DEP0050577DA - Process for the production of resins from phenolic alcohols and reactive carbonyl compounds - Google Patents

Description

Copy. 27.7-49

Applicant

company

Dr. Kurt. Herberts -: x Go,

formerly Otto Louis Herberts

-, Yuppertal-Barae n
Ciiristbussch 25

"Process for the production of vox. · Resins from Pheiiol alcohols and r e alt t i ο ns f äh i g e η C a r b ο ny 1 ν e r b i nd ung en".

Represent ss is known that ümsetauiigaprociukte of phenols and i.> ^S ora.aldehyd fuel-soluble type of Phenclalkohole or ouch these gained hühermolekularen products through '. "/ Low-curable resins," oak in the cured state the disadvantage of very large o ^ rödigkeit have "13s various methods are known to aua such xiienolälkohclen to curable marches. form which are soluble not only in alcohol but also in other solvents such as in particular Bensolkohlenwasserstoffen and ßuäl ^ ile can be plasticized with oils of the other plasticizers such a way that these gowns are not excreted again during the hardening process and the resins are given the property of permanent elasticity. In order to achieve this goal, the procedure has sometimes been to use alkylated or arylated phenols, such as butylphenol or Cxydipheri, 71 instead of simple phenolic bodies Or you have the Benaol and öiverträ Attempts to achieve this possibility by partial etherification or esterification of the phenolic hydroxyl groups, above all subsequently also esterifying the alcoholic hydroxyl groups of the phenolic alcohols. In the processes mentioned so far, however, the interventions outlined significantly reduce the hardenability of the rhenol alcohols. Another method is known in which only the alcoholic hydroxyl groups of the phenol alcohols are etherified with the aid of aliphatic Lüonoalkoholen. This method has been used to a large extent in practice and leads to usable end products with certain pharmaceutical coolings.

It has now been found that curable resins of technically 'valuable properties are obtained if phenolic alcohols with reaction

capable of converting over 80 fi boiling carbony compounds until solubility in benzene hydrocarbons is achieved. As phenolic alcohols those products come in Beth-racht that you Ainet by reacting phenols with formaldehyde in the presence of alkali * see receive contact means. It is expedient to use more than 1 mol of formaldehyde, preferably about 2 mol of formaldehyde, for 1 mol of the phenolic component. The reaction between the phenolic component and the formaldehyde is conducted in a known manner in such a way that reactive kethylol compounds are obtained. The advantage of the present process is that the starting products are not only methylol compounds from cresol, diphenylolpropane and similar substituted phenols, but also methylol -Compounds of unsubstituted phenol can be used. In addition to the mononuclear phenol alcohols, the term “methylol compounds” also includes polynuclear compounds which are obtained in the further condensation of the phenol alcohols. The prerequisite for the applicability of the phenolic alcohols in Dinne of the present method is that these compounds are reactive groups or reactive thyIo Me! Contain formaldehyde.

Reactive carbonyl compounds are to be understood as meaning those aldehydes and ketones whose boiling point is sufficiently high to be able to reach the temperature required in each case for the reaction with the phenol alcohols. Preferably, such aldehydes and ketones are suitable, in the water-immiscible or only slightly soluble, whose boiling point is about £ 80 and which contain no the reaction course interfering groups in the molecule. From a technical point of view, for example, cyclohexanone, acetophenone, benzophenone, benzaldehyde, salicylaldehyde and similar technically easily accessible products come into consideration conduct, be able to or influence the pH of the reaction medium in the undesired sense. "

The. Execution of the reaction is advantageously carried out in such a way that the phenol alcohols together with the carbohyl compound on the reflux condenser heated to boiling. The return flow system is set up in such a way that a water separator is placed in the condensate return built in, which allows the water formed during the reaction and accumulating in the return flow continuously from the Remove circuit. The boiling temperature increases accordingly

as the reaction progresses and: Jio, vasse.rabapaltung decreases. The level of the boiling temperature and the amount of water split off each represent an indication of the progress of the reaction. At the same time, the jrrobon removed shows how the product which is initially insoluble or only very sparingly soluble in benzene hydrocarbons is continuously dissolving the beaser in Eenzul it can finally be diluted with any amount of benzene. The length of the carbon oil compound used is generally 1 to 2 liters of phenol. used in the pora of Ihenol alcohols. 3s can, but also an excess of the carboxy compound, softer as a solvent and diluent, can be distilled off again later, but neutral ones that do not need to take part in the reaction can also be used depending on the diluent, e.g. those of an ester-like nature . oyer can be added from the outset BeriZolkohlenwasaerotoffe or similar products, which do not work with the high ion components, in the course of the reaction, but enter into a homogeneous solution with these,!, the reaction can in any desired turn abbrecnon. Besonlero when using very active phenolic polyols and an excess of Garoon / j »! connection getting an early termination of the reaction is advisable to obtain not a • / χι fix = '! + sighted networking whose u'ol _& e the elimination Hr Lassen would be.

The rate at which the reaction between the carboxyl and Phenolulkoholen runs is dependent upon the PLI (vert the Reakxionagemiaches. The same k ^ nn generally between

pH 2 and pH 6 lie, the fastest reaction usually occurs at pH 2-3. and this <I'ert should preferably be adhered to when it comes to the implementation of such rapidly hardening ihenol alcohol, for example from rieinphenul and mohr als 2.5 Iv ¹ Ol JiOmaldakyd. The implementation at this pH is already successful in 1-2 - -it ·, while the above-mentioned conversion of phenol alcohols requires many times this reaction time and therefore cannot be carried out at all with very reactive, rapidly hardening ihenol alcohols at all with difficulty.

The reaction described here involving the phenol alcohols and the carboxyl compounds could probably be used in the j. ^! orra go ahead that compounds of the aldehyde and respectively. Ketone, icetals or haloacetals are formed. The products which arise during the reaction of the carbonyl compound with the phenol alcohols are hard resins which are soluble in benzene hydrocarbons. oie are

contract! I use fur oxen and other substances known as x-elasticizing agents, so that I do not excrete a liar lung reaction, give sinners a uauor-elastic binding to the hoarded resins. x.iorio l-laetifiziorungomitLei may be jciion during üer Umsetzurigsreaktion zwiscnea the Ihenolaikoholen and the Jjrbonylverbinjungen zi% e _b s OAER even after the termination of this reaction was added vverdGi-, In the cured state aie resins are petrol feat and even generally against α s attack of solvents, Water and other chemicals are extremely resistant.

Examples i

1. Io ο parts of Pnenol

25o ". Formaldehyde 3o,; ig
6 "sodium hydroxide solution 2o, iig

be 2 days at left äimmertemporatur what aan 2oo parts brass "pure cyclohexanone is added and with vigorous lead with b n-ochwefels ^ ure the i-nenolalicohol ausf been assured, welcner immediately dissolves in the cyclohexanone. Lian regulates the acid build-up in such a way that the pH value of the aqueous layer that forms is between 2 and 3. Then nan separates the öchichfceri. Ui c solution of the rhenol alcohol formed in cyclohexanone / arcl is now heated on the Ituctcl'luss to the diederi in such a way that the return runs over a water separator and the sioii separating rtaaser can be drawn off. In the course of t>& ^, 1 -84tHft ^ e · the temperature in the interior of the liquid has risen from Io2 ° to 14o ^{above sea level} , while parts of the liquid have been separated out from the liquid Irobes removed, which at first were not at all thinned with benzene, now remain clear after adding 10 parts of benzene. Kun the excess cyclohexanone is removed in a vacuum, whereupon 173 parts of a very viscous resin os üuruckoleiben. Lieses resin ergiot iniL Jienzolkohlenwusseratoffen diluted and mixed with, for example , 5o /> Iticinuaöl a lacK of high elasticity that can be burned onto sheet metal at "bSi" 18o ° (/ clear and trouble-free. If the sheet is bent, the paint does not crack.

iSin Fhenolalicoholansatz as in, Example 1, stored for 5 days, mixed with 200 parts of tecnn.Cyclohexanon and neutralized as in Example I ₈ Then lbo parts λ / 1ο1 and t> b parts, ki are added, and β «- # 3w? d - This inhomogeneous mixture is heated with reflux with j / asaerabacheider. The temperature Temp rises in the second-fer ^ from 92 to 139 ^ .una will be IO8 parts water abgespalten.fahren C carbonization occurs iiomagenisierui ^ a of juoaung, and after tie endif ung ^ aer same approach is nil, ieaer belie own amount of benzene

ν dilutable. The batch can now be used immediately, if necessary with further dilution, Ji it Benzol huhlenwa.'JüerstoX'ü'en 2 to burn in »or the Kara can be used by Des ζ ± 11-iti on as in the example

/
1 can be isolated and then redissolved at will. When firing on sheet metal, they result in flawless and highly elastic coatings.

5 "loo i'oile cresol mash

14o "formaldehyde 3o / oig

28 "sodium hydroxide solution 2o; aig

are left to stand cold for 2 days, then neutralized with sulfuric acid = 22o g of the separating resin are each mixed with 200 g of cyclohexanone and 50 g of hicinus oil, respectively. Holüiöl, besj ,. iJartfettaäure added and this Anaätzey as ^ in example 2 treated further. Ks were deposited in the course of: about 1 1/2 <& 4 * # τ4 «&& bo-9o ecm wasöer and the temperature rose during this time from initially -es» 98 ° to 15o-16o °. In all three balls, finally, Haraldsongcn diluted with benzene, which were distilled and dissolved with benzene / hydrosol to a varnish. The varnish hardens completely clearly in all three cases on sheet metal; the improvement in elasticity compared with unplaatified resins varies depending on the type of additive used.

4. 165 Peile Kreaol, alcohol, made from 100 g of cresol with formaldehyde and sodium hydroxide solution, followed by deposition of the carbon dioxide using acid
loo "TJeiiZaJaehyd

i? 5 "hicine oil
200 "butyl acetate

ani / water condenser is heated with a water separator, the duration of operation "t> 1/2 -Srfctmd-eft. 58 ecm. / water are split off. The temperature rises from 96 to 128 , measured inside the liquid. After" the end of the reaction is the i-roduct can be diluted with benzene as required. The solvents and unreacted benzaldehyde are removed by vacuum exhaustion. Any remaining Hura - 2uo g is dissolved in cylinder oil. j, s results, on Blecü an ebr.nnt, coatings of high ullastiaity.

516b parts of cresol alcohol, as in Example 4, 100 ^{liters of benzaldehyde}
loo xylene

are treated as in Chapter 4. After the Jest J llation, 160 g of resin soluble in xylene are obtained, which are baked onto a sheet metal the IlarLlösung a trouble-free l ^ iliü of low elasticity. By adding hicinus oil or wood oil, the elasticity can be increased significantly has been increased. ,,,. . . , /

x * at e_L I '-iTiapru marriage : /

Claims (1)

Patent claims: 1. Process for the division of resins aua ihenolalkoholeri and reactive carbonyl compounds ^ dadcirch marked, that a phenyl alcohol is brought to react with a reactive carbonyl compound boiling over 80% until Solubility in benzene hydrogen is reached " 2 * Process according to claim l ^ characterized in that those aldehydes or ketones are used that do not work with water or are only difficult to mix, "j. Process according to claims 1 and 2, characterized in that the conversion between the phenol alcohol and the aldehyde respectively Ketone is carried out at a pH of 2-6, preferably at a pH of about 2-3. 4 "Process according to claims 1-3" characterized in that during or after the implementation of the - ^ henolalltohole with the Reactive Uurbony! compounds plasticizing agents are added.