristics .j siniila r 1 We claim: l

Y -;A,st b1 ..d ..n.

" position comprising Jan aroma .ride, said complex. diazgiiium; Isa

sucked dry, andstandardized a 'igldry mixed with sodium sulfate, aluminum sulfate and calcined magnesium sulfate; The crystalline product; thus obtained has characteristics similar to those, obtained as the PIQdHCQQQfEXEJIIPIG10."

jam-gm C. An excess nitrite. test .isfmdihtainedj sul fonated castor' oilare added to thediazosolw tion and a solution.,of.-'7.;gr.' z c12,. m.a1sma11 amount of water. ...The stabilizeddiaz ardi'zed by the addition'o'f 'sodii in' Surat lainminum sulfate. and calcined magnesium product of in. complex; -.combination. with .a

.. anionic suff-ace-activadgerit containinga cast v. one, long chain alkyl group land-having.

philic grouplaliphatically linked, a

having. a' gcrystallineyform. which retains less mother liquorin a filter .cake'pbtai edgy-filtrachloridef. a

21 A stable, dry, non-dusting clia position comprising an aromatic diazonium salt in complex combination with a mixture of an anionic surface-active agent containing at least one long chain alkyl group and having its hydrovphilic group aliphatically. linked, and cadmium chloride, said complex diazonium salt combination having a crystalline form which retains less mother liquor in a filter cake obtained by filtration of an aqueous suspension thereof than a filter cake of the corresponding aromatic diazonium salt combined as a complex solely with cadmium chloride.

3. A stable, dry, non-dusting diazonium composition comprising an aromatic diazonium salt in complex combination with a mixture of an anionic surface-active agent containing at least one long chain alkyl group and having its hydrophilic group aliphatically linked, and 1,5-naphthalene disulfonic acid, said complex diazonium salt combination having a crystalline form which retains less mother liquor in a filter cake obtained position" comprising an -aromatic diazonium' saltv diazonium salt in solid form which involves precipitationxof: anxaromatic: :diazonium risalt. from aqueous solution with a Fast Color Salt stabilizer, the improvementwhiolrcomprises-adding to the aqueous solution of said diazonium -salt, prior to said precipitation, a substantial amount of an' 7 aniionicsurface=active agentcontaining at least f .one'iflon'g fchain" lalkyl group and having" its hy- Pficlrdpfiiliagroupialiph'atically linked, and' e'ffect- 1t'ingj"theiaioresaiidprecipitation of i the stable diiazoniumisaltin solid iormiinthe"presence of:

1- I" sfaidsurfaceeactive agentjrto form a complex arov ematic :Ediazonium :double salt""part1yi with: said FTdiaZOnium" "salt "in" solid form which? involves ifpi'ecipitationbf an aromatic: 'diazonium salt from iagqueousfsolutioni with: a Fast "Color Salt. stai'bilizerjithe"improvement which comprises adding to"the'"aqueous'solution of said diazonium salt, prior to said precipitation,"an"'anionicisur-' face-active .agentcontaining at 1e'ast"one long fc'liain" alkyk'group and having its hydrophilic i j jg'roupiaiiphatica'lly linkedfi the surface active "agenti'being added in anramount 'equal' to at ?*leas't %ofthe' amount of'the"idia"zonium'salt,

' and?ifecting:the"aforesaid'precipitationiof. the f stablediazoniumsalt'infsolidgform thej pres- 'erme iiffsaidisu'rfa'cmactive agent'to form a 'comfpleraromatio'idiazoniumfdouble 's'altipai'tly with said anionic' surface-active agent and partly i,with:said"FastColorSalt stabilizer.

1. "9:5 stable; dry;non dustingiidiazonium' com- "iposition"comprising -an' "aromatic diazoniumsalt .in complex combination with a mixture of a; Fast anionicsui'face-active agent and partly with said Fast"Color."Salt stabilizer.

"lna'processforithe" preparation of: a stable Color?salt stabilizeiz andan aniomc surtaceiactive --a'gent -'containing at least zone longvchainfalkyl group and having its hydrophilicgroup-aliphatic'ally linked; said complex diazonium salt combi- 5 nation having a crystalline form which retains "lessmother liquor in a filter :cake obtained 'by filtration' of an aqueous suspension thereof' than a filter cake offlthe correspondingaromatic .*di i 'azonium' salt' combinedas -a complex: solely' with said -"Fastl color Salt stabilizer.

210.1% rstable; dr-y, nondusting;=Idiazonium:comzposition comprising: an raromaticirdiazoniumaisalt in complex combination with a mixturasof a Fast Color Saltvstabilizerz and an anionic surl5 face-active .agent.containing .at least one long i chaimalkyl"grouptandi. havingfiits "hydrophilio figroup aliphatioa'l'ly linked, tithe *"suiface-aotive "agent being-present in an amount equal'rto from '5 to of the"amounto *thefliiazoniumts'alt, said'complexi diazoniums'alt combination'having ".a; crystalline form'"whicht'retains less 'moth'er; liqnor "in a "filter "cake. obtained. by filtrationoft an 'of' the' corresponding" aromaticdiazonium"?salt combined" asa "complex" solely'with" said Fast Color Salt stabilizer.

WILLIAM H. VON GLAHN. v..I-IIE RMAN: -:A. BERGSTIROM.

REFERENCESLCITED The'ifollowing "references'are of record tin the Number .'..Name JTDate 2,107,159 "Martone '"Feb. 111938 2,196,985 Flett Apr. 16, 1940 2,381,145 vVon Glahnet al Aug. 7, 1945 0 2,402,106 Vori'Glahmet'al. "June"11, 1946 I FOREIGN PATENTS Number Country 1 Date aqueous suspension ithereof than; a filter cake I

Claims (1)

  1. 5. A STABLE, DRY, NON-DUSTING DIAZONIUM COMPOSITION COMPRISING AN AROMATIC DIAZONIUM SALT IN COMPLEX COMBINATION WITH A MIXTURE OF SODIUM OLEATE AND 1,5-NAPHTHALENE DISULFONIC ACID.
US2612494A 1948-10-22 1948-10-22 Stabilized diazonium salts and process of effecting same Expired - Lifetime US2612494A (en)

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FR991566A FR991566A (en) 1948-10-22 1949-08-02 Process for the preparation of diazonium salts stabilized
DE1949G0000079 DE855117C (en) 1948-10-22 1949-10-13 A process for the preparation of stabilized diazonium salt complex preparations
GB2633049A GB661533A (en) 1948-10-22 1949-10-13 Stabilized diazonium salts and process of effecting same

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US2707181A (en) * 1955-04-26 Method for preparing solid diazonium
US2809189A (en) * 1957-10-08 Method of producing stabilized
US2812321A (en) * 1955-11-15 1957-11-05 American Cyanamid Co Process for diazotization and coupling
US3847614A (en) * 1971-09-13 1974-11-12 Scott Paper Co Diazo photopolymer composition and article comprising carboxylated resin
US4403028A (en) * 1981-01-26 1983-09-06 Andrews Paper & Chemical Co., Inc. Light sensitive diazonium salts and diazotype materials
US5616443A (en) * 1993-08-05 1997-04-01 Kimberly-Clark Corporation Substrate having a mutable colored composition thereon
US5643356A (en) * 1993-08-05 1997-07-01 Kimberly-Clark Corporation Ink for ink jet printers
US5645964A (en) * 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US5681380A (en) * 1995-06-05 1997-10-28 Kimberly-Clark Worldwide, Inc. Ink for ink jet printers
US5700850A (en) * 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US5709955A (en) * 1994-06-30 1998-01-20 Kimberly-Clark Corporation Adhesive composition curable upon exposure to radiation and applications therefor
US5721287A (en) * 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US5733693A (en) * 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5739175A (en) * 1995-06-05 1998-04-14 Kimberly-Clark Worldwide, Inc. Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5747550A (en) * 1995-06-05 1998-05-05 Kimberly-Clark Worldwide, Inc. Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US5773182A (en) * 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US5782963A (en) * 1996-03-29 1998-07-21 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5786132A (en) * 1995-06-05 1998-07-28 Kimberly-Clark Corporation Pre-dyes, mutable dye compositions, and methods of developing a color
US5798015A (en) * 1995-06-05 1998-08-25 Kimberly-Clark Worldwide, Inc. Method of laminating a structure with adhesive containing a photoreactor composition
US5811199A (en) * 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
US5849411A (en) * 1995-06-05 1998-12-15 Kimberly-Clark Worldwide, Inc. Polymer film, nonwoven web and fibers containing a photoreactor composition
US5855655A (en) * 1996-03-29 1999-01-05 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US5865471A (en) * 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US5885337A (en) * 1995-11-28 1999-03-23 Nohr; Ronald Sinclair Colorant stabilizers
US5891229A (en) * 1996-03-29 1999-04-06 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6008268A (en) * 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
US6017661A (en) * 1994-11-09 2000-01-25 Kimberly-Clark Corporation Temporary marking using photoerasable colorants
US6017471A (en) * 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6033465A (en) * 1995-06-28 2000-03-07 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US6063551A (en) * 1995-06-05 2000-05-16 Kimberly-Clark Worldwide, Inc. Mutable dye composition and method of developing a color
US6071979A (en) * 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
US6099628A (en) * 1996-03-29 2000-08-08 Kimberly-Clark Worldwide, Inc. Colorant stabilizers
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US6228157B1 (en) 1998-07-20 2001-05-08 Ronald S. Nohr Ink jet ink compositions
US6242057B1 (en) 1994-06-30 2001-06-05 Kimberly-Clark Worldwide, Inc. Photoreactor composition and applications therefor
US6265458B1 (en) 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6277897B1 (en) 1998-06-03 2001-08-21 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6294698B1 (en) * 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6331056B1 (en) 1999-02-25 2001-12-18 Kimberly-Clark Worldwide, Inc. Printing apparatus and applications therefor
US6368395B1 (en) 1999-05-24 2002-04-09 Kimberly-Clark Worldwide, Inc. Subphthalocyanine colorants, ink compositions, and method of making the same
US6368396B1 (en) 1999-01-19 2002-04-09 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same
US6503559B1 (en) 1998-06-03 2003-01-07 Kimberly-Clark Worldwide, Inc. Neonanoplasts and microemulsion technology for inks and ink jet printing
US6524379B2 (en) 1997-08-15 2003-02-25 Kimberly-Clark Worldwide, Inc. Colorants, colorant stabilizers, ink compositions, and improved methods of making the same

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US2707181A (en) * 1955-04-26 Method for preparing solid diazonium
US2809189A (en) * 1957-10-08 Method of producing stabilized
US2812321A (en) * 1955-11-15 1957-11-05 American Cyanamid Co Process for diazotization and coupling
US3847614A (en) * 1971-09-13 1974-11-12 Scott Paper Co Diazo photopolymer composition and article comprising carboxylated resin
US4403028A (en) * 1981-01-26 1983-09-06 Andrews Paper & Chemical Co., Inc. Light sensitive diazonium salts and diazotype materials
US5643356A (en) * 1993-08-05 1997-07-01 Kimberly-Clark Corporation Ink for ink jet printers
US5643701A (en) * 1993-08-05 1997-07-01 Kimberly-Clark Corporation Electrophotgraphic process utilizing mutable colored composition
US5616443A (en) * 1993-08-05 1997-04-01 Kimberly-Clark Corporation Substrate having a mutable colored composition thereon
US5645964A (en) * 1993-08-05 1997-07-08 Kimberly-Clark Corporation Digital information recording media and method of using same
US6211383B1 (en) 1993-08-05 2001-04-03 Kimberly-Clark Worldwide, Inc. Nohr-McDonald elimination reaction
US5683843A (en) * 1993-08-05 1997-11-04 Kimberly-Clark Corporation Solid colored composition mutable by ultraviolet radiation
US5700850A (en) * 1993-08-05 1997-12-23 Kimberly-Clark Worldwide Colorant compositions and colorant stabilizers
US6017471A (en) * 1993-08-05 2000-01-25 Kimberly-Clark Worldwide, Inc. Colorants and colorant modifiers
US5721287A (en) * 1993-08-05 1998-02-24 Kimberly-Clark Worldwide, Inc. Method of mutating a colorant by irradiation
US6127073A (en) * 1993-08-05 2000-10-03 Kimberly-Clark Worldwide, Inc. Method for concealing information and document for securely communicating concealed information
US6066439A (en) * 1993-08-05 2000-05-23 Kimberly-Clark Worldwide, Inc. Instrument for photoerasable marking
US6060200A (en) * 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms and methods
US5773182A (en) * 1993-08-05 1998-06-30 Kimberly-Clark Worldwide, Inc. Method of light stabilizing a colorant
US5865471A (en) * 1993-08-05 1999-02-02 Kimberly-Clark Worldwide, Inc. Photo-erasable data processing forms
US6060223A (en) * 1993-08-05 2000-05-09 Kimberly-Clark Worldwide, Inc. Plastic article for colored printing and method for printing on a colored plastic article
US6120949A (en) * 1993-08-05 2000-09-19 Kimberly-Clark Worldwide, Inc. Photoerasable paint and method for using photoerasable paint
US6054256A (en) * 1993-08-05 2000-04-25 Kimberly-Clark Worldwide, Inc. Method and apparatus for indicating ultraviolet light exposure
US5733693A (en) * 1993-08-05 1998-03-31 Kimberly-Clark Worldwide, Inc. Method for improving the readability of data processing forms
US5858586A (en) * 1993-08-05 1999-01-12 Kimberly-Clark Corporation Digital information recording media and method of using same
US5908495A (en) * 1993-08-05 1999-06-01 Nohr; Ronald Sinclair Ink for ink jet printers
US6342305B1 (en) 1993-09-10 2002-01-29 Kimberly-Clark Corporation Colorants and colorant modifiers
US5709955A (en) * 1994-06-30 1998-01-20 Kimberly-Clark Corporation Adhesive composition curable upon exposure to radiation and applications therefor
US6071979A (en) * 1994-06-30 2000-06-06 Kimberly-Clark Worldwide, Inc. Photoreactor composition method of generating a reactive species and applications therefor
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US6008268A (en) * 1994-10-21 1999-12-28 Kimberly-Clark Worldwide, Inc. Photoreactor composition, method of generating a reactive species, and applications therefor
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US6235095B1 (en) 1994-12-20 2001-05-22 Ronald Sinclair Nohr Ink for inkjet printers
US5811199A (en) * 1995-06-05 1998-09-22 Kimberly-Clark Worldwide, Inc. Adhesive compositions containing a photoreactor composition
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DE855117C (en) 1952-11-10 grant
GB661533A (en) 1951-11-21 application
FR991566A (en) 1951-10-08 grant

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