Patent GB-679765-A (GB)
Title: A condensation process and the products resulting therefrom
Filed: 1950-06-06
Abstract: Condensation products made by treating an addition product of an a ,b -ethylenically unsaturated aldehyde and a salt, an amide or an ester of a polyethylenic acid having at least two ethylenic linkages in conjugated relationship with an inter-type condensation catalyst may be used as plasticizers in synthetic resins or they may be polymerized or copolymerized or used in alkyd-resin manufacture.  The catalyst is defined as a material, such as aluminium isopropoxide, which initiates a condensation of two aldehyde groups to form an ester linkage.  Aldehydes may be aliphatic, alicyclic or aromatic and may have inert substituents such as halogen or ether radicles. Preferred are aliphatic aldehydes of 3 to 12 carbon atoms.  Many aldehydes are specified, representative being acrolein, cinnamaldehyde, 2,4-pentadienal, 2,5,7-octatrienal, 4-cyclohexyl-2-heptenal, 3-chlorophenyl-2,5-octadienal, 1-cyclohexene - 1 - carboxaldehyde, 5,6 - dihydro - 1,2 - pyran - 3 - carboxaldehyde, 3,5 - diethyl - 2 - octenal and furfural.  The ethylenic linkates of the salt, amide or ester may be in an open-chain or cyclic structure and the free bonds may be attached to aliphatic, alicyclic or aromatic radicles which may contain inert substituents, e.g. halogen, ether and ester radicles. Representative of salts, amides and esters, many of which are specified, are sodium 5,7-decadienoate, potassium 6,8,11-pentadecatrienoate, sodium abietate, abietamide, ethyl a -elaeostearate, butyl b -thioelaeostearate, methallyl 9,11-octadecatetrenoate, cyclohexyl 5,7,9,12-octadecatetrenoate, phenyl 7,9-octadecadienoate, glycol bis (7,9-octadecadienoate), glycerol trielaeostearate and triglyceride oils such as tung, po-yoak, dehydrated castor, loofah and linseed oil.  Many polyethylenic acids from which the salts, amides and esters may be derived are also specified, together with many hydroxy compounds from which the esters may be derived.  Esters are preferred particularly those of open-chain and rosin polyethylenic acids of at least 12 carbon atoms and aliphatic alcohols of 1 to 10 carbon atoms, and drying oils the acid residue of which contains at least 30 per cent of open-chain acids of at least 12 carbon atoms. Preferred catalysts are lower alcoholates of polyvalent metals in the second period of the Periodic Table.  For reaction conditions of the production of addition products and the condensation reaction (see Group IV (b)).  The products, especially those derived from simple esters, are plasticizers for polyvinyl and polyvinylidene chlorides, vinyl acetate, cellulose nitrate, acetate, acetobutyrate and ethyl cellulose.  They are softening agents for lignin plastics, polyamide, phenol-aldehyde and ureaaldehyde resins.  Products derived from partial esters contain free hydroxy groups and may be further reacted with polycarboxylic acids to give alkyd-resins.  Many polycarboxylic acids are specified, representative being adipic, suberic, fumaric, glutaconic, phthalic, tetrachlorophthalic and trimellitic acid.  The products may be polymerized or copolymerized with, e.g., maleic acid and its esters, ethylene and polyhalo-substituted ethylenes. Preferred monomers for copolymerization are vinyl-type monomers, representative of many specified being butadiene-1,3, 2,3-dimethylbutadiene, chloroprene, styrene, vinyl-phenol, a -butylacrylic acid, methyl acrylate, vinyl chloride, methacrylonitrile, vinyl chloroacetate, divinyl adipate, allyl chloride, diallyl phthalate, vinyl butyl ether and vinyl ethyl ketone.  Conventional means and catalysts are used for polymerization and copolymerization which may be performed in bulk, in solvents or aqueous suspension, at temperatures of 60-200 DEG  C., preferably 60-150 DEG  C.  The resins may be used in paints, enamels and lacquer.  In examples, products obtained by condensing (4) an addition product of acrolein and methyl esters of tung oil fatty acids, with aluminium isopropoxide (5) an addition product of acrolein and methyl octadecadienoate with aluminium butoxide, and (7) an addition product of acrolein and methyl abietate with aluminium isopropoxide afford plasticizers for polyvinyl chloride; in (10) the condensation product of (4) is copolymerized with methyl methacrylate and 5 per cent benzoyl peroxide; and in (11) the condensation product of (5) is copolymerized with acrylonitrile using the catalyst of (10).ALSO:Condensation products are made by treating an addition product of a a ,b -ethylenically unsaturated aldehyde and a salt, an amide or an ester of a polyethylenic acid having at least two ethylenic linkages in conjugated relationship, with an ester-type condensation catalyst which is defined as a material, such as aluminium isopropoxide, which initiates a condensation of two aldehyde groups to form an ester linkage.  Aldehydes may be aliphatic, alicyclic or aromatic and may have inert substituents such as halogen or ether radicles.  Preferred are aliphatic aldehydes of 3 to 12 carbon atoms.  Many aldehydes are specified representative being acrolein, cinnamaldehyde, 2,4-pentadienal, 2,5,7-octetrienal, 4-cyclohexyl-2-heptenal, 3-chlorophenyl-2,5-octadienal, 1 - cyclohexene - 1 - carboxaldehyde, 5,6 - dihydro - 1,2 - pyran - 3 - carboxaldehyde, 3,5 - diethyl - 2 - octenal and furfural.  The ethylenic linkages of the salt, amide or ester may be in an open-chain or cyclic structure and the free bonds may be attached to aliphatic, alicyclic or aromatic radicles which may contain inert substituents, e.g. halogen, ether and ester radicles. Representative of specified salts, amides and esters are sodium 5,7-decadienoate, potassium 6,8,11-penta-decatrienoate, sodium abietate, abietamide, ethyl-a -elaeostearate, butyl b -thioelaeostearate, methallyl 9,11-octadecatetrenooate, cyclohexyl 5,7,9,12 - octadecatetrenoate, phenyl 7,9 - octadecadienoate, glycol bis-(7,9-octadecadienoate) and glycerol 6,8,11-pentadecatrienoate.  Many acids are also specified from which salts, amides and esters may be derived representative being 5,7-octadecadienoic, 5,7,9 - octadecatrienoic, 5,7,13,15-eicosatetrenoic, 1,3 - cyclopentadienyl - 4 - pentanoic, 4,7 - dichloro - 9,11 - octadecadienoic and 3 - acetoxy - 6,8 - pentadecadienoic acids and resin acids such as abietic and l-pimaric acid.  Esters are the preferred derivatives and amongst many specified hydroxy compounds from which esters may be derived are methyl, isoamyl, methallyl, benzyl and furfuryl alcohols, cyclohexanol, phenol, 2-pyridinemethanol, glycol, glycerol and mannitol.  Many preferred esters are specified representative being butyl b -elaeostearate, methallyl 9,11-octadecadienoate, cyclohexenyl 5,7-octadecadienoate and glycerol trielaeostearate and also oils (triglycerides) derived from the said polyethylenic acids, e.g. tung, po-yoak, dehydrated castor, linseed and loofah oil (cf. Group III). Particularly preferred esters are those of open-chain and rosin polyethylenic acids of at least 12 carbon atoms and aliphatic alcohols of 1 to 10 carbon atoms, and drying oils, the acid residue of which contains at least 30 per cent of open-chain acids of at least 12 carbon atoms.  Amongst particularly preferred esters and oils specified are tung and oiticica oils, methyl elaeostearate, allyl and glycol 7,9-octadecadienoate, octyl abietate and glycerol dielaeostearate.  The addition products are preferably made by heating the reactants together at e.g. about 50-300 DEG  C., preferably 70-200 DEG  C. and optionally in the presence of conventional catalysts, diluents, solvents, inhibitors and inert atmospheres many of these classes of compounds being specified. Preferably, the salt, amide or ester and the aldehyde are reacted in a molar ratio of 1.5 : 1 to 1 : 3 respectively.  The pressure is optional.  In the condensation reaction a single addition product or a mixture of addition products may be treated. Preferred ester-type catalysts are lower alcoholates of the polyvalent metals in the second period of the Periodic Table, e.g. aluminium butoxide, propoxide, pentoxide hexoxide and ethoxide. They are used in amounts of 0.05-5 per cent, preferably 0.1-4 per cent, by weight of addition product optionally with diluents and generally under anhydrous conditions.  Room or higher or lower temperatures may be used, preferred being 20-40 DEG  C.  Pressure is optional and conventional inert solvents may be present.  In examples, addition products are made of acrolein with (1) tung oil, (3) oiticica oil, (4) methyl esters of tung oil fatty acids, (5) methyl octadecadienoate, (7) methyl abietate and (8) sodium elaeostearate and condensed in carbon tetrachloride with aluminium isopropoxide in (1), (4), (7) and (8) and with aluminium butoxide in (3) and (5); in (2) methacrolein is reacted with tung oil, (6) crotonaldehyde with butyl licanate and (9) 3,4-dihydro-1,2-pyran-6-carboxaldehyde with tung oil and the products treated in carbon tetrachloride with (2) aluminium isopropoxide and (9) aluminium ethoxide, and in (6) with aluminium isoproxide. Hydroquinone is used as an inhibitor in all of the above examples except (3) and (8).ALSO:Condensation products are made by treating an addition product of an a, b -ethylenically unsaturated aldehyde and a salt, an amide or an ester of a polyethylenic acid having at least two ethylenic linkages in conjugated relationship, with an ester-type catalyst which is defined as a material, such as aluminium isopropoxide, which initiates a condensation of two aldehyde groups to form an ester linkage.  Esters are preferred in the reaction and those specified include triglyceride oils such as tung, oiticica, po-yoak, neon dehydrated castor, essang, loofah, linseed and soya bean oil.  Preferred are oils the acid residue of which contains at least 30 per cent of open-chain polyethylenic acids of at least 12 carbon atoms.  Aldehydes may be aliphatic, alicyclic or aromatic and may have inert