Patent GB-1002321-A (GB)
Title: Improvements in or relating to the transesterification of aryl phosphites
IPC: C07F9/141
Filed: 1961-09-11
Abstract: An aromatic phosphite having the formula <FORM:1002321/C3/1> wherein R1, R2 and R3 are selected from aryl and haloaryl is trans-esterified, with removal of the corresponding phenol by distillation, by reaction with an alcohol selected from alkanols, cycloalkanols, 1,2- or 1,3-alkane-diols, polymethylene and polyethylene glycols, polypropylene glycols, thiodiglycol, sulphonyl diglycol, pentaerythritol, monoalkyl or monoaryl ethers of ethylene glycol, monoalkyl ethers of polyethylene glycol, and tetrahydrofurfuryl alcohol in the presence of a secondary phosphite having the formula <FORM:1002321/C3/2> wherein R4 and R5 are selected from aryl, haloaryl, alkyl, haloalkyl and cycloalkyl radicals as a catalyst, e.g. in an amount of 0.1 to 1% by weight of the triaryl or trihaloaryl phosphite. The preferred alcohols are C10-C18 alkanols, 1,2- and 1,3-alkanediols, pentaerythritol and monoalkyl ethers of ethylene and polyethylene glycol.  Mixed ester products can be obtained by a two-step reaction, e.g. one mol. of pentaerythritol can be reacted with 2 moles of triphenyl phosphite and one mol. of the 3,9-diphenoxy - 2,4,8,10 - tetraoxa - 3,9 - diphosphaspiro (5,5) undecane thus formed can then be reacted with 2 mols. of a monohydric alcohol, e.g. decyl alcohol, to form the corresponding 3,9-didecycloxy compound, the catalyst being present in each step of the reaction.  The transesterification can be carried out until one, two or three mols. of the phenol are removed per mol. of the triaryl phosphite starting material or can be controlled by limiting the amount of alcohol which is added, e.g. by adding 1,2 or 3 mols. of a monohydric alcohol or 1 or 1.5 mols. of glycol per mol. of triaryl phosphite.  The preferred alcohols are C10-C18 alkanols, 1,2-and 1,3-alkanediols, pentaerythritol and monoalkyl ethers of ethylene and polyethylene glycol and in making bis-dioxaphosphorinanes the use of polyethylene or polypropylene glycol, thiodiglycol and sulphonyl diglycol is useful for forming a bridge between the two dioxaphosphorinane rings.  Among the phosphite products obtainable by the process and which may involve additional stepwise transesterification procedures are (a) ether phosphites having the formula <FORM:1002321/C3/3> wherein R1 is alkoxy (or aryloxy) ethoxyethyl, alkoxy (or aryloxy-) polyethoxyethyl and R2 and R3 are the same as R1 or are alkyl or aryl; (b) dioxaphospholanes and dioxaphosphorinanes having the formula <FORM:1002321/C3/4> wherein R1, R2, R3, R4, R5 and R6 are hydrogen or C1-C4 alkyl groups, n is 0 or 1 and R7 is aryl, alkyl, cycloalkyl, alkoxyalkyl, alkoxypolyalkoxyalkyl, aryloxyalkyl or aryloxypolyalkoxyalkyl; (c) tetra-oxadiphosphaspiro undecanes of the formula <FORM:1002321/C3/5> wherein R1 and R2 are aryl, alkyl, aryloxyethyl, alkoxyethyl, alkoxy (or aryloxy) ethoxyethyl, or alkoxypolyethoxyethyl; (d) linked phosphorinanes and phospholanes of the formula <FORM:1002321/C3/6> wherein R1 to R6 are hydrogen or C1-C4 alkyl, Z is <FORM:1002321/C3/7> or alkyl-substituted -ethyleneoxy or -propyleneoxy, x being an integer of at least one and n being 0 or 1; (e) phosphites of the formula <FORM:1002321/C3/8> wherein R1 to R4 are alkyl or aryl and Z is <FORM:1002321/C3/9> wherein x is an integer of at least 2; and (f) monomeric and polymeric phosphites of the formula <FORM:1002321/C3/100> wherein R is alkyl or aryl, m is O or an integer, Y is S, O, NR2, (OCH2CH2O)x, <FORM:1002321/C3/111> or CH2, n is zero or an integer, preferably not over 10, Z is zero or one, R2 is hydrogen, alkyl or aryl, R3 is H or CH3 and x is an integer or at least one.  The latter type of phosphite may be prepared by reacting the appropriate 3,9-dialkyl (or diaryl) - 2,4,8,10 - tetraoxa - 3,9 - diphosphaspiro (5,5) undecane with the appropriate dihydric alcohol in a mol. ratio of 1 : 1 in the presence of the diorgano phosphite and the reaction can be stopped by adding excess monohydric alcohol, e.g. methanol, decanol or octadecanol or a phenol as a chain stopper.  Examples are given for the production of various phosphites including tris methoxy carbowax 350 phosphite, methoxyethoxyethoxyethyl diphenyl phosphite, diisodecyl (or distearyl) pentaerythritol diphosphite, bis-methoxy-carbowax 350 pentaerythritol diphosphite, tris - (methoxyethoxyethoxyethyl) phosphite, tris-methoxy carbowax 550 phosphite, bis-(methoxyethoxyethoxyethyl phenyl phosphite, 2 - isododecyloxy - 5,5 - dimethyl - 1,3,2 - dioxaphosphorinane and the corresponding 2-stearyloxy, 2 - methoxyethoxyethoxyethyl and methoxy carbowax 350 - neopentylene phosphites, 2 - isododecyloxy - 5 - ethyl - 5 - methyl - 1,3,2-dioxaphosphorinane, 2-isodecyloxy-4-methyl-1,3,2 - dioxaphosphorinane and the corresponding 4,4,6-trimethyl and 4-propyl-5-ethyl compounds, diisodecyl pentaerythritol diphosphite and the corresponding dioctadecyl-, bismethoxy carbowax-350-and bis-(butyl carbitol)-pentaerythritol diphosphites, diethylene glycol dineopentylene diphosphite and the corresponding triethylene glycol and thiodiglycol-dineopentylene diphosphites, diethylene glycol dihexylene diphosphite, triethylene glycol dineohexylene diphosphite, tetraphenyl (and tetraisodecyl) - diethylene glycol diphosphites, a phosphite of the formula <FORM:1002321/C3/122> wherein x has an average value of 5.5, and high molecular weight polyphosphites by reacting di-decyl pentaerythritol diphosphite with ethylene glycol, diethyl glycol, trimethylene glycol, dipropylene glycol, thiodiglycol and diethanolamine respectively in the presence of diphenyl phosphite.  Compounds of types (a), (e) and (f) as defined above and compounds of type (b) in which R7 is alkoxyethyl, alkoxypolyethoxyethyl, aryloxyethyl and aryloxy polyethoxyethyl, compounds of type (c) in which R1 is aryloxyethyl, alkoxyethyl, aryloxyethoxyethyl, alkoxyethoxyethyl or alkoxypolyethoxyethyl and R2 is the same as R1 or is alkyl or aryl, and compounds of type (d) in which Z contains an ether, thioether or sulphonyl linkage are stated to be novel and the invention includes such compounds per se. Compounds of type (a) are useful as stabilizers for polyurethane rubbers, nylon, polyethers, high molecular weight formaldehyde polymer and acrylonitrile polymers and as scavengers for removing carboxyl groups from polyesters.  The new compounds of type (b) are useful as antioxidants for polyethylene, polypropylene, polyethylene glycols and natural and synthetic rubber, the new compounds of type (c) are useful as stabilizers for polyurethanes and polyolefines, e.g. polyethylene or polypropylene, and as curing agents for epoxy resins, the new compounds of type (d) are useful as antioxidants for polyethylene and polypropylene and as stabilizers for polyurethanes and acrylonitrile polymers, the compounds of type (e) are useful as antioxidants for polyethylene, polypropylene, or natural rubber and as stabilizers for polyurethane-forming materials and the compounds of type (f) are useful as antioxidants for polyethylene, polypropylene and polystyrene.  Specification 943,731 is referred to. Reference has been directed by the Comptroller to Specification 954,071.ALSO:An aromatic phosphite having the formula <FORM:1002321/C2/1> wherein R1, R2 and R3 are selected from aryl and haloaryl is transesterified, with removal of the corresponding phenol by distillation, by reaction with an alcohol selected from alkanols, cycloalkanols, 1,2- or 1,3-alkane-diols, polymethylene-and polyethylene-glycols, polypropylene glycols, thiodiglycol, sulphonyl diglycol, pentaerythritol, monoalkyl or monoaryl ethers of ethylene glycol, monoalkyl ethers of polyethylene glycol, and tetrahydrofurfuryl alcohol in the presence of a secondary phosphite having the formula <FORM:1002321/C2/2> wherein R4 and R5 are selected from aryl, halo-aryl, alkyl, haloalkyl and cycloalkyl radicals as a catalyst, e.g. in an amount of 0.1 to 1% by weight of the triaryl or trihaloaryl phosphite. The preferred alcohols are C10-C18 alkanols, 1,2-and 1,3-alkanediols, pentaerythritol and monoalkyl ethers of ethylene and polyethylene glycol. Mixed ester products can be obtained by a two-step reaction, e.g. one mol. of pentaerythritol can be reacted with 2 moles of triphenyl phosphite and one mol. of the 3,9-diphenoxy-2,4,8,10-tetraoxa - 3,9 - diphosphaspiro (5,5) undecane thus formed can then be reacted with 2 mols. of a monohydric alcohol, e.g. decyl alcohol, to form the corresponding 3,9-didecycloxy compound, the catalyst being present in each step of the reaction. The transesterification can be carried out until one, two or three mols. of the phenol are removed per mol. of the triaryl phosphite starting material or can be controlled by limiting the amount of alcohol which is added, e.g. by adding 1, 2 or 3 mols. of a monohydric alcohol or 1 or 1.5 mols. of glycol per mol. of triaryl phosphite. The preferred alcohols are C10-C18 alkanols, 1,2- and 1,3-alkanediols, pentaerythritol and monoalkyl ethers of ethylene and polyethylene glycol and in making bis-dioxaphosphorinanes the use of polyethylene or poly-propylene glycol, thiodiglycol and sulphonyl diglycol is useful for forming a bridge between the two dioxaphosphorinane rings.  Among the phosphite products obtainable by the process are (a) ether phosphites having the formula <FORM:1002321/C2/3> wherein R1 is alkoxy (or aryloxy) ethoxyethyl alkoxy-(or aryloxy-)polyethoxyethyl and R2 and R3 are the same as R1 or are alkyl or aryl; (b) dioxaphospholanes and dioxaphosphorinanes having the formula <FORM:1002321/C2/4> wherein R1, R2, R3, R4, R5 and R6 are hydrogen or C1-C4 alkyl groups, n is 0 or 1 and R7 is aryl, alkyl, cycloalkyl, alkoxyalkyl, alkoxypoly-alkoxyalkyl, aryloxyalkyl or aryloxypolyalk-oxyalkyl; (c) tetra - oxadiphosphaspiro undecanes of the formula <FORM:1002321/C2/5> wherein R1 and R2 are aryl, alkyl, aryloxy-ethyl alkoxyethyl, alkoxy (or aryloxy) ethoxyethyl, or alkoxypolyethoxyethyl; (d) linked p