Patent GB-859640-A (GB)
Title: Diisocyanate-modified polyesters and a process for their preparation
IPC: C08G18/10
Filed: 1957-04-15
Abstract: A method of preparing a resinous composition comprises reacting a lactone or a mixture of lactones each having at least six carbon atoms in the ring with a bifunctional compound (as defined below) for forming a lactone polyester having terminal hydroxyl groups. reacting the resulting polyester with an organic diisocyanate to form a substantially linear polyester-polyurethane diisocyanate; and reacting the latter with an excess of polyfunctional compound (as defined below) to form a millable gum product.  The term "bifunctional compound" or "bifunctional initiator" is used to denote a bifunctional compound which contains two hydroxyl groups, two amino groups or one hydroxyl group and one amino group.  The term "polyfunctional compound" refers to water or to a compound which contains at least two functional groups which are hydroxyl, amino or carboxyl groups.  The products contain groups of the formula:- <FORM:0859640/IV(a)/1> in which R is an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, the Zs stand for -O-, NH, or NR1, R1 is an alkyl, aryl, aralkyl or cycloalkyl radical, n is at least 5 and the sum of the x's is at least three; and each terminal oxygen is connected to a CO group of an organic diisocynate.  Preferably the polyester-polyurethane is prepared in three separate and successive stages and converted into an elastomer by reaction with a polyisocyanate, but it is also possible to combine several stages or to change their order.  The diols employed in the first stage include alkylene glycols, cyclohexanediols, xylenediols, hydroxymethyl-phenethyl alcohols, hydroxymethyl-3-phenyl-propanols, phenylenediethanols or dipropanols, heterocyclic diols and polyoxyalkylated derivatives of compounds having two reactive hydrogen atoms which may be present in phenolic hydroxyl, mercapto, amido, sulphonamido or carboxyl groups.  Useful amino-alcohols may be aliphatic, aromatic or cycloaliphatic.  The diamines may contain primary or secondary amino groups and may be aliphatic, aromatic, cycloaliphatic or heterocyclic.  Other bifunctional initiators are polymers of monoepoxides.  Catalysts for the first stage include lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, borium, strontium, zinc, aluminium, cobalt, titanium, tin, lead, antimony, arsenic, cerium, alkoxides thereof alkali- and alkaline earth metal carbonates, organic tin oxides and titanates, titanium, chelates and acylates, litharge, zinc oxide, antimony trioxide, germanium dioxide, cerium trioxide, cobaltous acetate, zinc borate, lead salts, mono- or dicarboxylic acids, hydrochloric, sulphuric or phosphoric acid, zinc chloride, aluminium trichloride, tin di- or tetrachloride and boron trifluoride.  The reaction is preferably conducted in an inert atmosphere.  In the second stage the reaction of the polyester with the excess diisocyanate may be effected in the presence of such catalysts as inorganic or tertiary organic bases, e.g. dimethyl-aniline, dimethylhexahydroaniline, N, N1-dimethylpiperazine, N-methylmorpholine, tribenzylamine, N, N-dimethylbenzylamine, triethylamine, trialkyl phosphines, dialkylphenylphosphines or alkyldiphenyl phosphines.  Suitable retarders for the reaction are hydrochloric, sulphuric, phosphoric, boric and organic acids; acyl halides, sulphonyl halides, inorganic acid halides, sulphur dioxide and acidic sulphones.  Any alkaline material present should be neutralized before the reaction.  A list of polyisocyanates is given.  In the third stage there may be used as cross-linking compounds those specified as bifunctional reactants for the first stage.  Water and dicarboxylic acids can also be used, particularly where a foamed product is required.  In the fourth stage curing is effected with a polyisocyanate preferably 3 to 7% by weight based on the cross-linked material.  As modifying agents there may be added at any stage (after the production of the polyester) fillers such as carbon black, clay, zinc oxide, titanium oxide; dyes; plasticizers such as polyesters, stearic and other fatty acids and their organic esters, metal salts of fatty acids, dioctyl phthalate or tetrabutylthiodisuccinate; mould release agents such as polytetrafluoroethylene, silicone oils, polyethylene greases, paraffin wax, petroleum jelly, "Carbowaxes" or mineral or vegetable oils.ALSO:A method of preparing a resinous composition (which may be a foamed product) comprises reacting a lactone or a mixture of lactones each having at least six carbon atoms in the ring with a bifunctional compound (as defined below) for forming a lactone polyester having terminal hydroxyl groups, reacting the resulting polyester with an organic diisocyanate to form a substantially linear polyester-polyurethane diisocyanate; and reacting the latter with an excess of polyfunctional compound (as defined below) to form a millable gum product.  The term "bifunctional compound" or "bifunctional initiator" is used to denote a bifunctional compound which contains two hydroxyl groups, two amino groups or one hydroxyl group and one amino group.  The term "polyfunctional compound" refers to water or to a compound which contains at least two functional groups which are hydroxyl, amino or carboyxl groups.  The products contain groups of the formula:-  <FORM:0859640/V/1> in which R is an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, the Z's stand for -O-, NH, or NR1, R1 is an alkyl, aryl, aralkyl or cylcoalkyl radical, n is at least 5 and the sum of the x's is at least three; and each terminal oxygen is connected to a CO group of an organic diisocyanate.  Preferably the polyester-polyurethane is prepared in three separate and successive stages and converted into an elastomer by reaction with a polyisocyanate, but it is also possible to combine several stages or to change their order.  The diols employed in the first stage include alkylene glycols, cyclohexanediols, xylenediols, hydroxymethyl-phenethyl alcohols, hydroxymethyl-3-phenyl-propanols, phenylenediethanols or dipropanols, heterocyclic diols and polyoxyalkylated derivatives of compounds having two reactive hydrogen atoms which may be present in phenolic hydroxyl, mercapto, amido, sulphonamido or carboxyl groups.  Useful amino-alcohols may be aliphatic, aromatic or cycloaliphatic.  The diamines may contain primary or secondary amino groups and may be aliphatic, aromatic, cycloaliphatic or heterocyclic.  Other bifunctional initiators are polymers of monoepoxides.  Catalysts for the first stage include lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, borium, strontium, zinc, aluminium, cobalt, titanium, tin, lead, antimony, arsenic, cerium, alkoxides thereof, alkali- and alkaline earth metal carbonates, organic tin oxides and titanates, titanium chelates and acylates, litharge, zinc oxide, antimony trioxide, germanium dioxide, cerium trioxide, cobaltous acetate, zinc borate, lead salts, mono- or dicarboxylic acids, hydrochloric, sulphuric or phosphoric acid, zinc chloride, aluminium trichloride, tin di- or tetrachloride and boron trifluoride.  The reaction is preferably conducted in an inert atmosphere.  In the second stage the reaction of the polyester with the excess diisocyanate may be effected in the presence of such catalysts as inorganic or tertiary organic bases, e.g. dimethylaniline, dimethylhexahydroaniline, N, N1-dimethylpiperazine, N-methylmorpholine, tribenzylamine, N, N-dimethylbenzylamine, triethylamine, trialkyl phosphines, dialkylphenylphosphines or alkyldiphenyl phosphines.  Suitable retarders for the reaction are hydrochloric sulphuric, phosphoric, boric and organic acids; acyl halides, sulphonyl halides, inorganic acid halides, sulphur dioxide and acidic sulphones.  Any alkaline material present should be neutralised before the reaction.  A list of polyisocyanates is given. In the third stage there may be used as cross-linking compounds those specified as bifunctional reactants for the first stage.  Water and dicarboxylic acids can also be used, particularly where a foamed product is required.  In the fourth stage curing is effected with a polyisocyanate preferably 3 to 7% by weight based on the cross-linked material.  As modifying agents there may be added at any stage (after the production of the polyester) fillers such as carbon black, clay, zinc oxide, titanium oxide; dyes; plasticisers such as polyesters, stearic and other fatty acids and their organic esters, metal salts of fatty acids, dioctyl phthalate or tetrabutylthiodisuccinate; mould release agents such as polytetrafluoroethylene, silicone oils, polyethylene greases, paraffin wax, petroleum jelly, "Carbowaxes" or mineral or vegetable oils.