Патент USA US2128879код для вставки
mama Aug. so, 193s . 2,128,879 UNITED STATES PATENT OFFICE 2,128,879 BESINOUS IMPBEGNATING MATERIAL Kenneth M. irey and Lawrence M. Debing, Pali sadel Park, N. 1., asslgnors to Resinox Corpo ration, New York, N. Y., a corporation of Dela No Drawing. Appllcation November 14, 1936, Serial No. 49.138 ‘ g '1 Claims. (01. 106-2!) Our invention relates to the production of res inous impregnating materials. More speci?cally, our invention relates to the production of an im proved impregnating material having a resinous 5 base formed by the condensation of aldehydes with bis- [hydroxy aryl] di-alkyl methanes and/or their ketone condensation produc . . Numerous impregnating agents having phe nolic resin bases have been recommendedin the 10 past but these have in most cases been prepared by the reaction of aldehydes with free phenols or materials containing free phenols. Such prod ucts are, therefore, disadvantageous for many Purposes, especially for impregnating objects‘ 15 which come in contact with foodstu?s. One object of our invention, therefore. is the ' preparation of a resinous impregnating material having as a base a condensation product of sub stances containing no free phenols. A further ob m ject of our invention is the preparation of an im pregnating material which, upon application and heat treatment. will have satisfactory bonding properties, ?exibility, toughness, and water re sistance. Further objects and advantages of our invention will be apparent from the following description. The impregnating agents of our invention com ample below with reference to the preferred ma- - terial, i. e.. a mixture of beta.beta-bis- [4-hy droxy-phenyll-propane and beta.beta-bis- [4-hy droxy - phenyll-propane-acetone condensation product. ‘ 5 Beta.beta-bis- [4-hydroxy-phenyll-propane is a white crystalline material with a melting point of 150 to 154°‘ C. This material may be prepared by any of the known methods, as for example, by the method described by W. A. Beatty in U. S. 10 Patent No. 1,225,748, granted March 15, 1917. Betabeta-bis- [4 - hydroxy - pheny1l-propane- acetone condensation product may be prepared by reacting approximately equal molecular propor tions of acetone and the crystalline product de- 15 scribed above, in the presence ‘of an acid catalyst such as hydrochloric acid, at'temperatu'res of '70 to 80° C. This material may also be prepared by . any other suitable procedure as, for example, that disclosed in co-pending application U. 8. Serial 20 No. 680,230 referred to above. The beta.beta-bis [4-hydroxy-phenyll-propane-—acetone conden sation product prepared by any‘of these proce dures is a reddish colored resinous material hav ing a melting point around 50° C. * '- ' 25 The mixed intermediate which we' prefer to utilize in the present process cpnstitutes a mix ture of approximately equal proportions of the prise ‘suspensions, in relatively non-volatile sol beta.beta-bis- [4-hydroxy -'phenyll-propane and of vheat reactive condensa vents, or plasticizers, the beta.beta-bis-[4-hydroxy-phenyll-propane- 30 ” tion products of aldehydes with bis- [hydroxy ' acetone condensation product. This intermediate aryll-di-alkyl methanes, or mixtures of such sub may be prepared by simply mixing the materials stituted methanes with their ketone condensation prepared as above described, or, as has been pre-' products. We’prefer to: employ such a mixture, viously pointed out, this intermediate may be . as for example, a mixture of beta.beta-bis-[4 formed- in a single reaction from‘the correspond- .35 hydroxy-phenyll-propane and beta.beta-bis-[4 hydroxy-aryl compound and hetone. The hydroxy-phenyll -propane-'-acetone condensation ing proportions of the two ingredients of the mixed product. _Mixed reaction products of this type intermediate may be varied within rather wide of hydroxy may be formedby the interaction aryl compounds and ketones. Bis- [hydroxy aryll-di-alkyl methane constitutes the primary crystalline reaction product of 2 mols of the corresponding hydroxy-éaryl compound with _1 mol. of a ketone. Bis- [hydroxy-aryl] -di-alkyl methane-ketone condensation product repre sents the further reaction ‘of the primary crys-_ These _ talline product with additional ketone. prepared separately and subse products may be quently mixed as described below, or a mixture of the materials may suitably be‘prepared in a single 50 reaction from the. corresponding .hydroxy-aryl compounds and ketones, in accordance with the ‘ process described in co-pending application Serial ' No. 680,230 by K. M. Irey and L. C. Swallen. The ' method of preparing the compounds separately ‘5 and subsequently mixing is described in the ex limits and, in fact, either one of the materials may beused separately. However. in general we 40 prefer to utilize a mixture of approximately the proportions described above. ' The second step of the process for preparing our improved impregnating materials constitutes the reaction of the mixedintermediate product 45 described above with an aldehyde such as form aldehyde or one of its polymers. This reaction islcarried to a definite stage as indicated by the “dry rubber". test, after which the product is immediately mixed with a high boiling solvent, 50 _ or plasticizer, to yield the ?nal impregnating ma terial. The "dry rubber" test utilized in this connection measures the degree of heat reactivity of the resinous product in terms of the time required to eliminate tackiness in a sample placed 55 2,128,879 on a hot plate maintained at 150° C. The re sults of this test, as given in the example be low, refer to time in seconds for a sample of the product to lose its tacklness on the hot plate. The aldehyde reaction proceeds at an ex tremely slow rate in the absence of a catalyst and we therefore prefer to utilize an ‘alkaline The impregnating agents prepared as above described may be employed for any of the pur poses for which previously known materials of this general type have been used, e. 3., as ad hesives, coating materials, etc. The usual meth ods of application may be employed and the usual methods" of heating may- be used to transform the impregnating material to the insoluble stage. employed as ‘condensation catalysts, give rise For example, various fibrous materials may be to a marked acceleration of ‘the ‘reaction but coated with the impregnating agent by dipping, brushing, spraying and the like, and may subse nevertheless require a considerable period of time to carry the reaction’to the preferred stage quently be baked in an oven until the resinous condensation catalyst for this reaction. Ma 10 terials such as barium hydroxide, which are often coating or bond reaches the desired stage of for the present process. We have found that lime 15 exerts a more pronounced accelerating e?ect and that a mixture of lime and barium hydroxide insolubility and toughness. Various other uses, such as the application of an “enamel" coating constitutes an eminently satisfactory catalyst for ' to wire, will also be'apparent to those skilled in this purpose. Utilizing a'catalyst comprising‘ four parts of barium hydroxide and one part 20 of lime, this reaction may generally be carried to the desired stage in a period of about 30 minutes. Although we prefer to employ a mix ture of this nature, it may be said that any alkaline earth catalyst will be operative in our 25 process. The condensation reaction may be illustrated by the ‘following speci?c example: 100' parts of the mixed intermediate product described above are placed in a resin kettle, melted and 30 then cooled to approximately 60° C. The mass is then thoroughly’ mixed vwith '70 parts of a 40% formaldehyde solution after which 4 parts of barium hydroxide and one part of lime are added in the form of-an aqueous suspension. The 35 ‘resulting mixture is then reacted under heat until a sample exhibits a dry rubber test of approximately 15 to 25 seconds. When this ‘point is reached, the application of heat is im mediately stopped and the plasticizer, e. g., di 40 ethylene glycol, is added as quickly as possible. The amount to be added will depend upon the the art. The desirable properties of our im pre'gnating material will best be taken advantage 01', however, in the impregnation of materials which comein contact with foodstuffs. In such uses the desirable properties of our impregnating agents, such as water impermeability and free dom from taste and odor are highly advanta geous. I It is to be understood, of course, that our 25 invention is not to be limited to the particular examples given above by way of illustration. Equivalent reactants and varying proportions or reaction conditions may be employed depending upon the exact nature of the product desired. 30 For example, instead of employing beta.beta-bis [4-hydroxy-phenyl]-propane and its acetone condensation product, any of the homologues of these materials could be employed, Also, in place of formaldehyde, its polymers such as paraform 35 aldehyde or hexamethylene-tetramine, or its homologues such as acetaldehyde could be uti lized. Likewise, any suitable high boiling solvent orpla'sticizer', such as glycerine, which is com patible with the resinous reaction product and desired plasticity of the impregnating material, ' the‘water contained in such product, and which 40 but for most purposes should be just su?icient is chemically inactive at the temperatures em to‘ bring the material to the state of a thin liquid ' ployed, could suitably be substituted for the di 45 having a dry rubber test of approximately '40 , ethylene glycol specified in the example. In seconds. - a The dry rubber, value of the material maybe varied within rather wide limits, e. g.. 15 sec. to 90 sec., depending on the desired degree of 60 heat reactivity of the product. For some pur poses /it is preferred I to carry the reaction at ' this stage as far as possible without transform ing the product to the insoluble or rubbery stage. The dry rubber test of 15 to 25 seconds repre 65 sents a safe practical limit, but the reaction may, of course, be carried further if precautions are taken to cool the material by adding the plas-' ticizer before the insoluble stage is reached. The plasticizer apparently acts only‘in a physi general it may be stated that any equivalents or modi?cations of procedure which would natu 45 rally‘occur to one skilled in the art are included within the scope of our invention. ' Our invention now having been described what we claim is: ‘ - 1. Ina process for the production of a resinous 50 material by heat reacting a mixture ofv a bis [hydroxy-aryll-di-alkyl methane and a bis [hydroxy-aryll-di-alkyl methanHetone con densation product with a‘ su?lcient proportion of an aldehyde to form an insoluble infusible product when fully reacted, the improvement which comprises carrying ‘the reaction to an 60 cal manner as a solvent or plasticizing agent and advanced stage evidenced by a dry rubber test does not enter into reaction with the resinous 4 of 15 tol25 seconds, ,and then immediately pre- . venting substantial further reaction by ceasing mass. The increased time value of the dry rub ber test, after addition of the plasticizing agent ‘ the application of heat and introducing a plas the condensation product ‘does not indicate a change in the nature of the ticizer compatible with » 65 resin but merely a physical e?'ect of- the presence thus produced. 2. ‘In a process for the production of a resinous of the plasticizer. It will be apparent, there fore, that any other organic solvent-or placticizer material by heat reacting a mixture of beta. beta-bise[4-hydroxy-phenyll-propane and beta‘. for the particular resin produced may be suc - cessfully employed‘. beta-b'is- [qt-hydroxy-phenyl] v-propane — acetone Any such material, how condensation product with a sufficient proportion 70 ever, should preferably be su?'lciently non-vola of formaldehyde to form an ‘insoluble infusible tile to exerta plasticizing e?'ect in the ?nal mass product when fully. reacted, the‘ improvement 70 ""of impregnating material after application and which comprises carrying the reaction to an ad heating, and should, of course, be chemically inactive towards the resinous mass and the ma 75 terlals to be impregnated. vanced stage evidenced by a dry rubber test of 15 to 25 seconds, and then immediately prevent ing substantial further reaction by ceasing the 76 3 2,128,879 application of heat and introducing a plasticizer compatible with the condensation product thus produced. I 3. In a process for the production of a resinous material by heat reacting a mixture of beta.beta bis-l4-hydroxy-phenyll-propane and beta.beta ‘ bis-[*i-hydroxy-phenyl]-propane-acetone con densation product with a su?‘icient proportion of formaldehyde to form an insoluble infusible 10 product when fully reacted, the improvements which comprise effecting the reaction in the presence of an alkaline earth catalyst contain ing lime, carrying the reaction to an advanced stage evidenced by a dry rubber test of 15 to 25 seconds, and then immediately preventing substantial further reaction by ceasing the ap plication of heat and introducing a plasticizer compatible with the condensation product thus produced. 20 4. In a process for the production of a‘ resin ous material by heat reacting a mixture of beta. beta-bis- [4-hydroxy-phenyll-propane and beta. beta-bis- [4 -hydroxy-phenyl] -propane — acetone condensation product with a su?icient propor tion of formaldehyde to form an insoluble in fusible product when fully reacted, the-improve ments which comprise effecting the reaction in the presence of a catalyst consisting of four parts of barium hydroxide and one part of lime,’ carrying the reaction to an advanced stage evi denced by a dry rubber test of 15 to 25 seconds, and then immediately preventing substantial 10 further reaction by ‘ceasing the application of heat' and introducing diethylene glycol into the condensation product thus produced in an amount su?icient to increase the dry rubber test of the ?nal product to approximately 40 seconds. 15 5. The product of the process of claim 1. _ 6. The product of the process of claim 2. 7. The product of the process of claim 2 char acterized by a degree of reactivity evidenced by a dry rubber test of approximately 40 seconds. 20 KENNETH M. lREY. ' LAWRENCE M. DEBING.