Patent GB-984278-A (GB)
Title: New organic phosphoric amido compounds for use as cross-linking agents, compositions containing them and materials cross-linked by them
IPC: D04H1/58
Filed: 1961-03-28
Abstract: The invention comprises compounds of formula <FORM:0984278/C2/1> where A is a bivalent aliphatic hydrocarbon radical, a cycloaliphatic hydrocarbon radical, or a bivalent aliphatic radical interrupted by a hetero atom, e.g. oxygen or sulphur, X1 and X2 are each oxygen or sulphur, R and R1 are each hydrogen or alkyl and Y1 and Y2 are each -OR11 or <FORM:0984278/C2/2> where R1 and R2 are each hydrogen or alkyl and R11 is alkyl. They are prepared by reacting HO-A-OH and PSCl3 or POCl3 to give Cl2P(X2)-O-A-O-P(X2)Cl2 and then reacting this with an ethyleneimine in the presence of K2CO3, or first with the theoretical amount of an alcohol R11OH and then with the ethyleneimine. The products are used to cross-link natural and synthetic macro-molecular compounds (see Divisions B2, B6, C3 and D1).  The compound Cl2P(S)-OCH2CH2-O-CH2CH2O -P(S)Cl2 is obtained from diethylene glycol and PSCl3.ALSO:Natural and synthetic macromolecular substances are cross-linked by means of an organophosphorus compound of formula <FORM:0984278/C3/1> where A is a bivalent aliphatic hydrocarbon radical, a cycloaliphatic hydrocarbon radical, or a bivalent aliphatic radical interrupted by a hetero atom, e.g. oxygen or sulphur, R and R1 are each hydrogen or alkyl and Y1 and Y2 are each -OR11 or <FORM:0984278/C3/2> where R1 and R2 are each hydrogen or alkyl and R11 is alkyl (for preparation see Division C2).  Specified macromolecular substances include starch, alginic acid, gelatin, cellulose fibres, cellulose esters and ethers, polyesters, alkyd resins, polyamides, polyurethanes, polyacrylic compounds, polyvinylacetate, polyvinylalcohol, polyvinylchloride and copolymers thereof, natural rubber and synthetic rubbers such as butadiene-styrene copolymers, butadiene-acrylonitrile copolymers and polyisoprene. Cross-linking may be effected at 100-200 DEG  C., preferably 130-150 DEG  C. using 1-15% by weight of cross-linking agent.  The cross-linking agent is suitably added to an aqueous solution or dispersion of the macromolecular substance. Plasticizers, epoxy resins, unsaturated polyesters, alkyd resins and/or precondensates of thermosetting resins, e.g. etherified methylol urea or etherified methylol melamine may also be added. The following compositions which contain in addition a cross-linking agent of the above type are prepared in examples: (2) a printing paste by homogenizing a butyl acrylate-acrylonitrile-acrylamide copolymer latex, methylcellulose, ammonium nitrate, mineral spirit, pigment and water; (3) an adhesive for preparing non-woven fabric from the above latex and water; (4) an adhesive for preparing non-woven fabric from a butadiene-acrylonitrile copolymer latex, polyvinylalcohol and water; (5) a paste for sticking flocks to rubber sheet from natural rubber latex, polyvinyl alcohol, colloidal sulphur, a vulcanization promoter, an ageing retardant and water; (6) a paste for sticking flock to fabric from polyvinylacetate emulsion, butyl phthalate, ammonium nitrate, pigment and water; and (7) a coating composition from butadiene-acrylonitrile copolymer, sulphur and methylethylketone.  The latex used in Examples 2 and 3 is prepared by copolymerizing butyl acrylate, acrylonitrile and acrylamide (78 : 20 : 2 weight ratio) in aqueous suspension using potassium persulphate as catalyst.ALSO:Polmeric coating compositions contain as cross-linking agent an organophosphorus compound of formula: <FORM:0984278/B1-B2/1> where A is a bivalent aliphatic hydrocarbon radical, a cycloaliphatic hydrocarbon radical, or a bivalent radical interrupted by a hetero atom, e.g. oxygen or sulphur, X1 and X2 are each oxygen or sulphur, R and R1 are each hydrogen or alkyl, and Y1 and Y2 are each -OR11 or <FORM:0984278/B1-B2/2> where R1 and R2 are each hydrogen or alkyl and R11 is alkyl.  The composition may be in the form of a printing paste for fabrics or may be used to stick flock on to flexible substrates such as fabrics, rubbers, leather, paper or metal.  In examples: (2) cotton and rayon cloths are printed with a paste prepared by homogenizing a butyl acrylate-acrylonitrile-acrylamide copolymer latex, methylcellulose, copper phthalocyanin pigment, ammonium nitrate and one of the above cross-linking agents; the print is fixed by heating at 130 DEG C.; (5) a rubber sheet is treated with a paste prepared from a natural rubber latex, polyvinyl alcohol, colloidal sulphur, water and one of the above cross-linking agents, exposed in a wet state to viscose rayon flocks in an electrostatic field, dried, and heated at 130 DEG C.; (6) cotton fabric is printed with a paste comprising polyvinylacetate emulsion, butyl phthalate, ammonium nitrate, pigment, water and one of the above cross-linking agents, treated while wet with viscose rayon flocks in an electrostatic field, dried, and heated at 130 DEG C.; (7) a metal surface cleaned by removal of grease followed by acid percolation is brushed or sprayed with a methyl ethyl ketone solution containing butadiene-acrylonitrile copolymer, sulphur and one of the above cross-linking agents, dried and heated at 130 DEG C. under 100-1000 p.s.i. pressure.ALSO:A treatment for imparting crease resistance to fabrics made of natural and synthetic fibres and for increasing their affinity to direct and basic dyes comprises soaking the fabric with an aqueous dispersion or organic solvent solution of an organophosphorus compound of formula <FORM:0984278/D1-D2/1> where A is a bivalent aliphatic hydrocarbon radical, a cycloaliphatic hydrocarbon radical, or a bivalent radical interrupted by a hetero atom, e.g. oxygen or sulphur, X1 and X2 are each oxygen or sulphur, R and R1 are each hydrogen or alkyl, and Y1 and Y2 are each -OR11 or <FORM:0984278/D1-D2/2> where R1 and R2 are each hydrogen or alkyl and R11 is alkyl.  The fabric is then dried and heated.  In Example 1 an aqueous emulsion comprising a polyoxyethylene alkyl ether surface active agent and the compound <FORM:0984278/D1-D2/3> is padded on to viscose rayon cloth, which is dried and thermally set at 150 DEG C.  It is then dyed with Brilliant Scarlet 3R (acid dye).  Non-woven fabrics are prepared by using as adhesive a macromolecular substance together with one of the above organophosphorus compounds as cross-linking agent.  Various fibres of animal, vegetable, mineral and synthetic origin are specified.  In examples: (3) a random web of polyester fibre is sprayed with and then dipped in an aqueous dispersion of a butylacrylate-acrylonitrileacrylamide copolymer latex and the compound <FORM:0984278/D1-D2/4> squeezed between rollers, dried and heated at 150 DEG C.; (4) a viscose rayon random web is similarly treated with an aqueous dispersion of a butadiene-acrylonitrile copolymer and polyvinyl alcohol containing the same phosphorus compound as (3).