DD296286A5 - METHOD FOR PRODUCING NITROGEN-BASED LUBRICATING OIL COMPOSITIONS - Google Patents

Abstract

The invention relates to a process for the preparation of nitrogen-containing lubricating oil additives which are used as corrosion inhibitors, dispersants dispersants and Viskositaetsindexverbesserer. In the process according to the invention, the epoxidized polymers are reacted with primary or secondary amines in substance or in polar solvents or solvent mixtures with polar components at a temperature of 50 to 200 ° C. {nitrogen-containing lubricant additives; epoxidized polymers; primary or secondary amines; Dissolvents mixtures}

Description

Field of application of the invention

The invention relates to a process for the preparation of nitrogen-containing polymers which are used as corrosion inhibitors, dispersant dispersant additives and viscosity index improvers.

Characteristic of the known state of the art

The preparation of nitrogen-containing polymers used as multifunctional lubricating oil additives is known. They are manufactured in two main ways:

a) by copolymerization of higher methacrylates with various nitrogen-containing monomers

b) by graft copolymerization of vinylpyridines or other nitrogen-containing monomers on ethylene / propylene copolymers, ethylene / propylene / diene terpolymers or diene copolymers.

Thus, EP 164.807 describes a multifunctional lubricating oil additive which comprises a base copolymer of C ₁ - and C 18 -alkyl methacrylates and various graftable nitrogenous monomers (N-vinylimidazole, N-vinylpyrrolidone, vinylpyridines, N, N-dialkylaminoethyl methacrylates). will be produced.

Similarly, the procedure is in USP 4,161,392. There are butyl methacrylate, C ₁₂ -2o alkyl methacrylates and dimethylaminoethyl methacrylate used.

Also in U.S.P. 4,183,732, SUP 783,337 and GBP 985,019 describe the preparation of such lubricating oil additives.

DE-OS 2,634,033 describes the grafting of 2-vinylpyridine onto ethylene / propylene / diene-co- or terpolymers or onto hydrogenated butadiene-styrene copolymers.

In EP 29622 2-vinylpyridine is grafted onto a divinylbenzene / polyisoprene copolymer.

Less commonly used are processes based on nitrogen functionalization of polybutadienes, as described in DE-OS 2,554,093. Here, polybutadienes prepared by means of Li-butyl were partially hydrogenated, epoxidized and then reacted with H-acid compounds.

All of these processes have the disadvantage that complex polymerization reactions must be carried out to prepare the desired target products.

Object of the invention

It is an object of the invention to find a process for the preparation of nitrogen-containing lubricating oil additives in which the nitrogen content of the reaction product can be varied within wide limits.

Explanation of the essence of the invention

The invention has for its object to develop a process for the preparation of nitrogen-containing lubricating oil additives.

According to the invention the object is achieved by a method in which the epoxidized polymers are reacted with primary or secondary amines in substance or in polar solvents or solvent mixtures with polar components at a temperature of 50 to 200 ⁰ C.

The epoxidized polybutadienes are used with an average molecular weight <10000 g / mol.

The amines used are open-chain or cyclic, branched and unbranched amines having 4 to 20 carbon atoms in pure form or as a mixture.

Solvents containing polar components are, for example, mixtures of halogenated hydrocarbons and alcohols, e.g. a mixture of chloroform and ethanol.

Polyolefins can ζ. Example, epoxidized polyisobutenes or polydienes of different molecular weight and structural composition, with one or more epoxide structures in the molecule, or partially hydrogenated polydienes, which are partially or completely epoxidized after the hydrogenation double bonds or reactive hydrocarbon resins whose olefinically unsaturated structural units are partially or completely epoxidized ,

As open-chain and cyclic, branched and unbranched amines having 4 to 20C atoms, for. For example, n-butylamine, diisobutylamine, dioctylamine, dodecylamine, n-hexadecylamine or benzylamine can be used in pure form or as a mixture. In comparison with the production of multifunctional lubricant additives from higher alkyl methacrylates or ethylene / propylene / diene copolymers and terpolymers and nitrogen-containing monomers, commercial products can be converted into the desired target products by relatively simple process steps in the process set forth here.

embodiments

1. In a glass vessel provided with a stirrer and reflux condenser, the solution of an epoxidized polybutadiene, which was epoxidized according to an "in situ" process with formic acid / hydrogen peroxide (EEG = 690 g / mol of oxygen), is reacted with the appropriate amount of diisobutylamine. The polybutadiene used has a molecular weight of 5600 g / mol and a structural composition of 36% 1,4- and 64% 1,2-structural units, of which only the 1,4-units are epoxidized The epoxidized polybutadiene is used in a concentration of 100 g / l are dissolved in a mixture of equal volumes of ethanol and chloroform and reacted with a twofold excess of amine with respect to the epoxide groups The reaction is refluxed until no further reaction can be detected by quantitative monitoring of the turnover by means of titration (approx 6 to 8 h) The solvent and excess amine are removed by means of a rotation thin-film evaporator. This gives a highly viscous amine-functionalized polybutadiene having a nitrogen content of 0.70%, which forms a stable solution as a 5% solution in a mineral oil (ZETRII).

2. Instead of the epoxidized polybutadiene in Example 1, a polybutadiene of the same microstructural composition but with a slightly higher epoxide group concentration is used (EAG = 630 g / mol of oxygen). The polybutadiene epoxide is dissolved in dioxane at a concentration of about 50 g / l and reacted with the equimolar amount of dioctylamine. After completion of the reaction, the solvent is removed on a rotary evaporator and washed unreacted dioctylamine with alcohol. This gives a nitrogen-containing polybutadiene having a nitrogen content of 1.10%.

3. Instead of the dioctylamine used in Example 2, octadecylamine is used as the amine component. In this way a product soluble in mineral oil (ZETRII) with a nitrogen content of 1.12% is obtained.

4. Instead of the low epoxidized polybutadiene in Example 1 is a polyisobutene, which was epoxidized by means of formic acid / hydrogen peroxide (EÄG = 2040g / mol of oxygen) is used. Using a two-fold excess of the epoxide groups on diisobutylamine gives a product with a nitrogen content of 0.82%.

5. Instead of the epoxidized polybutadiene in Example 3, an epoxidized polybutadiene (EAG = 730 g / mol of oxygen) having a molecular weight of 2000 g / mol and the following microstructural composition is used: 56% 1,4- and 44% 1,2-structural units. When dioctylamine is used as the amine component, a nitrogen-containing polybutadiene having a nitrogen content of 1.37% is obtained.

6. Instead of the epoxidized polybutadiene in Example 1, an epoxidized polybutadiene (EAG = 520 g / mol of oxygen) having a molecular weight of 1800 g / mol and the following microstructural composition is used: 99% 1 A and 1% 1,2-structural units. The amine component used is dodecylamine. To simplify the procedure described in Examples 1 to 5 is carried out without solvent at a temperature of 180 ⁰ C. The molar ratio epoxide groups / amine is 1: 2. After a reaction time of 10 h and subsequent separation of the unreacted amine by extraction with ethanol to obtain an oil-soluble reaction product having a nitrogen content of 1.63%.

7. Instead of the procedure in Example 6 is worked at 100 ⁰ C. A reaction product having a nitrogen content of 0.99% is obtained.

Claims (4)

1. A process for the preparation of nitrogen-containing lubricating oil additives, characterized in that epoxidized polymers reacted with primary or secondary amines in substance or in polar solvents or amines in substance or in polar solvents or solvent mixtures with polar components at a temperature of 50 to 200 ⁰ C. become. 2. The method according to claim 1, characterized in that are used as polymers polyolefins having at least one epoxidized structural unit. 3. The method according to claim 1, characterized in that epoxidized polybutadienes having an average molecular weight <10000g / mol are used. 4. The method according to claim 1, characterized in that are used as amines open-chain and cyclic, branched and unbranched amines having 4 to 20C atoms in pure form or as a mixture.