Patent GB-1089697-A (GB)
Title: Process for production of reinforced polyamide compositions
IPC: C08G69/18
Filed: 1964-11-27
Abstract: In a process for preparing a reinforced polyamide composition the anionic polymerization of a lactam is carried out in the presence of a filler or reinforcing agent in the surface of which the number of hydroxyl groups has been reduced by either (a) the use of sufficient anionic polymerization catalyst to react with the hydroxyl groups and to catalyse the polymerization, (b) the use of sufficient initiator to react with the hydroxyl groups and to initiate the polymerization or (c) the addition to a slurry of anhydrous lactam and filler or reinforcing agent of a compound of formula <FORM:1089697/C3/1> where L is H, alkyl or alkoxy, having up to 6 carbon atoms, M is an element other than an inert gas, Si, C, a halogen, N or O, R is a hydrocarbon group, d is an integer and e and f are zero or integers.  The lactam may be of formula <FORM:1089697/C3/2> where R is a C2- 11 alkylene radical.  Lactams specified include epsilon-caprolactam.  The reinforcing agent may contain 50% or more of a silaceous mineral having a 3-dimensional crystal structure, a m.p. above 800 DEG  C., a Moh hardness of at least 4 and a water solubility of less than 0.1 g./l., e.g. felspar, mullite and wollastonite. However, other fillers and reinforcing agents are specified including cellulose fibres, glass and metal fibres, non-silaceous minerals, metal oxides and salts. The particles size of the filler or reinforcing agent may be 200 mm -1 inch. 1-90% of reinforcing agent or 40-65% of filler may be used.  The catalyst may be a metal, metal complex or metal compound which forms a Lewis acid of sufficient strength to form a lactam salt.  Catalysts specified include NaH and EtMgBr/Et2O.  0.01-20% may be used.  Initiators specified are aromatic polyisocyanates, e.g. toluene diisocyanate, N-acyl lactams and many other nitrogenous compounds. If the initiator is an isocyanate a polyurethane catalyst may be added.  This may be a Lewis base free from active hydrogen atoms.  Polyurethane catalysts specified include triethylene diamine, bismuth nitrate, lead oleate, sodium propionate, butyl tin trichloride, stannic chloride, stannous ocotate, ferric chloride, antimony trichloride N-ethyl ethyleneimine and triphenyl aluminium. 0.1-5% initiator may be used in conjunction with 0.1-10 times as much polyurethane catalyst. The polyurethane catalyst, filler, and isocyanate should be allowed to react before the polymerization catalyst is added. Compounds of type (c) specified include tetraethyl orthosilicate, aluminium ethoxide, magnesium hydride dimethyl sulphate, and zinc diethyl 0.01-2% may be added, the treatment being effected either before or during polymerization.  The polymerization may be carried out in the presence of a coupling agent which also reacts with the surface hydroxyl groups.  The coupling agent may be of formula (i) <FORM:1089697/C3/3> where X=a group which will react with an inorganic compound, Y=an inert group, R=a C2- 20 alkylene or alkenylene group, Z=a group capable of being incorporated into the polymer chain, a and c=1-3, b=0-2, and a+b+c=4; (ii) <FORM:1089697/C3/4> in which R1=a group which will react with an inorganic compound, R11=a polymer reactive group and R111=an inert group or a group R1 or R11 or (iii) Werner complexes.  Coupling agents specified include 3-aminopropyl triethoxysilane. The coupling agent and filler or reinforcing agent may be mixed together in the presence or absence of a solvent, e.g. water, alcohol, benzene, dioxan or a molten lactam and the mixture dried.  This treatment may be followed by removal of the remaining surface OH groups by one of the other methods. Alternatively the molten lactam, coupler, filler or reinforcing agent, dispersing agent, initiator and catalyst may all be mixed at once.  In the examples a nitrogen atmosphere is used.