DE850811C - Process for the manufacture of polymeric products - Google Patents

Description

Process for making polymeric products, The invention relates to focus on the production of polymer compounds and the production of webs, Fibers, threads and the like, hereinafter generally referred to as webs, made from them Products.

It is known that epichlorohydrin reacts with aliphatic, aromatic or heterocyclic secondary amines and non-polymeric products can generate e.g. B. British Patent 275,622 describes the reaction of epichlorohydrin and secondary amines to form a-tetraarylaminoepihydrins, which are then brought into reaction with bases and substituted unsymmetrically Diaminopropanols result.

A method has also been proposed for making thermoplastic Resins by heating essentially equal molecular proportions of epichlorohydrin and at least one aromatic dioxy compound in which the hydroxyl groups Show phenolic character and the carbon atoms, which with the hydroxyl groups are connected, separated by at least one other carbon atom, together with such an amount of alkali that the number of molecules of the alkali becomes number of the molecules of the dioxy compound is at least 1.0, and heating is continued until a fiber-forming, resinous product is obtained.

French patent 933219 describes the preparation of resinous products which are suitable for use as anionic agents in the condensation of at least 2: molecules of an α-chlorine, @ -,; - epoxy compound, such as epichlorohydrin, with a molecule of a polyalkylene polyamine, preferably in Suitable in the presence of a strong alkali. The purpose of the present invention is to produce a new class of polymeric compounds which are generally suitable for the production of webs.

According to the present invention there is a method of manufacture polymeric compounds therein, essentially equal molecular amounts of epichlorohydrin and to heat a compound with dual function together, which as one their functional groups have a secondary amino group and as another functional group has a secondary amino group or a hydroxyl group, together with one Alkali in an amount which is at least essentially its chemical equivalent the chlorine content of the epichlorohydrin used.

In other embodiments of the invention is indicated above secondary amino compound with double function partly e.g. B. by a bivalent Replaced phenol or by a monoxybenzoic acid such as p-oxybenzoic acid. acid, whereby mixed polymeric products are obtained.

The invention therefore also includes a method for making mixed polymeric products, which consists of epichlorohydrin, a compound with double Function which has a secondary amino group as one of its functional groups and as the other functional group either a secondary amino group or a hydroxyl group, an aromatic dioxy compound in which the hydroxyl groups are phenolic show and the carbon atoms bonded to the hydroxyl groups by at least another carbon atom are separated, and an alkali in such an amount that is at least chemically equivalent to the chlorine content of the epichlorohydrin used, to be heated together, the proportions of said double-functional compound and said aromatic dioxy compound together are essentially equimolecular Are equivalent of the epichlorohydrin used.

The invention also includes a method of making blends polymeric products, which consists in heating the following components together: Epichlorohydrin, a monoxybenzoic acid, a double functional compound which the first functional group from a secondary amino group and the other Functional group either from a secondary amino group or from a hydroxyl group are formed, and an alkali in an amount which is at least the chemical The equivalent of the chlorine content of the Epichlorhy.drins used, where the Proportions of the double functional compound mentioned and of monoxybenzoic acid together essentially the equimolecular equivalent of the epichlorohydrin used represent.

In the preparation of mixed polymeric products according to the invention forms said double-functional secondary amino compound, preferably at least ioo / ormixture which reacts with the epichlorohydrin and the alkali is brought.

Suitable secondary doubly functional amino compounds for use in the present invention are 4,4-dipiperidyl p-methylaminophenol and other N-alkyl-substituted aminophenols and bis-4, 4 '- (N-methylaminophenyl) methane, Suitable dihydric phenols for use in making mixed polymeric products are hydroquinone, resorcinol and 3,3'- or 4,4-dioxydiphenyl.

The process according to the invention for the preparation of polymeric products can be carried out in a single reaction step by heating the epichlorohydrin, the bifunctional secondary amino compound and the alkali together, preferably under a reflux condenser, until a resinous polymer separates out. A two-step process can also be used by e.g. B. first reacts the epichlorohydrin with 50 to 100% of the specified bifunctional compound and then heats the product with the alkali and any remaining bifunctional compound until a resinous polymer separates out. In another two-step reaction, one molecule of the bifunctional compound can first be heated with 2 molecules of epichlorohydrin and its alkali equivalent to form a diepoxy compound, which is then heated with a second molecule of the bifunctional compound which contains a small amount of an alkaline catalyst will.

Mixed polymeric products can be made according to the invention by putting the four specified reagents together, preferably under one The condenser is heated until a resinous, mixed polymer separates out. Two-step procedures can also be used. For example, the bifunctional secondary amino compound in one step and a dihydric phenol or a b-ionoxyhenzoic acid be applied in the other stage; z. B. can i molecule of the divalent Phenol, 2 molecules of epichlorohydrin and 2 molecules of alkali together in the first stage to be reacted to form an aromatic bisglycidyl ether according to the method described by Werner and F a r e n -h o r s t (Receuil des Traveaux Chimiques de Pays Bas, vol. 67 [1948], pp. 438 to 4.1i), and then the Bisglycidyl ether with i molecule of the bifunctional secondary amino compound react charges to obtain a resinous mixed polymerization product. On the other hand, mixtures of the bifunctional compound with one mentioned can also be used dihydric phenol or with an oxybenzoic acid can be used in both stages.

The methods of the invention are preferably carried out in the presence a diluent such as aqueous alcohol.

The epichlorohydrin can be formed in the reaction mixture, by using α- or β-glycerol dichlorohydrin, or a mixture of both with a molecular equivalent of caustic alkali in place of the epichlorohydrin. In this case the caustic used to react with the glycerine is chlorohydrin Alkali in addition to the alkali which is required to post the reaction to bring about the invention.

The polymers obtained according to the invention are generally thermoplastic High molecular weight products, drawn as usual or in the melt can be spun and form threads which are generally cold-drawn can.

In the following exemplary embodiments, the parts are understood according to Weight.

Example i io, i parts (i mol) of epichlorohydrin, a boiling solution fully 18.4 parts (iMol) 4,4-dipiperidyl in 10o parts ethyl alcohol and a cold one Solution before 4.55 parts (i, o-1 mol) of caustic soda in 2o parts of water were mixed together and heated under a reflux condenser for 3 hours. At the end During this period a finely divided precipitate had formed; the pasty Mass was poured into twice its volume of water, filtered and the Precipitate washed three times with hot water and dried hot ioov.

The polymer obtained had an actual viscosity of 0.42 in a 100% solution in metacresol and could be drawn into fibers in the heat.

Example e A product consisting of the mixed stereoisomers of 1,4-13is- (2,3-epoxypropoxy) -benzene, otherwise known as I3ydrocliinon-bis-glycidylether, was made from 1 molecule of hydroquinone, 2 molecules of epichlorohydrin and 2 Molecules of caustic soda, using the method given by Werner and Farenhorst (Receuil des Traveaux Chimiques de Pays Bas, vol. 67 [1948j pp. 438 to 441), and 12 parts of this- product, 9. r 5 parts 4. - Dipiperidyl, 0.25 part of caustic soda (as a catalyst) and 80 parts of ethyl alcohol were mixed and heated for 1/2 hour under a reflux condenser, after which time a finely divided, cream-colored, solid had separated out. This solid body was filtered off, washed with ethyl alcohol and then with water and finally dried first at 100 ° and then in a vacuum drying cabinet.

Example 3 17.2 parts of p-methylaminophenolsul @ fat, 9.25 parts of epichlorohydrin, 16 parts of alcohol, 20 parts of water and 4.2 parts of caustic soda, in slight excess about the amount required to liberate the free p-methylaminophenol was mixed in a vessel equipped with a stirrer and a condenser was. The apparatus was purged with oxygen-free nitrogen. The mixture was placed therein under a reflux condenser on a boiling water bath with stirring heated in an atmosphere of nitrogen for 45 minutes. A solution of 4 parts Caustic soda in 10 parts of water was then slowly poured through the Poured through the condenser while the reaction mixture is refluxed and vigorous Stirring was heated. After all the caustic soda was added, the mixture was made heated under reflux for 3 hours. The product turned out to be a plastic mass excreted, which separated, washed three times with boiling water and dried became.

The product melted at about 12ov 'and could be in the molten state State easily pulled into fibers.

Example i 3.6 parts (0.82-1.101) 4,4-dipiperidyl, 2.2 parts hydroquinone (0.2- \ f01), 9.25 parts epichlorohydrin (1 mob), 4.4 parts caustic soda (i, i mol), 80 parts of alcohol and 10 parts of water were mixed and continued for 7 hours vigorous stirring under reflux. The product that separates out was a tough, mass adhering to the walls of the vessel; 200 parts of water were added, the product deposited, washed four times with boiling water and dried. The product was a dark, thermoplastic polymer.

Example s 15.4 parts ( 0.93 Mob) 4,4-dipiperidyl, 1.38 parts (0.1 mole) p-oxybenzoic acid, 9.25 parts (i mole) epichlorohydrin, 4.4 parts (i, i Mol) caustic soda, 80 parts alcohol and ao parts water were mixed together and heated under reflux with vigorous stirring for 6 hours. The reaction mixture was diluted with 500 parts of water, brought to the boil and filtered hot to separate off. The product was washed twice with boiling water and dried.

The product was an off-white, fiber-forming, thermoplastic Powder which softened at 200 °. Its real viscosity in of a 10% solution in m-cresol was 0.04.

Claims (5)

PATENT CLAIMS, i. Process for the production of polymeric products from epichlorohydrin, a bifunctional compound and alkali, characterized in that essentially equal molecular proportions of epichlorohydrin and a bifunctional compound, one functional group of which consists of a secondary amino group and the other functional group of a secondary amino group or a hydroxyl group, together be brought into reaction with an amount of alkali which corresponds at least to the chemical equivalent of the chlorine content of the epichlorohydrin used. 2. Process for the production of mixed polymeric products from epichlorohydrin, bifunctional compounds and alkali, characterized in that the epichlorohydrin with a bifunctional compound as described in claim i, and also an aromatic dioxy compound in which the hydroxyl groups are phenolic show and the carbon atoms connected to the .Hydroxylgruppen by at least another carbon atom are separated, preferably hydroquinone, together be reacted with an alkali in such an amount that at least corresponds to the chemical equivalent of the chlorine content of the epichlorohydrin used, where the proportions of the specified bifunctional compound and the one used aromatic dioxy compound together have essentially the equivalent molecular weight of the epichlorohydrin used. 3. Method of making mixed polymeric products made from epichlorohydrin, bifunctional compounds and alkali, characterized in that the epichlorohydrin is associated with a according to claim i described bifunctional compound and also with a monoxybenzoic acid, preferably p-lltonoxybenzoic acid, together with such an amount of alkali, which is at least the chemical equivalent of the chlorine content of the epichlorohydrin used corresponds, the proportions of the specified bifunctional compound and the Monoxybenzoic acid together are essentially the equivalent molecular weight of that used Epichlorhydrins correspond. 4. The method according to claim i, 2 or 3, characterized in that that 4, -Dipiperidyl is used as the bifunctional compound. 5. Procedure according to Claim i, 2 or 3, characterized in that as a bifunctional compound p-methylaminophenol is used.