Патент USA US2406217код для вставки
‘' 2,406,217, ' Patented Aug. 20, 1946 UNITED STATES ‘PATENT . OFFICE UCTS AND METHODS FOR PRODUCING THE SAME Mortimer '1‘. Harvey, South Orange, N. 1., and Solomon Caplan, New York, N. Y., assignors to Harvel Research Corporation, a corporation 0 New Jersey No Drawing. Application October 23, 1942. Serial No. 463,132 2 Claims‘. > . (Cl. 260-69) 2 , 1 Example ‘Tertiary butyl urea _____________ "grams" 11d Formaldehyde solution (371/2%‘)_____do____ 10o It is an object of the present invention to pro duce stable aqueous solutions of the urea-form aldehyde type of condensation product. , The present application is a continuation in part of our copending application Ser. No. 294, Ammonia solution (26°) ____________ __cc_.. 2.7 This mixture was re?uxed at boiling temperature 480, ?led September 12, 1939. for one hour and allowed to cool. . ' When employing thermosetting resins for such purposes as impregnation of porous compositions, as coatings for laminating purposes, for plywood Example 2 _ Tertiary butyl urea ,_ ________ -_‘..___'grams_- 116 adhesives, and the like,‘ it is usually necessary 10 Formaldehyde solution (SW/2%) -_-_do____ 160 Ammonia solution (26") ____________ .._cc_.. 2.7 Organic solvents have almost ‘universally been ‘This mixture was re?uxed at boiling tempera‘ employed for the purpose of obtaining such solu to utilize solutions of such‘ thermosettingoresins. tions and in the subsequent operations of con ture for one hour and allowed to cool. . verting the thermosetting resin to the infusible 15 Example 3 v state, the organic solvents have been ‘driven off _ and lost. It/ would therefore be desirable to use water as the solvent for the thermosetting resin. Tertiary butyl urea ____; ________ "grams" 116 Formaldehyde solution (371/2%) ____do____ 240 Ammonia solution (26°) _________ _1__.._cc__ 2.7 Such water soluble thermosetting resins have‘ been developed in the nature of urea-formalde 20 This mixture was refluxed at boiling tempera hyde condensatiomproducts. The great disad ture for one hour and allowed to cool. vantage of such aqueous solutions of urea-form aldehyde resins has been their short storage life. Examples 4, 5 and 6 ' The above series of experiments was repeated This objection has long been recognized and vari ous means of overcoming it have been proposed. 25 but instead or 116 grams of tertiary butyl urea, Thus, for example, in an article published in In 130 grams of tertiary amyl urea was used. dustrial and Engineering Chemistry, vol. 31, page v673 (1939), the authors have drawn attention to this failing of vaqueous Solutions of urea-form aldehyde resins and have proposed the addition of glycols for the purpose of stabilizing the solu tions. Owing to the water solubility of the gly cols, the ?nished products, even after conversion to the infusible state, have rather poor water resistance. 30' the use of 144 grams of tertiary hexyl urea in stead of the 116 grams of tertiary butyl urea. In all of the above examples the resulting aque ous solutions showed substantially no increase in viscosity after months of storage at room tem . - densation products of the monotertiary-alkyl . 40 resulting combined solutions were stabilized to a The present invention is based upon the ?nd- ‘ 1 ing that aqueous solutions of formaldehyde con perature. Aqueous solutions of the formaldehyde conden sation products where then mixed with aqueous solutions of freshly prepared urea-formaldehyde condensation products and it was found that the It is further an object of the present invention to produce stable aqueous solutions of the urea. formaldehyde type of resin in which'the stabiliz ing agent is itself-capable of reacting with the formaldehyde with the production of thermos'et ting resins having high moisture resistance. Examples 7, 8 and 9 Examples 1, 2 and 3 were repeated but with degree varying with the proportion of the ter tiary‘ alkyl urea-formaldehyde condensation product added. ' , Instead of performing two separate formalde- , ureas are extremely stable and that mixtures of 45 hyde reactions, one with urea and the other with the tertiary alkyl urea and then mixing the prod urea with monotertiary-alkyl ureas, upon reac ucts, the more economical procedure would con tion with formaldehyde, produce stable aqueous sistin mixing urea with the tertiary alkyl ureas solutions of thermosetting resins. For the meth-' and reacting upon that mixture with formalde od of preparing such tertiary-alkyl ureas, refer 50 hyde. This was tried and found to produce sta ence is made to our Patent 2,247,495, issued July bilized solutions, the degree of stability again 1, 1941. _ As illustrative examples of the formaldehyde being dependent upon the amount of tertiary condensation products of the mono-tertiary-alkyl alkyl urea added to the urea. ' The following examples are presented for illus ureas, the following are given: - tratlve purposes. 1 I Example 10 Urea 4 I , grams" - This solution was re?uxed at boiling temperature for one hour and allowed to cool. The solution gelled to a non-?owing state within two weeks at 60 ‘Formaldehyde solution (37%%) ---_do_-..--200 ' Ammoniasolution (26°) _____________ --cc__ room temperature. 2.3 This was re?uxed at boiling tempera ture for ‘one hour and then permitted to cool. The solution became a non-?owing gel within ~ 10 Ammonia solution (26°).__'__‘_____.#___-_cc__ 1.4 60 This mixture was re?uxed for one hour at boil Example 11 ’ . . ‘Urea grams" ‘80 Tertiary butyl urea ______________ .._..do_-.._ 12 Formaldehyde solution (37%%) ____ _..do_..__ 120 \ two weeks of storage at room temperature. ' Urea I Example 18 grams.._ ing temperature and allowed to cool. There was only a slight increase in'viscosity after two months " Tertiary butyl urea ______ _.'______ _-do_-__ Formaldehyde solution (37%%) ,-..__do-___ 200 '- Ammonia solution‘ (26°) _____________ ..-cc-.. 2.3 15 standing at room temperature. This solution was re?uxed at boiling tempera ‘ - Example 19 ‘ p - ture for one hour and permitted to cool. Upon Urea ‘ grams" Tertiary amyl urea ...... ..-_ ....... --do-.._- standing at room temperature, it became a non ?owing gel after three weeks. 4 ‘ Example 12 Urea _ 20 Formaldehyde solution (37%%) .... .._do__-- 120 Ammonia solution (26°)_..__' ..... __'____cc..- 1.4 . grams" 60 Tertiary amyl urea _______________ "do-.." This mixture was re?uxed for one hour‘ at boil‘ ing temperature and allowed tov cool. There was 6 Formaldehyde solution (37%%) _---do--_- 200 Ammonia solution (26") _____________ --cc-..- 2.3 25 This mixture was re?uxed at‘boiling temperature iorone hour and allowed to cool at room temper ature. The solution gelled to a non-?owing state 30 Formaldehyde solution (37%%) .... -..do.....- 120 Ammonia solution- (26") ..--.' ........ _-cc_- 1.4 Example 13 grams“ This mixture was re?uxed for one hour at boll ing temperature and allowed to cool. There was Formaldehyde solution (37%%)--___do_--- 275 Ammonia solution (26°) _____________ _.cc._ 3 35 only a slight increase in viscosity after two months This solution was re?uxed for one hour at boll ing temperature and allowed to cool. The solu standing at room temperature. In each ofthe above examples, where mixtures tion gelled to a non-?owing state after two weeks ' on standing at, room temperature. . Erample 14 _ only a slight increase in viscosity after two months ‘ standing at room temperature. Example 20 Urea grams.._ 80 Tertiary hexyl urea............... ..-do_-..-' 12, I I after four weeks at room temperature. Urea I of urea and tertiary‘urea were employed, the so lution of the reaction products, upon acidi?ca- ' 40 tion and heating at 110° 0., produced intusible v ?lms which had good water resistance. . Urea _ ' 60 12 grams..- 60 , . In addition to the urea and substituted ureas . Formaldehyde solution (37 $6 %) ----_'_do-;.-_ 275 disclosed in the preceding examples, other sub- . stances may be present for the purpose‘ of modi 45 iying the properties or the resins obtained and in This solution was re?uxed for one hour at.boil particular those addition substances which pos sess the property of reacting with formaldehyde ing temperature and allowed to cool. There was no change in viscosity after two months standing with the production or water soluble condensa- . at room temperature. ' tion products. Such a substance, for example, Tertiary butyl urea .... -_>__- ________ --do-.._Ammonia solution (26°) _____________ -..cc-.. Example.- 15 ‘Urea ‘ g 18 3 .. _ - grams-_ 60. would be melamine. 60 Tertiaryamyl urea ................ -..do...__ 18 _ Formaldehyde solution (37 Vz%) .... ...do.... 27; ' Ammonia solution (26‘) ____________ ....‘-cc- This solution was re?uxed for one hour at boil proportions of from ten to thirty per cent of the 55 alkyl urea, based on theweight or the urea. are suitable for 1 the production or water-resistant - coatings, laminated products. plywood veneers and ‘ I ing temperature‘ and allowed to cool. There was the like. no change in viscosity after two' months standing at room temperature. 7 ' As previously stated, the aqueous solution oi the reaction products or formaldehyde with the mixtures of urea\and tertiary alkyl ureas in the , Although‘ the present invention is particularly ' suited for the production or aqueous solutions of resins, there are occasions when the solutions or. these resins in organic solvents are desirable, par 3 'Urea > grams 80 ticularly when it is desired to incorporate such Tertiary hexyl urea_____ __' ________ __do..--_ 18 resins into oleoresinous varnishes. For such pur . "Formaldehyde solution (37%%)-___..do..--_ 275 pose, the aqueous solutions obtained in accord ‘ Ammonia solution (26°) _____________ -_cc__ 365 ance with the preceding examples are acidi?ed This mixture was re?uxed for one hour at boiling and then shaken with such solvent as butyl al- . r I Example 16 so _ temperature and allowed to cool. There was no 3 change in viscosity after two months standing ‘at room temperature. . . - 70 Example 17 Urea ' grams" cohol, a'mylalcohol. octyl alcohol or combinations 60 ‘ Formaldehyde solution (37%%) .... -_do._-_- 120 or these. It has been found that the solutions in organic solvents or the joint resins disclosed in this invention are capable of dilution with appreciably greater proportions of mineral sol-V vents,~such as the various paint thinners obtained ' from petroleum, than is possible with similar so ‘ Ammonia solution (26°)-_- ___________ -..cc__ 1.4 75 ,iution or urea-formaldehyde condensation prodw - 2,400,917 . - 5 ‘ uctspreparedintheahsenceoithetertiarraikyi ureas. 1. The method of produoinl not which comprises heat - It is aiso possible to prepare moidins' powders from the aqueous solutions or the joint, resins disclosed inthisinventionbytheadditionoi ab ‘ sorhent nllers, suoh as wood solutions or the resins and hour. to the aqueous removal ot-the wa-v. _ astahisaqueous' I solution of urea-iormaidehriie condensation prod moiesoiaqueousi } de-withamixture containing one moie of urea ‘ 5. a mono-tertiary- i-urea havina from tour to six carbon-atoms in the'aikyi group equal to from tentothirtyperoentoitheurea. ter either by “Dilution so! suction and heat or ' 2. A composition oi matter comprisins a heat bymeans oihotmixinsroiis. Acidicaaentsmay reaction product of iron; one to three moles of be incorporated either with the aqueous solution 10 aqueous iormaidehyde with a mixture containins iinai molding powder. \ottheresinsorwiththe suchmoidins one moleioi urea and an amount of a mono-ter powders ' It has been found that tiary-aikyi-urea havinl'i’roin four to six carbon have a ionser storase iii'e thanisthecasewith ‘ atoms in the aikyi sroup‘equol totromtento' similar moidins compositions prepand from the thirtypercent oi theurea. straisht urea-formaldehyde condensation prod Having thus described our invention, what we claimanddesinetoproteot hyletterlratent is: 15 uonkrnm '1'; mm. ‘ sonouon .