Патент USA US2405806код для вставки
Patented Aug. 13, 1946 2,405,805 UNITED STATES PATENT OFFICE ‘2,405,806 DERIVATIVES OF RESINOUS ETHERS OF HYDROXYARYL COMPOUNDS Otto Albrecht, Neue-Welt, near Basel, Charles Graenacher, Riehen, Richard Sallmann, Bott mingen, and Carlo Rossi, Basel, Switzerland, as signors to Society of Chemical Industry in Basie, Basel, Switzerland > ‘No Drawing. Application February 2, 1942, Se- ' rial No. 429,336. . In Switzerland February 7, 1941 14 Claims. (Cl. 260—51) 1 2 It has been found that new condensation prod ucts are obtained if resinous compounds which contain at least one etherbridge derived from a hydroxyaryl group are converted into derivatives ucts being formed which contain at least once the very reactive atomic grouping ——CH2-— halogen. The reactive halogen atoms present in the hal ogen derivatives can be very easily converted into water-solubilizing groups by known methods. ‘By causing them to react with tertiary amines, such as pyridine, triethylamine, or with primary and containing halogenmethyl‘ groups by treatment with agents known to introduce halogenmethyl groups, for instance, with formaldehyde and a secondary amines, radicals containing quater hydrogen halide, or with compounds derived from nary ammonium groups or amino‘groups can be these components, and, if desired, if at least one of the halogen atoms contained in these deriva 10 introduced. By treatment with thioureas, which are capable of reacting in the iso-form, or with tives be exchanged for a group which confers or cyanamide or dicyandiamide and similar com ‘ pounds, the corresponding radicals, which also Resinous compounds which contain at least confer water-solubility in the salt form, can also one ether bridge derived from a hydroxyaryl group and which may be used as parent mate 15 be introduced. The compounds mentioned above, i. e. ‘amines, thioureas and dicyandiamide con rials in the present invention are, for example, tain nitrogen atoms. They di?er from other com resinous ethers, which may be derived, on the one pounds used to introduce groups lending water; hand, either from aromatic mono; or polyvalent solubility by the fact that they are either basic hydroxy compounds, forrexample, from phenol, resorcinol, hydroquinone, a-naphthol, p-naph; 20 themselves or may easily be transformed into basic derivatives, for instance, by reaction with thol, parahydroxydiphenyl, parazpara'-dihydrox enhances solubility in water. ydiphenylmethane, halogenmethyl derivatives. Therefore, the prod 1 : l-di- (para — hydroxyphen ucts obtained by condensing halogenmethyl d'e-‘ rivatives with amines, thioureas capable of react pounds of the aromatic series, such as cresols, para-tertiary amyl-phenol, or from substituted 25 ing in the isoform or dicyandiamide contain basic nitrogen atoms, are cationactive, and owing to aromatic hydroxy compounds, such as chloro this cationactivity they are easily absorbed by phenol, para:para'-dihydroxydiphenyl sulfone, textile ?bers‘. In other words, those products para-hydroxydiphenyl ether and, on the other of the invention which contain a basic nitrogen hand, from terpene‘alcohols or from terpene hy yl) -ethane, or from alkylated hydroxy com drocarbons. Among the terpene alcohols or ter 30 atom are especially effective for the improvement -penes mentioned above, the following may be mentioned in particular: terpineols, pine oil, pi nene, dipentene, terpinolenes, terpinenes and sim ilar compounds. These resinous ethers, which of textiles; compartively low quantities of these cation-active compounds will be su?‘icient to pro duce valuable e?ects, since they are readily ab sorbed by ?bers such as cellulose ?bers. Thiourea's‘ capable of reacting in the isoform may also contain unetheri?ed hydroxy groups 35 united to aryl nuclei, can be obtained in known manner, for example, by heating the components, for instance, to 100-160" C., in the presence of acid reacting compounds, such as sulfuric acid or paratoluene sulfonic acid. Such resinous 40 ethers are also described, for example, in French Patent No. 539,494 and in British Patent No. 504,417. contain at least one hydrogen atom, as every ex pert knows. They react as if the atom group ing - N % H—S—-O\N / \ were present in the molecule. Therefore, in the For the conversion into the derivative contain ing the halogenmethyl group, the resinous ethers 45 reaction of a halogenmethyl derivative with a thiourea capable of reacting in the isoform an are preferably treated with u:a'-dihalogendi isothiourea radical of the formula methyl ethers, for example, with dro?-dichloroé' or azo?-dibromodimethyl ether, that is to say, . Nw with compounds which are derived from formal % dehyde and hydrogen halides. This reaction is 50 -s~o\N/ preferably carried out at about 40—100° 0., if de » \ sired, in the presence of substances which act as accelerators, such as anhydrous zinc chloride. in salt form is introduced, the substitution tak The‘ qrd-dihalogen-dimethyl ethers used in this reaction react in an unsymmetrical manner, prod ing place at the sulfur atom. If dicyandiamide is used instead of the above 2,405,806 3 4 mentioned thioureas a radical derived from dicy thiourea are added, and the reaction mixture is stirred for about 4 hours at 40-45“ C. After andiamide, however of unknown constitution, is introduced. Furthermore, thiosulfate or poly» glycol ether radicals can also be introduced in known manner by means of thiosulfates or poly glycols or ethylene oxide. By suitable choice of the parent materials, the standing overnight, the acetone solution thus obtained is separated from a small quantity of resin which has separated on to the sides of the container, and petroleum ether is added. The reaction product, which separates out, is freed products of the present invention can ?nd vappli from traces of solvent. It is a powder that dis cation as auxiliary products, for example, "in the solves in water to form a weakly opalescent solu textile, leather and paper industries. The water 10 tion. This solution becomes very turbid on boil soluble, cationactive products are especially suit ing and loses its foaming power. The new prod able for rendering rayon fabrics fast to slipping, not can be used to make fabrics fast to slipping. the tendency of the warp and weft threads to The ether-like condensation product of slip under mechanical strain being reduced. The a-naphthol and dipentene which is used as par water-soluble compounds of high molecular 15 ent material can be prepared in the same way weight can also be used to in?uence the handle as the ether obtained from carvene and naph of textile materials and to make them Water thol, described in French Patent No. 539,494. repellent, insofar as they are cationactive, to Example 2 increase the iastness to water of dyeings which have been made with dyestuffs containing sul 20 5 parts of the ether-like condensation product fonic acid groups. vWhen the products of the from vp-naphthol and dipentene (B. P. 180-l90° present invention are used to make textiles fast C./-,0.5 mm.) are heated with_ 4.1 parts of am’ dichlorodimethyl ether and 0.05 part of powdered to slipping or water-repellent, ‘an aftertreatment at raised temperature can prove advantageous. anhydrous zinc chloride whilst stirring 'for 1 The products can be used alone or in conjunc 25 hour in a bath at 60-650 C., and the volatile por tion with other substances in ‘common use .in tion of the reaction mixture is then removed by textile ?nishing, such as salts of weak acids. distillation under reduced pressure in a bath at The products of the present invention may Gil-80° C. 13 parts by volume of ‘pyridine are be designated as methylene compounds in which added to the residue obtained, and the reaction a ring carbon atom of a resinous ether of a 30 mixture is heated for about 15 minutes ‘in a‘boil hydroxyaryl compound ‘is connected through a ing water bath, then allowed ‘to stand at vroom bridge derived from‘at least one and at .most temperature for some hours, when the solution two molecules of formaldehyde with a water is separated from any undissolved resin and solubilizing group, which products are liquid to petroleum ether is added. The reaction product solid substances soluble to easily dispersiblein which is precipitated, when freed from traces of water to form solutions to dispersions which are. solvent, is a powder which is readily soluble in decomposed by boiling or by treating with alka water. The aqueous solution foams and pre lies, water-insoluble compounds ‘being "formed. cipitates dyestuffs which contain sulionic acid By a bridge which is derived from at least one groups from their solutions. The ‘new product and at most two molecules of formaldehyde there can be used to make fabrics fast-to slipping. is to be understooda bridge derived from one or The ether-likev condensation product from two molecules of formaldehyde. The methylene p-naphthol and dipentene can be prepared in bridge -—CHz-— is a bridge deriving from one the same manner as the ether from carvene and molecule of formaldehyde. A bridge which is p-naphthol described in French Patent No. derived‘from two molecules of formaldehyde is 539,494. contained in the bridge —CH2—O--CH2—. The Example 3 existence of a bridge whichis derived ‘from at least one and at most two molecules of formal 2.5 parts of the ether-like condensation prod dehyde brings about the ‘technically valuable uct from dipentene and para-hydroxydiphenyl properties of the products of the present process, 50 (B. P. Zed-262° (1/14 mm.) are heated with 2.8 viz. their capability of being decomposed ‘in ‘the parts of dzw-dichlorodimethyl ether for about 5 heat. If materials, suchas textiles ‘from cellu hours in a bath at 90-100” 0. whilst stirring. The lose, are impregnated with :the water-soluble volatile portionqof the reaction mixture is then products of this invention and heated after dry removed by distillation vunder reduced pressure ing, for instance to 120-150° 0., residues which 55 at the same bath temperature. The residue thus originate from the products of the present inven obtained is dissolved in 15 parts by volume of tion can ‘be ?xed onthe treated material in‘ a dry acetone, small quantities of undissolved mat manner fast to washing, whereby especial effects, ter are removed by ?ltration. ‘1.5 parts of ?nely for instance a non-slip ?nish which is fast to powdered thiourea are .added, and the “reaction washing, may be attained. 60 mixture is stirred for 4 hours in a bath at 40-45“ The following examples illustrate the inven C. Petroleum ether is then added, and the pre tion, the parts being by weight: cipitate is separated from the mother liquor and freed from traces of volatile matter. An almost Example 1 colorless powder is obtained which, when dis solved in a little alcohol, gives ‘a clear, roaming 3 parts 'of the ether-like condensation product solution on addition of water. The solution ‘pre of a-naphthol with dipentene (B, P. 223-226" cipitates dyestuffs which contain sulionic ‘acid C./12 mm.) are stirred with 3.7 parts of 0120:’ groups and, ‘on boiling, especially after addition dichlorodimethyl ether, ?rstly for 1 hour in a of sodium acetate, decomposes with ‘loss of ‘foam bath at 90-100° C., then for 3 hours in a bath at _ 110-120° C. The volatile portion of the reaction 70 ing power. . The ether-like (condensation product from di mixture is then removed by distillation under pentene and para-hydroxy-diphenyl which serves reduced pressure in a bath at 90-100" C. The as parent material can'be prepared in a similar residue :is dissolved in 30 parts by volume 'of manner to the ethers from a- or B-naphthol in dry acetone, undissolved matter is removed, if desired, by ?ltration, 116 parts of .?ne‘lyrpowdered 75 accordance with the data given in French "Pat 2,405,806 5 6 3. ‘A methylene compound in which a' carbon out No. 539,494. It is preferable to work as fol atom belonging to an aryl nucleus of a resinous lows: ether of a hydroizynaphthalene with dipentene is 10 parts of sulfuric acid monohydrate are al connected through a bridge selected from the lowed to drop into a paste of 170 parts of pow dered para-hydroxydiphenyl in 136 parts of di 1 group consisting of. -—CH2— and -—-CH2OCH2— pentene over a period of 10 minutes whilst stir with the ring at 50° C. The temperature rises rapidly to I ¢NH 110° C. by the heat of reaction. Stirring is con -s-0 tinued for a further 5 hours at 110-115“ (3., when NH: the temperature is raised to 170° C. and is main 101 tained for 2 hours at 170-175° C. The reaction radical in salt form. product is poured into water whilst still liquid 4. A methylene compound in which a carbon‘ and is freed from phenolic matter by exhaustive atom belonging to an aryl nucleus of a. resinous boiling with dilute sodium hydroxide solution and ether of a hydroxy diphenyl with dipentene is washing with water. It is then dried at about 16 connected through a bridge selected from the 90-95“ C. in vacuo. An exceedingly sticky, yel group consisting of -—CH2- and —CH2OCH2—> low‘ mass is obtained which may be still further with the puri?ed by distillation under reduced pressure. ' . Instead of the ether above described resinous ' I ‘72in -s-o ethers of other hydroxyaryl compounds, for in 20; NH} stance, ethers of resorcinol, lzl-di-(para-hy droxyphenyl) -ethane with suitable alcohols such radical in salt form. as terpineol, benzylic alcohol may be used. Fur ther, a radical of the thiosulfuric acid may be introduced by condensing the chloromethyl de rivatives described above with sodium thiosulfate. Instead of thiourea another thiourea capableof reacting in the isoform, for instance, allyl thiourea may be condensed with the chloromethyl deriva tives mentioned above. 25 : 5. A methylene compound in which a carbon. atom belonging to an aryl nucleus of a resinous ether of u-naphthol with dipentene is connected through a bridge selected from the group con- - sisting of -—CH2—-— and —CH2OCH2—- with the. sulfur atom of the g ‘ /NH .H 01 radical _ — S ~C/ ‘The 'condensation'product obtained by reac tion with thiourea which is described above can H: be used as follows to make fabrics fast to slipping: 6. A methylene compound in which a carbon A viscose rayon fabric, which has a tendency to slip, that is, the warp and weft threads of : 2 atom belonging to an aryl nucleus of a resinous ether of parahydroxydiphenyl with dipentene is which are easily caused to slip over each other by connected through a bridge selected from the mechanical strain, is impregnated with an aque group consisting of —CH2— and —-7CH2OCHz—ous solution of 0.5 per cent. strength of the prod with the sulfur atom of the uct described above. It is then soueezed and dried NH on the calender at about 105+110° C. The ma terial thus treated is very much faster to slipping -'-S-O .HCl radical. than the untreated fabric. What we claim is: 1. A methylene compound in which a ring car bon atom belonging to an aryl nucleus of a resin ous ether of a hydroxyaryl compound with a member selected from the group consisting of’ I I . NH: > r 7. A process for the manufacture of a con 45 densation product, which compises condensing a resinous ether from a hydroxyaryl compound and from a member selected from the group con cyclic terpene alcohols and cyclic terpene hydro- ‘ sistlng of cyclic terpene alcohols and cyclic ter carbons is connected through a bridge selected pene hydrocarbons with an equimolecular quan from the group consisting of —CI-I2-- and 50 tity. of a:u'-dich1orodimethyl ether to form a chloromethyl derivative of the said ether. —CH2OCH2-—- with a water-solubilizing radical selected from the group consisting of quaternary 8. A process for the manufacture of a con— ammonium groups and the densation product, which comprises condensing a resinous ether from a hydroxyaryl compound NH % 55 and from a member selected from the group con -s—o sisting of cyclic terpene alcohols and cyclic ter \ NH: pene hydrocarbons with an equimolecular quan tity of a:m'-dichlorodimethyl ether to form a radical in which the basic nitrogen atom is neu chloromethyl derivative of the said ether, and tralized with one equivalent of an acid. '2. A methylene compound in which a carbon 60 eifecting a water-solubilizing step by condensing the resultant product with a solubilizing agent atom belonging to an aryl nucleus of a resinous containing at least one nitrogen atom directly ether of a hydroxyaryl compound containing at linked to at least one carbon atom and selected least two benzene nuclei with a cyclic terpenic from the group consisting of tertiary amines, alcohol is connected through a bridge selected from the group consisting of —-CH2—- and 65 thioureas capable of reacting in the iso-form and dicyandiamide, whereby reactable chlorine of —CH2OCH2—— with a water-solubilizing radical the chloromethyl group is transformed into "a selected from the group consisting of quaternary water-solubilizing group. ammonium groups and the 9. A process for the manufacture of a con 70 densation product, which comprises condensing a. resinous ether from a hydroxyaryl compound and from a cyclic terpenic alcohol with an equimo lecular quantity of mud-dichlorodimethyl ether, radical in which the basic nitrogen atom is neu tralized with one equivalent of an acid. to form a chloromethyl derivative of the said 75 ether, and e?ecting a water-solubilizing step by 2,405,806 7 8 condensing the resultant; product. with a solubil izing agent containing at least one nitrogen atom directly linked to at: least.- one: carbon atom and selected from the group consisting of tertiary amines, thioureas capable of reacting in‘ the iso form and dicyandiamide, whereby reactable' chlo rine of the ehloromethyl group is transformed into a. water-solubilizing'group. of azd-dichlorodimethyl ether, to form a chlo-> romethyl derivative of the said ether, and trans forming at least one» chlorine atom of the chlo romethy-l derivative into a radical of the‘ for ‘ mula ' 10. A process for the manufacture of a con densation product, which comprises condensing a resinous ether from a hydroxylaryl compound containing at least two benzene nuclei and from a in which the basic‘ nitrogen is neutralized with one equivalent of an acid, by condensing’ with a thi'ourea capable of‘ reacting in the iso-form. cyclic terpenic alcohol with an equimolecular 13. A process for the manufacture of a con quantity- of md-dichlorodimethyl ether, to form densation product, which comprises condensing a chloromethyl derivative of the said ether, and 15? the resinous other from p-naphthol and from e?ecting a water-solubilizing step by condensing dipentene with an equimolecular quantity of the resultant product with a solubilizing agent md-dichlorodimethyl ether to form a. chloro containing at least one nitrogen atom directly methyI derivative of’ the said‘ other, and trans linked to at least one carbon atom and selected forming a chlorine atom of‘ a, chloromethyl' group from the group consisting of tertiary amines, thio 20 into the radical of't‘he/f‘ormula ureas capable of reacting in the iso-form and di oyandiamide, whereby reactable chlorine of the chloromethyl group is transformed’ into a water solubilizing group. 11. A process for the manufacture of‘ a con 25 by condensing with thiourea. densation product, which. comprises. condensing 14. A process for they manufacture of a con a resinous ether from a hydroxynaphthalene and densation, product, which comprises. condensing from dipentene with an equimolecular quantity the resinous other from para-hydroxy-diphenyl of mM-dichlorodimethyl ether, to form a chlo romethyl derivative of the said ether, and trans 30 and from dipentene with an eduimolecular quantity of a:a'-dichlorodimethyl ether to form forming at least one chlorine atom of the chlo a chloromethyl derivative of the said ether, and. romethyl derivative into a radical of the for transforming a chlorine atom of a chloromethyl mula group into the radical of the formula 35 in which the basic nitrogen is neutralized with one equivalent of an acid, by condensing with a thiourea capable of reacting in the iso-form. 12. A process for the manufacture of a con by condensing. with thiourea. OTTO ALBRECHT. densation product, which comprises condensing CHARLES a resinous ether from a hydroxydiphenyl and RICHARD SALL1\&ANN,. from dipentene with an; equimolecular quantity CARLO ROSSL - .GRAENACHER." '