MXPA97006775A - Copolymers of unsaturated dicarboxilic acids, or anhydrides of these and oligoolephines in vinyl, and the products of reaction of these nucleofili egents - Google Patents

Abstract

The present invention relates to copolymers I carrying functional groups and consisting of: from 30 to 70 mol% of at least one C4-C12 monoethylenically unsaturated dicarbixyl acid or the anhydride thereof, and from 30 to 70 mol% of at least one oligomer of a 1-olefin of 3 to 14 carbon atoms, at least 85% of which is present as an isomer having a terminal vinyl group of the formula -CH = CH2 and having an average molecular vinyl group from 300 to 10,000. The reaction products of the copolymers I with compounds containing NH, OH or SH functional groups are suitable as dispersants for detergent formulations and cleaning agents, water repellents for skins, flow improvers and paraffinic dispersants for unrefined oils and fractions of refined mineral oils and additives for lubricants and fuel

Description

COPOLYMERS OF UNSATURATED DICHARBOXYLIC ACIDS, OR ANHYDRIDES OF THESE AND OLIGOOLEPHINES FINISHED IN VINYL, AND THE PRODUCTS OF REACTION OF THESE WITH NUCLEOFILIC AGENTS The present invention relates to novel copolymers which carry functional groups and are obtained from unsaturated dicarboxylic acids or anhydrides thereof and vinyl-terminated oligoolefins, a process for the preparation of these copolymers and the reaction products thereof with nucleophilic agents. The present invention also relates to the various uses of these reaction products. The published German patent application P 43 30 971.2 (1) describes the terpolymers which contain functional groups and are obtained from. 20-60 mol% of C4-C6 monoethylenically unsaturated dicarboxylic acids and the anhydrides thereof, 10-70 mol% of propene oligomers and branched 1-olefins of 4 to 10 carbon atoms having an average molecular weight of 300 to 5000, and 1-50 mol% of monoethylenically unsaturated copolyzable compounds. The reaction products, soluble in oils, of these terpolymers with amines are suitable as fuel additives and lubricant additives. O-A 90/03359 (2) describes the polymers that can be used as additives in lubricating oils and in some cases have dispersing properties to form suspensions and solid particles contained therein. Some of these polymers are also viscosity index improvers, that is, they ensure that, when the temperature increases, the viscosity of the lubricating oil decreases to a substantially lesser degree than in a lubricating oil without this additive. The polymers described in (2) are compounds of maleic acid or fumaric acid or derivatives thereof and an olefin whose molecular weight is sufficiently high for the polymer prepared from these monomers to be soluble in oil, and are made react with amines. This olefin must carry at least 20% alkylvinylidene groups. The polymers described in the publication (2) do not have satisfactory properties for all applications, in particular the viscosity / temperature behavior of the lubricating oils, which contain these polymers as additives, is still unsatisfactory in many cases. In addition, the dispersing action of these compounds in industrial use is not satisfactory in all cases.

An object of the present invention is to provide lubricating oil additives that no longer have the disadvantages of the prior art. We have found that this objective is achieved with copolymers I that carry functional groups and consist of: (a) from 30 to 70 mol% of at least one dicarboxylic acid of monoethylenically unsaturated 1-C12 or the anhydride thereof, and (b) from 30 to 70 mol% of at least one oligomer of a 1-olefin of 3 to 14 carbon atoms, at least 85% of which is present as an isomer having a terminal vinyl group of the formula -CH = CH2 and having an average molecular weight from 300 to 10,000. The novel copolymers I contain no more comonomers than (a) and (b). The novel copolymers I are used as intermediates for the preparation of a very wide range of industrial compositions which have, in some cases, outstanding performance characteristics, as described below. Preferred monomers (a) are monoethylenically unsaturated C4-C6 dicarboxylic acids or the anhydrides thereof, for example, maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride and methylenemalonic anhydride and mixtures thereof with each other. Maleic anhydride is preferred. Suitable monomers (b) are oligomers of propene or a linear 1-olefin of 4 to 14 carbon atoms. These oligomers are, as a general rule, composed of at least three olefinic molecules. They contain at least 85%, in particular at least 90%, of the vinyl-terminated isomers. The vinyl-terminated oligo-olefins are more reactive than the corresponding vinylidene-terminated macromers. Therefore, during free radical copolymerization it is possible to achieve high degrees of polymerization and consequently higher molecular weights, which have an advantageous effect on the performance characteristics of the final products. Their average molecular weight is from 300 to 10,000, in particular from 500 to 5000. Examples are oligomers of propene, n-butene, n-pentene, n-hexene and n-decene, at least 85% of the terminal groups copolymerizable oligomers are present in the form of a vinyl group. Oligopropenes and mixtures of oligopropenes from 9 to 400, in particular from 12 to 300, carbon atoms are preferred. These vinyl-terminated oligo-olefins can be obtained, for example, according to EP-A 268 214 (example 2), by means of a metallocene catalyst of the bis-pentamethylcyclopentadienylzirconium dichloride type. the copolymers I contain the monomers (a) in amounts from 30 to 70, preferably from 40 to 60 mol% and the monomers (b) in amounts from 30 to 70, preferably from 40 to 60 mol%. Particularly preferred are copolymers I. which carry functional groups and in which component (a) is maleic anhydride and component (b) is an oligopropene or a mixture of oligopropene, each of from 9 to 400 carbon atoms. The present invention also relates to a process for the preparation of the copolymers I carrying functional groups, which comprises subjecting: (a) from 30 to 70 mol% of at least one C4-C12 monoethylenically unsaturated dicarboxylic acid or the anhydride thereof for the free radical polymerization with (b) from 30 to 70 mol% of at least one oligomer of a 1-olefin of 3 to 14 carbon atoms, at least 85% of which is present as an isomer which has a terminal vinyl group of the formula -CH = CH2 and which has an average molecular weight from 300 to 10,000. The copolymers I can be prepared by all known conventional polymerization methods, for example, by mass polymerization, emulsion, suspension, precipitation and solution. All the polymerization processes mentioned are generally carried out in the absence of oxygen, preferably in a stream of nitrogen. Conventional appliances, such as autoclaves and kettles, are used for all polymerization methods. The bulk polymerization of monomers (a) and (b) is particularly preferred. It can be carried out from 60 to 300 ° C, preferably from 80 to 200 ° C, the lowest polymerization temperature that can be chosen preferably will be around 20 ° C above the glass transition temperature of the polymer formed. The polymerization conditions are chosen according to the desired molecular weight of the copolymers. High temperature polymerizations generally result in copolymers having lower molecular weights, while polymers having higher molecular weights are usually formed at lower polymerization temperatures. The copolymerization is preferably carried out in the presence of compounds that form free radicals. Of these compounds, up to 10, preferably 0.2 to 5% by weight, based on the monomers used, are required for copolymerization. Examples of suitable polymerization initiators are peroxide compounds, such as tert-butyl perpivalate, tert-butyl per-decanoate, tert-butyl-perethylhexanoate, tert-butyl perisobutylate, di-tert-butyl peroxide, di-tert-amyl peroxide, diacetyl peroxodicarbonate and di-cyclohexyl peroxodicarbonate, and the azo compounds, for example, 2,2'-azobisisobutyronitrile. These initiators can be used alone or as a mixture if yes. During bulk polymerization, they are preferably introduced separately or in the form of a solution in the polymerization reactor. The monomers (a) and (b) can be copolymerized at 200 ° C also in the absence of polymerization initiators. In order to prepare the low molecular weight polymers, it is usually advantageous to perform the copolymerization in the presence of regulators. Conventional regulators, such as C1-C4 aldehydes, formic acid or compounds containing organic SH, such as 2-mechaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butyl mercaptan, n-octylmercaptan, n-dodecyl mercaptan or Ter-dodecyl mercaptan can be used for this purpose. Polymerization regulators are usually used in amounts from 0.1 to 10% by weight based on the monomers. In order to prepare the higher molecular weight copolymers, it is usually advantageous to carry out the polymerization in the presence of chain extenders. These chain extenders are compounds that have diethylenically or polyethylenically unsaturated groups, such as divinylbenzene, pentratritrilyl triallyl ether or esters of glycols, such as glycol diacrylate, glyceryl triacrylate or polyethylene glycol diacrylates. These can be added in the polymerization in amounts of up to 5% by weight. The copolymerization can be carried out continuously or in the form of batches. The molecular weight of the copolymers I are, as a general rule, from 1000 to 100,000, in particular from 5,000 to 50,000. The copolymers I can be reacted with nucleophilic agents, that is, with compounds containing the NH, OH or SH functional groups, and can thus be derivatives for the various fields of use. Accordingly, the present invention also relates to these reaction products II. In this way, the reaction of the copolymers I with an aqueous alkali metal or alkaline earth metal hydroxide, for example, with aqueous potassium or sodium hydroxide solution, gives stable aqueous dispersions (reaction products lia) which are suitable as dispersants for detergent formulations and cleaning agents and as water repellents for the skin. The present invention also relates to detergent formulations and aqueous cleaning agents containing the reaction products as dispersants in conventional amounts. The reaction of the copolymers I with saturated or unsaturated aliphatic alcohols of 8 to 30, in particular of 10 to 22 carbon atoms, ie fatty alcohols, such as stearyl alcohol or behenyl alcohol, give rise to the reaction products Ilb soluble in oil, which are suitable as flow improvers and paraffinic dispersants for impure oils and refined mineral oil fractions. The present invention also relates to impure oils and refined mineral oil fractions containing oil-soluble reaction products IIb as flow improvers and paraffinic dispersants in conventional amounts. The reaction of the copolymers I with primary, secondary or tertiary mono- or polyamines or mixtures thereof carrying at least one C6-C0 alkyl radical, in particular C3-C22 alkyl or alkenyl, ie fatty amines, as tridecylamine, give reaction products that are suitable as corrosion inhibitors for metal substrates. The reaction of the copolymers I with amines of the formula NHR: R2, wherein R1 and R2 may be identical or different and each may be hydrogen, an aliphatic or aromatic hydrocarbon radical, a primary or secondary aminoalkylene radical, aromatic or aliphatic, a polyaminoalkylene radical, a hydroxyalkylene radical or polyoxyalkylene radical, which may bear terminal amino groups, or may each be a heteroaryl or heteroaryl radical, which may bear terminal amino groups, or, together with the nitrogen atom to which they are attached , forming a ring in which heteroatoms may also be present, give the reaction products lid which are suitable as additives for the lubricants and fuels. Examples of the appropriate HNRXR2 amino components are: ammonia; - aliphatic and aromatic, primary and secondary amines of 1 to 50 carbon atoms, such as methylamine, ethylane, propylamine, di-n-butylamine or cyclohexylamine; amines in which R1 and R2 together with the nitrogen atom to which they are attached, form a common ring which may also contain other heteroatoms, such as morpholines, pyridine, piperidine, pyrrole, pyrimidine, pyrroline, pyrrolidine, pyrazine or pyridazine; amines bearing hydroxyalkylene and polyoxyalkylene radicals in which R1 and / or R2 are a radical wherein R3 is a C2-C2 alkylene and m is an integer from 1 to 30, such as ethanolamine, 2-aminopropan-l-ol or neopentanolamine; polyoxyalkyleneamines bearing terminal amino groups and in which R1 and / or R2 are a radical.

R4- s _L_ R3 or -J- R5 NR6R7 IV wherein R3, R4, and R5 are each C2-C6 alkylene, or m has the above-mentioned meanings and R6 and R7 each are hydrogen, Ci-Cio alkyl or C6-C? aryl substituted in the hydroxyl or amino group, or unsubstituted, such as polyoxypropylenediamines or bis (3-aminopropyl) tetrahydrofurans. However, the preferred amino components are the polyamines in which R1 and / or R2 are a radical of the formula V.

R "wherein R3, R6 and R7 have the meanings mentioned above and n is an integer from 1 to 6. Particularly suitable polyamines are ethylenediamines, propylene diamines, dimethylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, ethylaminoethylamine, dimethylaminoethylamine, isopropylaminopropylamine, ethylenedipropylenetetramine, 2-diisopropylethethylamine, aminoethylethanolamine, ethylenepropylenetriamine, N, N, N ', N' -tetra (3-aminopropyl) ethylenediamine, 2- (3-aminopropyl) cyclohexylamine, 2,5-dimethylhexan-2,5-diamine and N, N, N ', N ", N" -penta- (3-aminopropyl) dipropylenetriamine. Other preferred polyamines are those which contain a heterocyclic structure as a structural component, for example aminoethylpiperazine.

As the amine component it is also possible to use mixtures of different amines. The novel reaction products are obtained in a manner known per se, by reacting the copolymers I with the mentioned amines. The molar ratio of the components depends on the number of acid or anhydride groups in the copolymer I. This can be determined in a known manner, for example, by titration with a strong base. In general, 0.1 to 3 equivalents of the acid or anhydride groups in the polymer are used per mole of amine. For the reaction, as a general rule, the initmater are mixed and heated from 30 to 200 ° C. The reaction of preference is carried out under an inert gas atmosphere. The reaction can be carried out in the presence or absence of solvents. Examples of inert solvents are aliphatic and aromatic hydrocarbons, such as toluene and xylene, as well as mineral oils. The progress of the reaction can be monitored by IR spectroscopy. The present application also relates to lubricants and fuels containing lid reaction products soluble in oil, in the amounts mentioned below. Lubricants are synthetic, semi-synthetic and mineral oils that contain additive, preferably those that are used as motor oils. Synthetic oils comprise the esters and synthetic polymers of the α-olefins. The reaction products lid are added to the lubricants in general as a concentrate in an inert solvent, such as in a mineral oil. These concentrates may also contain conventional additives such as corrosion inhibitors, antiabration agents, detergents, antioxidants and pour point improvers. The reaction products lid are added to the lubricants in amounts from 1 to 15, preferably from 0.5 to 10% by weight. In fuels, such as gasoline or diesel fuel, the lid reaction products are used as detergents to keep the intake system clean. Due to their dispersing properties, they also have an advantageous effect on engine lubricants, which can enter during engine operation. For this purpose, 20 to 5000 ppm, preferably 50 to 1000 ppm, are added based on the fuel. The novel oil-soluble reaction products IIb generally have excellent viscosity / temperature behavior in almost all lubricants. They also present an excellent dispersing effect in almost all cases. The superior performance characteristics of the reaction products lid are illustrated in the following examples.

Example 1. Preparation of the vinyl-terminated oligopropenes (b) General preparation method: 30 ml of a 1.5 molar solution of methylalumoxane in toluene was initially introduced into a 2 L autoclave with stirring, and 900 ml (13.3 mol) of a liquid propene was condensed and heated to the temperature set in Table 1. The resulting pressure was 20 bar. After this, 64.3 mg (0.17 mmol) of bis-pentamethylcyclopentadienylzirconium dichloride were added and dissolved in 7 ml of a 1.5 molar solution of methylalumoxane in toluene, and the oligomerization was carried out for the time set forth in Table 1. The aluminum / zirconium atomic ratio was 250: 1. A yield of 590 ml of the oligomer mixture was obtained. The average molecular weights were determined by means of gel permeation chromatography and using the polystyrene standards having a narrow molecular weight distribution.

Table 1: data of the oligopropenes (b) used 2. Preparation of copolymers I Example 2.1 200 g of the oligomer bl were heated to -100 ° C in a slight stream of nitrogen in a reactor, and 32.7 g of maleic anhydride (in liquid form as a melt around 75 ° C) was administered for 4 hours. At the same time, a solution of 3.5 g of perbutyl peroctanoate, dissolved in 10 g of toluene, was administered for 4 hours. After this, the mixture was heated to 150 ° C and a solution of 2.3 g of di-tert-butyl peroxide of 10 g of toluene was dosed for one hour and, after the end of the reaction, the polymerization continued for another half an hour at this temperature. The copolymer thus obtained had a molecular weight of 12,000.

Example 2.2 95 g of oligomer b2 were heated to 250 ° C in a slight stream of nitrogen in a reactor and 10.3 g of maleic anhydride (in liquid form as a melt at about 75 ° C) was administered for 4 hours. At the same time, a solution of 2.1 g of di-tert-butyl peroxide dissolved in 5 g of toluene was administered for 4.5 hours. The polymerization then continued for another hour at this temperature. The copolymer thus obtained had a molecular weight of 48,000.

Example 2.3 201.5 g of oligomer b3 were heated to 150 ° C in a slight stream of nitrogen in a reactor, and 7.3 g of maleic anhydride (in liquid form as a melt around 75 ° C) was administered for 4 hours. At the same time, a solution of 3.1 g of di-tert-butyl peroxide. dissolved in lOg of toluene was administered for 4.5 hours. The polymerization then continued for another hour at this temperature. The copolymer thus obtained had a molecular weight of 15,600. The molecular weights of the copolymers of Examples 2.1, 2.2 and 2.3 were determined with the aid of high pressure gel permeation chromatography. The eluent that was used was tretrahydrofuran. The calibration was carried out with polystyrene fractions having a narrow molecular weight distribution. 3. Preparation of oil-soluble lid reaction products Method of "general preparation: A copolymer according to Examples 2.1 and 2.3 in xylene was initially taken at 70 ° C, an amine or polyamine was added and reflux was carried out until that the expected amount of water was separated from the reaction.After removing the solvent, the product was obtained in the form of a viscous residue of pale yellow to amber.The absorption bands in the IR of the products was around 1770 and around 1700 cm "1. The reactions were carried out as shown in Table 2 below: Table 2 Polymer Example of amino component Molar ratio according to anhydride / amine Example 4. Preparation of the comparative products Comparative additive VI Reaction product of the copolymer according to Example 6 of WO-A 90/03359 (2) and triethylene tetramine.

The aforementioned starting materials were reacted in the same manner as in the above for Examples 3, in a 1: 1 molar reaction. Comparative Example V2 Reaction product of the copolymer according to Example 6 of (2) and triethylenetetramine. The aforementioned starting materials were reacted in the same manner as in the previous Examples 3, in a molar ratio of 2: 1. 5. Verification of the viscosity / temperature behavior the additives were tested in a concentration of 6% by weight in a motor oil 5W-30. The results are listed in Table 3. Table 3 The novel additives (3.1, 3.2, 3.5, 3.8 and 3.9) are obviously superior to those of the prior art (VI and V2) due to their greater viscosity improving effect at high temperatures. The viscosity at low temperature of the oils to which the additives according to the invention were added is in the range of the prior art. 6. Test of the dispersing effect The dispersing effect was verified by means of a spot test as described in Les Huiles pour Moteurs et la Graissage des Moteurs, A. Schilling, Vol. 1, page 89 et seq., 1962. For this purpose they prepared 3% mixes by weight of the additives in a diesel fuel. The dispersions thus obtained were developed on a filter paper in the same way as a chromatogram. The evaluation scale was extended from 0 to 1000: the higher the value obtained, the better the dispersant effect of the additive. The results are listed in Table 4. Table 4 TA = room temperature The novel additives (3.2, 3.5, 3.8, and 3.9) have significantly better dispersant effect than the additives of the prior art (VI and V2) in almost all cases.

Claims (17)

1. CLAIMS.
2. A copolymer I carrying functional groups and consisting of (a) from 30 to 70 mol% of at least one C4-C? 2 monoethylenically unsaturated dicarboxylic acid or the anhydride thereof; (b) from 30 to 70 mol% of at least one oligomer of a 1- olefin of 3 to 14 carbon atoms, at least 85% of which is present as an isomer having a terminal vinyl group of the formula CH = CH2 and having an average molecular weight from 300 to 10,000; and is composed of at least 3 olefin molecules. .
3. The copolymer I carrying functional groups, according to claim 1, in which the component (a) is maleic anhydride and the component (b) is an oligopropene or a mixture of oligopropene, each of 9 to 400 carbon atoms . .
4. A process for the preparation of a polymer I carrying functional groups, according to claim 1 or 2, which comprises subjecting: (a) from 30 to 70 mol% of at least one monoethylenically unsaturated CC? 2 dicarboxylic acid or the anhydride thereof, to the polymerization by free radicals with (b) from 30 to 70 mol% of at least one oligomer of a 1- olefin of 3 to 14 carbon atoms, at least 85% of which is present as an isomer having a terminal vinyl group of the formula CH = CH2 and having an average molecular weight from 300 to 10,000 and is composed of at least 3 olefinic molecules.
5. The reaction product II of a copolymer I, according to claim 1 or 2, with the compounds containing NH, OH or SH functional groups.
6. A reaction product of a copolymer I, according to claim 1 or 2, with an alkali metal or alkaline earth metal, aqueous hydroxide.
7. The use of a bundled reaction product, according to claim 5, in the form of an aqueous dispersion as a dispersant for detergent and cleaning agent formulations.
8. An aqueous detergent or cleaning agent formulation containing a reaction product, according to claim 5, as a dispersant in a conventional amount.
9. The use of a reaction product Ia, according to claim 5, in the form of an aqueous dispersant as a water repellent for skins.
10. The water-soluble reaction product Ilb of a copolymer I, according to claim 1 or 2, with a saturated or unsaturated aliphatic alcohol of 8 to 30 carbon atoms.
11. The use of an oil-soluble reaction product IIb, according to claim 9, as a flow improver or paraffinic dispersant for impure oils and fractions of refined mineral oils.
12. An impure oil or a fraction of refined mineral oil containing a water-soluble reaction product IIb, according to claim 9, as a flow improver or paraffinic dispersant in a conventional amount.
13. A reaction product of a copolymer I, according to claim 1 or 2, with a primary, secondary or tertiary mono- or polyamine carrying at least one C4-C3o alkyl radical or alkylene of the use of a product of the reaction, according to claim 12, as a corrosion inhibitor for metal substrates.
14. An oil-soluble reaction product of a copolymer I, according to claim 1 or 2. with an amine of the formula HNR ^ 2, wherein R1 and R2 may be identical or different and each may be hydrogen, aliphatic or aromatic hydrocarbon radical, a primary or secondary aminoalkylene radical, aromatic or aliphatic, a polyaminoalkylene radical, a hydroxyalkylene radical or polyoxyalkylene radical, which can carry terminal amino groups, or can each be a heteroaryl or heteroaryl radical which can carry terminal amino groups, or, together with the nitrogen atom to which they are attached, form a ring in which heteroatoms may also be present.
15. 15. The use of an oil soluble reaction product according to claim 14, as an additive for lubricants and fuels.
16. 16. A lubricant containing from 1 to 15% by weight of an oil-soluble lid reaction product according to claim 14.
17. 17. A fuel containing from 20 to 5000 ppm of an oil-soluble lid reaction product. according to claim 14.