DE1191577B - Process for the preparation of organic polymers containing phosphorus and nitrogen - Google Patents

Description

Process for the production of phosphorus and nitrogen containing organic polymers The invention relates to the production of novel, Organic polymers containing phosphorus and nitrogen, which are excellent suitable as lubricating oils or as high-pressure additives for such oils and moreover improve the temperature-viscosity behavior of lubricating oils.

It is already known that lubricating oil additives suitable as cleaning agents, to prevent the formation of sludge and varnish in the engine by moving a olefin polymer obtained using Friedel-Crafts catalysts to produce with a phosphorus sulfide. In this way, both phosphorus and sulfur atoms are also incorporated into the molecular chain. The reaction product is then completely or partially neutralized, preferably with a metal-containing base, but an amine can also be used as a neutralizing agent. These polymers However, detergents do not act as extreme pressure additives in the Ulen concerned, and they also have the disadvantage of hydrolytic decomposition during the Use on. You can do it before using an accelerated hydrolysis at elevated temperature and subject the formed inorganic phosphates means remove a solid adsorbent, but only the phosphorus, but not the sulfur content is lowered, and besides, the detergents are through Such a treatment is also not converted into extreme pressure additives.

The process according to the invention for the production of phosphorus and nitrogen containing organic polymers by reacting olefin polymers first with Phosphorus compounds and then with amines is characterized in that one uses olefin polymers, which in a known manner in the presence of a Ziegler catalyst are made from olefins with 4 to 25 carbon atoms in the molecule, that the phosphorus compound is chlorine, bromine or iodine compounds of the trivalent Phosphorus used and that the treatment of the olefin polymers with the phosphorus compound in the presence of oxygen.

The halides of trivalent phosphorus to be used according to the invention are the following phosphorus compounds: phosphorus trichloride, phosphorus tribromide. Phosphorus triiodide, Phosphine dichloride. Methyl phosphorus dichloride (CH3PCI2). Ethyl phosphorus dichloride (C2H5PCI2) and phenylphosphorus dichloride (C (, HPCI2). In the case of the invention, preference is given to Process the use of those compounds containing only phosphorus and halogen atoms contain, especially the chlorides or bromides, especially the phosphorus trichloride.

The phosphorus compound is used in amounts of 5 to 100 parts by weight used per 100 parts by weight of the polymer.

The oxygen becomes during the addition of the phosphorus halide are blown through the olefin polymer.

The reaction between an olefin polymer, phosphorus trichloride and oxygen can be represented by the following equation: The oxygen or the molecular oxygen-containing gas is blown through the reaction mixture in a considerable excess over the theoretically required amount, for example 1 mol per mol of the phosphorus halide or more.

The olefin polymer is preferably inert in a reaction Solvent dissolved, for example in carbon disulfide, carbon tetrachloride, Chloroform, Benzene, chlorobenzene or acetyl chloride.

Carbon tetrachloride is preferred as the solvent.

The physical conditions under which the reaction takes place depend to a considerable extent on the reagents used. So is for example the phosphorus trichloride is relatively volatile (boiling point: 760 76 ° C) and the temperature must therefore be kept below 76 "C, unless the Reaction is carried out under elevated pressure or that a device for recovery the phosphorus trichloride vapors are present. However, the temperature is generally expediently in the range from about 0 to 75 "C, for example about 30 to 50" C, and the pressure is maintained at about atmospheric pressure. Then it is treated with an amine.

The amine with which the further reaction not claimed here takes place, can be any aliphatic or aromatic compound which has a - Contains NH2 or WNH group. For example, primary and secondary can be aliphatic and aromatic amines, aliphatic polyamines, which have more than one - NH2- or Contain NH groups, mono- and dialkanolamines and heterocyclic compounds with an - NH group in the ring.

In general, the secondary amines are preferred to the primary and the same the saturated compounds precede the unsaturated ones. Furthermore, amines with less than 30 carbon atoms in the molecule and those that are aliphatic in nature are preferred In general, the long chain branched alkylamines, e.g. B. those of the formula RR1R2CNH2 in which R, R1 and R2 are alkyl groups and the total number the carbon atoms range from 12 to 14 or 18 to 21 are preferred Amines. A particularly suitable amine is di (2-ethylhexyl) amine.

The amine can be added to the olefin polymer by a process not claimed here are added as such and then heated, or the olefin polymer becomes initially in benzene, toluene, xylene, chlorobenzene, isooctane, aliphatic normal gasoline, Carbon tetrachloride or chloroform dissolved. Toluene or carbon tetrachloride are preferred.

The polymer already reacts to a certain extent with the amine at room temperature However, higher temperatures are preferred, for example from 40 to 100 "C.

The polymeric phosphonamide obtained in this way can by the customary methods by fractional distillation, steam distillation or distilling under separated from the reaction mixture under reduced pressure. With such distillation methods the desired product remains as a residue. Optionally, you can also do that Pour reaction mixture into an organic solvent containing all reagents apart from the polymer dissolves, for example in acetone, methanol or tetrahydrofuran, whereby the desired product fails.

The phosphonamide polymers obtained by the process according to the invention when added to a lubricating oil, generally exhibit good extreme pressure properties; in addition, they can also improve the viscosity-temperature behavior of the lubricating oil.

The proportion of the phosphonamide polymer to be added to a lubricating oil is preferably 0.1 to 20 percent by weight, in particular 1 to 5 percent by weight.

The polymers prepared according to the invention can be mixed with mineral oils or synthetic oils with lubricating properties are mixed, for example Hydrocarbon oils from a paraffinic, naphthenic crude oil, mixed polymers of alkylene glycols and alkylene oxides, di- (2-ethylhexyl) sebacate, dinonyl sebazate, Dinonyl adipate, dioctyl phthalate and tricetyl phosphate. polymeric tetrahydrofuran and Dimethylpolysiloxanes.

Example I 5 parts by weight of a cracked wax olefin with 13 carbon atoms in the molecule after cleaning with urea not here The claimed process using Ziegler catalysts were obtained Dissolved carbon tetrachloride in 50 parts by volume. Phosphorus trichloride was added to this solution added slowly, with commercially available oxygen steadily flowing through the reaction vessel was blown through. The total amount of phosphorus trichloride added amounted to 1.5 parts by volume and the amount of oxygen blown through about 100,000 room parts.

During the addition of phosphorus trichloride and oxygen declined the temperature of the reaction mixture to rise, but was stopped by water cooling kept at about 40 C. After the addition of the phosphorus trichloride was complete, the mixture was set the bubbling of oxygen continued until all heat generation ceased.

The reaction mixture was then pumped into another vessel and heated to 100 ° C. under reduced pressure. around carbon tetrachloride, phosphorus trichloride and remove the oxidation products. The residue was a brown wax.

The phosphonyl chloride of the olefin polymer, d. H. the brown wax. was then dissolved in 10 parts by weight of hot benzene, di- (2-ethylhexyl) amine added in 100% excess and, when the reaction is complete after about 3 hours was, the mixture was evaporated to a small volume and in excess Poured acetone, whereby the desired polymer was precipitated.

Example II The procedure of Example 1 was repeated using the Ziegler polymer of (a) a cracked Cl3 wax olefin and (b) a cracked one Clo wax olefin.

The following amounts of carbon tetrachloride, olefin polymer and phosphorus trichloride were used: Olefin tetrachlorophosphorus polymensat i carbon tnchloride Parts by weight parts of space Parts of space (a) 10 100 3.0 (b) 10 100 4.0 When the phosphonamide polymers obtained in this way were dissolved in Cardon-65 mineral oil, the mixtures showed good maximum pressure properties and good viscosity-temperature behavior in both cases.

Example III Following the procedure of Example 1, a cracked "Ziegler polymer" obtained from C, 3-wax olefin treated with phosphorus trichloride, 12 parts by volume of phosphorus trichloride per 60 parts by weight of the olefin polymer. dissolved in 500 parts by volume carbon tetrachloride. came into use. then about 30 parts by volume of carbon tetrachloride removed by evaporation and 100 parts by volume Di - ('- ethylhexyl) amine added.

The mixture formed upon completion of the reaction was then under Evaporated under reduced pressure at 100 "C. until it was a viscous 51, and then poured into acetone as in Example 1. The polymer precipitated by acetone was soluble in toluene.

Example IV Using the same procedure as in the example 1 was made from a cracked C12 wax olefin by a process not claimed here "Ziegler polymer" obtained (60 parts by weight) in 500 parts by volume of carbon tetrachloride dissolved. whereupon by the solution with stirring according to the invention more commercially available Oxygen was passed.

According to the invention, 25 parts by volume of phosphorus trichloride were in small Subsets added. the reaction temperature by cooling to about 40 - C was held. Once the reaction was over, the carbon tetrachloride became and excess phosphorus trichloride from a small portion of the reaction mixture distilled off, being a Polymer remained which contained about 4.8 percent by weight of phosphorus contained.

The remainder of the reaction mixture was not claimed here Process for several hours under reflux with di (2-ethylhexyl) amine in the above Treated excess and then poured into acetone, with a precipitate formed.

Claims (3)

Claims: 1. Process for the production of phosphorus and nitrogen containing organic polymers by reacting olefin polymers first with Phosphorus compounds and then with amines, characterized in that one uses olefin polymers, which in a known manner in the presence of a Ziegler catalyst are made from olefins having 4 to 25 carbon atoms in the molecule. that the phosphorus compound used is chlorine, bromine or iodine compounds of trivalent phosphorus used and that the treatment of the olefin polymers with the phosphorus compound in the presence of oxygen. 2. The method according to claim 1, characterized in that 5 to 100 parts by weight of the phosphorus compound per 100 parts by weight of the olefin polymer used. 3. The method according to claim 1 and 2, characterized in that one the reaction between the olefin polymer and the phosphorus compound in the presence an inert solvent. References Considered: U.S. Patents No. 2,316 082.2 688 612.