Patent GB-912530-A (GB)
Title: New phosphorus boron polymers and processes for their production
Inventor: BURG ANTON BEHME
IPC: C07F9/02
Filed: 1960-07-25
Abstract: The invention comprises a phosphinoborine polymer comprising one or more series of structural units of the formula R1R11PBH2 the units in any one series being linked together by phosphorus-to-boron tetra-co-ordinate bonds, in which a terminal unit of each series is bonded to an organic secondary or tertiary amine or phosphine, preferably a linear polymer of the formula (R1R11PBH2)n wherein R1 and R11 represent separate alkyl, alkenyl or aryl hydrocarbon groups bonded to the phosphorus atom or together represent a divalent hydrocarbon radical bonded by each of the two valencies to the phosphorus atom, n represents the degree of polymerization and may be an integer of 3-1,000 and Y represents a secondary or tertiary organic amine or phosphine. The phosphinoborine polymer may be made by pyrolysing an adduct of diborane and a secondary phosphine in the presence of a secondary or tertiary amine or phosphine. Alternatively a mixture of an adduct derived from diborane and a secondary phosphine together with a minor proportion of an adduct of a primary phosphine and diborane is pyrolysed in the presence of a secondary or tertiary amine or phosphine to form a polymer comprising R1R11PBH2 structural units with units of the primary phosphinoborine interpolated between pairs of the said structural units which may give rise to branching or cross-linking.  The pyrolysis is carried out at temperatures between 130 DEG C. and 250 DEG C. for between 10 and 60 hours.  Inert solvents may be used.  Suitable reactants are the borane adducts of dimethylphosphine, methyl-ethyl-phosphine, diethylphosphine, methylallyl phosphine, methyl-n-propylphosphine, methyl-isopropylphosphine, cyclotetramethylphosphine, methyldodecylphosphine, methylphenylphosphine, and tetramethylbiphosphine with amines such as trimethylamine, triethylamine, tributylamine, piperidine, N-methyl-piperidine, pyridine or tetramethylguanidine and difunctional amines such as triethylenediamine, N,N,N1,N1-tetraethylethylene diamine and N,N,N1,N1-tetramethylethylenediamine or with dimethylphosphine. Methyl phosphine is a suitable primary phosphine.  Detailed examples are given.ALSO:The invention comprises a phosphino-borine polymer comprising one or more series of structural units of the formula R1R11PBH2 the units in any one series being linked together by phosphorus - to - boron tetra-coordinate bonds, in which a terminal unit of each series is bonded to an organic secondary or tertiary amine or phosphine, preferably a linear polymer of the formula (R1R11PBH2)n Y wherein R1 and R11 represent separate alkyl, alkenyl or aryl hydrocarbon groups bonded to the phosphorus atom or together represent a divalent hydrocarbon radical bonded by each of the two valencies to the phosphorus atom, n represents the degree of polymerization and may be an integer of 3-1000 and Y represents a secondary or tertiary organic amine or phosphine. The phosphinoborine polymer may be made by pyrolyzing an adduct of diborane and a secondary phosphine in the presence of a secondary or tertiary amine or phosphine.  Alternatively a mixture of an adduct derived from diborane and a secondary phosphine together with a minor proportion of an adduct of a primary phosphine and diborane is pyrolyzed in the presence of a secondary or tertiary amine or phosphine to form a polymer comprising R1R11PBH2 structural units with units of the primary phosphinoborine interpolated between pairs of the said structural units which may give rise to branching or cross-linking. The pyrolysis is carried out at temperatures between 130 DEG C. and 250 DEG C. for between 10 and 60 hours.  Inert solvents may be used. Suitable reactants are the borane adducts of dimethylphosphine, methyl-ethylphosphine, diethylphosphine, methylallyl phosphine, methyl-n-propylphosphine, methyl-isopropylphosphine, cyclotetramethylphosphine, methyldodecylphosphine, methylphenylphosphine, and tetramethylbiphosphine with amines such as trimethylamine, triethylamine, tributylamine, piperidine, N-methyl-piperidine, pyridine or tetramethylguanidine and difunctional amines such as triethylenediamine, N,N,N1,N1-tetraethyl-ethylenediamine and N,N,N1,N1-tetramethyl ethylenediamine or with dimethylphosphine.  Methyl phosphine is a suitable primary phosphine.  Detailed examples are given.