Patent GB-870940-A (GB)
Title: Improvements in and relating to foamed polymers
IPC: C08G18/42
Filed: 1958-01-14
Abstract: The invention comprises a foamed polymer comprising groups of the general formulae:  <FORM:0870940/IV (a)/1> wherein R represents hydrogen, alkyl, cycloalkyl, alkoxy, or single ring aromatic radicals, R1 represents a polyvalent aliphatic, cycloaliphatic, aromatic or heterocyclic radical, n is at least 4, at least n+ 2 Rs are hydrogen, x is at least 1, y is equal to the valence of R1, Y is-O-, -NH-or NR2, R2 is a monovalent hydrocarbon radical, R3 is a polyvalent hydrocarbon radical in which polymer groups represented by formulae (a) are linked to groups represented by formulae (b) and (c) by bonding between terminal oxygen atoms and terminal carbonyl groups and each group represented by (c) is linked to another group represented by (c) through a group represented by (b) by bonding between a nitrogen atom of (c) and a carbonyl group of (b).  It also comprises a process of preparing a foamed polymer in which a polyester of a lactone having at least six carbon atoms in the ring and an organic compound containing at least two reactive hydrogens in the form of hydroxyl or amino radicals is reacted with at least 100% molar excess over the amount necessary to react with such reactive hydrogens of a polyisocyanate and with water or a polycarboxylic acid.  The polyester, water and polyisocyanate can be reacted with excess polyisocyanate to form a prepolymer which is subsequently admixed with water.  A basic catalyst may be employed in either reaction.  A polyfunctional compound having at least two hydroxyl groups or at least one amino radical may be mixed with the polyester before the reaction with the polyisocyanate.  The polyester is obtained by reacting the lactone with polyfunctional compounds such as alkylene glycols, cyclohexanediols, alkylene bis-cyclohexanols, xylenediols, hydroxyalkylphenalkyl alcohols, phenylene dialkanols, heterocyclic diols, aminoalcohols, diamines (aliphatic, carbocyclic, and heterocyclic), higher functional initiators, such as triols, tetrols, pentols, hexols, alkyl glucosides, polyhydroxy fatty acid esters, polyoxyalkylated derivatives of polyfunctional compounds, higher functional aminoalcohols and polyamines.  To the polyester before its reaction with the polyisocyanate may be added such polyfunctional compounds as glycerol, 1, 2, 4-butanetriol, 1, 2, 6-hexanetriol, trimethylolethane or propane diethanolamine, triethanolamine and N, N, N1, N1-tetrakis (2-hydroxyethyl) ethylenediamine.  Catalysts for the esterification are acids such as sulphuric, hydrochloric, phosphoric, perchloric and Lewis acids. Basic and neutral interchange catalysts (e.g. metals, alkoxides, carbonates, organic tin compounds, chelates, metal oxides) are also listed.  Lactone polyesters having terminal carboxylic acid groups with or without also hydroxy or amino groups (from the use of hydroxy and aminocarboxylic or polycarboxylic acids as initiators) can also be used.  Aliphatic, and aromatic di- and higher functional acids are listed.  In using such polyesters or with polycarboxylic acids as foaming agents, water is used in addition to augment the carbon dioxide production.  Catalysts for the foaming and curing are sodium hydroxide, sodium methylate, sodium acetate, sodium phenolate, tertiary amines and phosphines.  Prepolymers, when employed can be stabilized with hydrochloric, sulphuric, phosphoric, boric, or organic acids, organic acid halides, sulphonyl halides, phosphorus halides, thiamyl chlorides, sulphur dioxide and acid sulphones.  As foam stabilizers there may be added ethoxylated cellulose, hydroxyethylated cellulose, benzyl cellulose, acetyl cellulose, acetyl butyryl cellulose, hydroxyethylated polyvinyl alcohol, polyvinyl chloride, vinyl chloride-vinylacetate copolymers, polyvinyl butyral, polymethyl methacrylate, polybutylmethacrylate, polyethylene oxide, bentone and fatty acid metal soaps.  Fillers, clays, diatomaceous earths, and silicone and paraffin oils can also be added to the mixture. In typical Examples (1) a polyester is prepared by reacting mixed methyl-epsilon-caprolactones and pentaeryththritol in the presence of dibutyltin oxide.  It is mixed with 2, 4-tolylene diisocyanate containing ethoxylated cellulose, emulsifier and N-methyl morpholine, and reacts to give a pre-polymer.  Water is then added to yield a foam; (6) the polyester is prepared from epsilon caprolactone, mixed methyl and trimethyl caprolactones and castor oil and reacted similarly.  In further examples the foam is formed in one step from such polyesters as the reaction product of methyl-epsilon caprolactones and (12) a triol from ethylene oxide and trimethylol propane; (15) a propylene oxide/trimethylol propane reaction product; (16) a castor oil-ethylene oxide product; (18) a polyether from ethylene glycol, ethylene oxide and propylene oxide.ALSO:The invention comprises a foamed polymer comprising groups of the general formulae <FORM:0870940/V/1> <FORM:0870940/V/2> <FORM:0870940/V/3> wherein R represents hydrogen, alkyl, cycloalkyl, alkoxy, or single ring aromatic radicals, R1 represents a polyvalent aliphatic, cycloaliphatic, aromatic or heterocyclic radical, n is at least 4, at least n+2 Rs are hydrogen, x is at least l2y is equal to the valence of R1 Y os -O-, -NH- or NR2R2 is a monovalent hydrocarbon radical, R3 is a polyvalent hydrocarbon radical, in which polymer groups represented by formulae (a) are linked to groups represented by formulae (b) and (c) by bonding between terminal oxygen atoms and terminal carbonyl groups and each group represented by (c) is linked to another group represented by (c) through a group represented by (b) by bonding between a nitrogen atom of (c) and a carbonyl group of (b).  It also comprises a process of preparing a foamed polymer in which a polyester of a lactone having at least six carbon atoms in the ring and an orgnaic compound containing at least two reactive hydrogens in the form of hydroxyl or amino radicals is reacted with at least 100% molar excess over the amount necessary to react with such reactive hydrogen of a polyisocyanate and with water or a polycarboxylic acid.  The polyester, water and polyisocyanate can be reacted with excess polyisocyanate to form a prepolymer which is subsequently admixed with water.  A basic catalyst may be employed in either reaction. A polyfunctional compound having at least two hydrosyl groups or at least one amino radical may be mixed with the polyester before the reaction with the polyisocyanate.  The polyester is obtained by reacting the lactone with poly-functional compounds such as alkylene glycols, cyclohexanediols, alkylene bis-cyclo-hexanols, xylenediols, hydroxyalkylphenalkyl alcohols, phenylene dialkanols, heterocyclic diols, amino-alcohols, diamines (aliphatic, carbocyclic, and heterocyclic), higher functional initiators, such as triols, tetrols, pentols, hexols, alkyl glucosides, polyhydroxy fatty acid esters, polyoxyalkylated derivativies of polyfunctional compounds, higher functional aminoalcohols and polyamines.  To the polyester before its reaction with the polyisocyanate may be added such polyfunctional compounds as glycerol, 1, 2, 4-butanetriol, 1, 2, 6-hexanetriol, trimethylol-ethane or propane diethanolamine, triethanolamine and N, N, N1, N1-tetrakis (2-hydroxyethyl) ethylenediamine.  Catalysts for the esterification are acids such as sulphuric, hydrochloric, phosphoric, perchloric and Lewis acids.  Basic and neutral interchange catalysts (e.g. metals, alkoxides, carbonates, organic tin compounds, chelates, metal oxides) are also listed.  Lactone polyesters having terminal carboxylic acid groups with or without also hydroxy or amino groups (from the use of hydroxy and amino-carboxylic or polycarboxylic acids as initiators) can also be used.  Aliphatic, and aromatic di- and higher functional acids are listed.  In using such polyesters or with poly-carboxylic acids as foaming agents, water is used in addition to augment the carbon dioxide production.  Catalysts for the foaming and curing are sodium hydroxide, sodium methylate, sodium acetate, sodium phenolate, tertiary amines and phosphines.  Prepolymers, when employed can be stabilized with hydrochloric, sulphuric, phosphoric, boric, or organic acids, organic acid halides, sulphonyl halides, pholphorus halides, thiamyl chlorides, sulphur dioxide and acid sulphorus.  As foam stabilizers there may be added ethoxylated cellulose, hydroxyethylated cellulose, benzyl cellulose, acetyl cellulose, acetyl butyryl cellulose, hydroxyethylated polyvinyl alcohol, polyvinyl chloride, vinyl chloride-vinylacetate copolymers, polyvinyl butyral, polymethyl methacrylate, polybutylmethacrylate, polyethylene oxide, bentone and fatty acid metal soaps.  Fillers, clays, diatomaceous earths, and silicone and paraffin oils can also be added to the mixture.  In typical examples (1) a polyester is prepared by reacting mixed methyl-epsiloncaprolactones and pentaerythritol in the presence of dibutyltin oxide.  It is mixed with 2, 4-tolylene diisocyanate containing ethoxylated cellulose, emulsifier and N-methyl morpholine, and reacts to give a prepolymer.  Water is then added to yield a foam; (6) the polyester is prepared from epsilon caprolactone, mixed methyl and trimethyl caprolactones and castor oil and reacted similarly.  In further examples the foam is formed in one step from such polyesters as the reaction product of methylepsilon caprolactone and (12) a triol from ethylene oxide and trimethylol propane; (15) a propylene oxide/trimethylol propane reaction product; (16) a castor oil-ethylene oxide product; (18) a polyether from ethylene glycol, ethylene oxide and propylene oxide.