CS210037B1 - Working composition on the oil base usable for the aluminium cold rolling - Google Patents

Description

The present invention relates to a new oil-based machining composite suitable for cold rolling aluminum. The co-operation according to the invention is considerably more advantageous in the cold rolling of aluminum than is known in the art.

In cold aluminum rolling composites, paraffinic mineral oils of lower viscosity are generally used as oil [Tarnovsszij, IJ: Cstmaja Meeallurgija 13 (11), 95-98 (1970); Shey, JA: The Journal of the Institutes of Metals 1-7 / 1960 //. In some liquids, it is proposed to add esters, alcohols, acids or mineral oils containing fat to mineral oils as reducing components, which produce a uniform shine on the surface of the rolled strip [ _> GumineSc, RD: The Journal of the Institute of Meeals, ^297-3 ° ^3/19 61 ^{1 /.} In ^US-P tentovém · s ise no. 3,340,194 proposes as an additive atactic polypropylene, polybutylene or an atactic. However, the cold-rolling quality of the aluminum has not yet been eliminated by any additive containing or emulsifying oil.

The invention aims to eliminate the drawbacks of the prior art compositions.

It has now been found that can be obtained by machining koi ^ OICE that when aluminum cold rolling mills with íisStStž prevents staining when the odparafénoannému oily raHnátu ov ^ goat ^ 2 ~ ³ O RNM ^m / ^s / 20 ° E / / 2 -30.10 ^-0 m ² / ^s at 20 ° C ^, with a range of 200-350 ° C, preferably

220-340 ° C / Hungarian standard MSz 117377, flash point! over 100 ° C, suitably 100 to 125 ° C / Hungarian standard MSz 1 1 743 3, with a solidification temperature below 0 ° C, suitably between -3 and -7 ° C (Hungarian standard MSz 11121), with sulfur content below 0.1 wt. Z, suitably 0.03-0.00 wt.% (Hungarian norpa MSz 1 1773), having an acid number below 0.1 mg K00 / g, suitably 0.02 to 0.05 mg KOH / g / Hungarian standard MSz 117223, an iodine value of less than 10 g J / 100 g, suitably 5-8 g J / 100 g / m and the standard MSz 19974 / (hereinafter: base oil) in addition to those known in the art; 10 wt.%, Preferably 2-5 wt. From a mixture of four components containing:

and / 10-75 Uooo. Suitably 30-50 wt. Of other alcohols having 9 to 19 carbon atoms or simulations of these alcohols, preferably 20 to 20% by weight, preferably 30 to 20% by weight of an ester formed by an aliphatic carboxylic acid having 1-0 carbon atoms and one or more allyl alcohols having 9-19 carbon atoms, c / · 0.1-5.0 pot. Suitably 0.2-1.5%, percent of a straight chain carboxylic acid having 8-20 carbon atoms, saturated or unsaturated, d / 1-30 µm. Preferably, 1-10 wt. From the aminomakanol ester of formula I or the aminoalkanol ester of formula II,

R ₂ "N / CH ₂ / _x '' or ₁

3/1 / R ₂ -N + - / CH ₂ / _x -OH.OR7 i

R _3/11 / wherein x is an integer between 1 and 5, R] represents a group of formula / 0 - / ^ СН2 / _{у -СНз}

-SO 2 -O- (CH 2) _y -CH 3 or -PO ₂ o- (ch ₂ ) _z -ch ₃ in which the values of yu * independently of one another are 4-20, preferably 8-18, ^r 2 denotes hydrogen, hydroxyalkyl a group having 1-5, in particular 2 or 3 carbon atoms, or a group - (CH2) x0Est in which the value for x is an integer between 1 and 5, preferably 2 or 3, and Est is an ester-forming group derived from a saturated or unsaturated straight chain carboxylic acids having 1-20, preferably 10-18 carbon atoms,

R 3 represents a group of the formula - / CH 22 χ0Εβt, which corresponds to the group - / Н N 2 / xOEst named as ^R 2.

The reduction capacity of the composite according to the invention was measured on aluminum sheets having a degree of purity of 99.5 (AlMg3 alloy) on a roller mill at a belt speed of 10 m / mio and exceeded the reduction capacity of known components. In addition, the rolling oils have a considerable abrasion-reducing effect and an ET effect (extreme pressure effect) and are therefore perfectly suitable for aluminum processing.

The composition according to the invention contains 80-96 wt% suitably 88-96 wt. % of the base oil, and further in an amount of 0.5-15 wt. % of at least one adhesion promoter known per se. Possible adhesion-promoting polymers are, for example, polyphenols (for example polyisobuylene) having a molecular weight of 800-50,000, polyacrylic or polymethacrylic esters (for example polyaceyl methacrylate) or other polymers. To improve the adhesion to the metal, or to wet the metal of the carboxylic acid with 8-20 carbon atoms.

The individual components of the add-on material system according to the invention, consisting of four components, namely aliphatic alcohols having 9 and 19 carbon atoms and their esters formed with carboxylic acids having 1 to 6 carbon atoms, have also been used unanimously as additive to comipaic-based oils suitable for aluminum processing. However, the aminoalcohol sulfate ethers or the aninoo-ahohophosphate esters of the formula I and the salts of the formula II contained in the copolymers according to the invention are novel compounds. They can be prepared in such a way that in both cases, as a first step, a compound of the general formula (III), ^{R 2 '} N 5 ^R 6 (III) where R 2 is as previously defined and R 5 and R 8 reacted with an equimolar amount or twice the equimolar amount of a saturated or unsaturated carboxylic acid having a? / m chain of 1-20, suitably 10-18 carbon atoms, or more preferably of such carboxylic acids in an aromatic solvent at 75 ° and 160 ° C 6-8 tadine, whereby the rising water is removed and azeatrapi is removed. distillation.

The compound of formula (IV) thus obtained,

R2R3NR7 / IV / wherein R2 and R3 have the previously-stated meaning and R 7 represents Oydraxyalkylovou group having ^{1-5, and} that ^{we in} hlí.ku vzorw group or ^- / ^{/ H} 2 ^/ Est ^xO for the manufacture of compounds of formula I left at 140-200 ° C for 4-6 hours to react with a compound suitable for introducing the R 1 group, leaving the water formed and filtered by azeotrapation and then the solvents and vacuum are removed.

The compounds of formula (II) are to be prepared, the compound of formula (IV) is freed from the solvent under vacuum and then reacted at 60-80 ° C with a compound suitable for the introduction of the R 1 group for one hour.

To prepare the smp8 compounds, an alcohol having 1-19 carbon atoms or a mixture of such alcohols is first prepared, followed by the addition of solvents and finally, with stirring, a carboxylic acid having 1-6 carbon atoms. A compound suitable for introducing the R1 group is then added . The reaction mixture is boiled at 100-180 ° C for 6-10 ° C and water formed as an intermediate product is removed by azeatropic distillation. Finally, the crude product is freed from the desiccant under vacuum. In this way, it is possible to obtain a mixture of compounds having a tubular composition.

Phosphate salts which have already been used in rolling oils since the structure of the phosphate esters of the formula I have already been used. However, the practice of the invention and the comparative data presented below show that the aromatic aliphatic alcohols having from 9 to 19 carbon atoms, or their esters with aliphatic fatty acids with 1 to 6 carbon atoms, or the alcohol-abundant complication, may also be present. or the carboxylic acid esters, also known phosphate esters are not suitable for removing stains in the cold rolling of aluminum. The beneficial effect of the compositions of the invention (no staining) is likely due to the synergistic effect produced between the individual components.

Pure compounds may also be used as aliphatic alcohols having 9-19 carbon atoms in the copolymers of the invention, but preferably mixtures of alcohols are used.

Among the esters of aliphatic alcohols having 9-19 carbon atoms with alpha-1-6 carbon acids, acetic acid esters have proved to be particularly suitable. Such esters are advantageously Gone ^o djSv: Al in the form of their smiěs.

Highly preferred representatives of the compounds of formulas (I) and (II) are the esters derivable from diethanol apii and tritanilal. When in these compounds the groups ^R 2 and R 3 both denote - (CH 2) x O Ess, one Olive of the Est group may be the same or different.

In the manufacture of the compositions of the invention, the ingredients of the additive, i.e. a 9-19 carbon aliphatic alcohol (or a mixture of alcohols), an ester of an aliphatic alcohol of 9-19 carbon atoms, and an aliphatic carboxylic acid of 1- The carboxylic acid having 8 to 20 carbon atoms as well as the compounds of the formulas I or II add separately (separately) to the basic adhesion promoter and to the polymer. However, it is also possible to prepare the additive mixture from the ingredients of the additive ^{to be} mixed. It is highly preferred that the additive is an admixture formed by an α-oopo reaction by a process which contains one component in advance in the desired denial.

The complications of the invention are explained in more detail in the examples below. Examples to illustrate protection of the invention ο ^ ιη ^^^

Example *

By mixing the individual components, the following composition is prepared:

hmpd. Base oil; oitCaziak ^at 20 ° ^{C 3.8} . ^{10 θ} p ^{2 /} sec; Force ¹ and the ^No. of ^s ranges from 230 to 310 ° C; mp 110 ° C;

freezing point: -3 ° C; sulfur content 0.07 wt. OF; acid number: 0.07 mg KOH / g; iodo-bromo Number 8,4 g J / 100 g,

1.6 wt.%, Of polyisobutylene, molecular weight 5,000 wt. From a mixture of aliphatic n-alcohols with 10-18 carbon atoms,

1.5 wt. From a mixture of aliphatic n-alcohols with 10-18 carbon atoms esterified with acetic acid,

0.5 wt. From a compound of formula I in which x - 2, R 1 = -SO ₂ O- / CH ₂ /12- ^CK 3 R ₂ = R 3 = - / СН2 / 2ОСО / СН2 / Ю-СН3

0.4 wt. From stearic acid.

Example 2

By mixing the individual components, a composition of the following composition is prepared;

wt. Base oil; viscosity at 20 ° C 4.72. 10 6 6 nk / s; distillation range 246-327 ° C; flash point 125 ° C; pour point - 7 ° C; sulfur content 0.04 wt.%; iodo-bromo number 7.2 g J / 100 g; acid number 0.02 mg KOH / g, wt. From 1 to 10 µm, the molecular weight is 10,000. From a mixture of aliphatic n-alcohols with 12-14 carbon atoms, wt. From a mixture of esters of aliphatic n-alcohols having 12-14 carbon atoms and propionic acid, wt. Of the compounds of formula I, where x = 2, k ₂ = H, R 3 = - / CH _2/2 ~ ^OCO '/ ^{C' H-1} 1.2 СН3 and / О- / СН2 / 8-СНЗ

Ri - PO \

O- (CH2) 3-CH3 wt. From dodecylic acid.

Example 3

The following ingredients were mixed together:

wt. Base oil; viscosity at 20 ° C 6.1. 10 ^- 6 m ² / s; distillation range 240-335 ° C; flash point 130 ° C; pour point -10 ° C, sulfur content 0.08 wt. OF; an acid number of 0.05 mg KOH / g; iodo-bromo number 9.01 g J / 100 g, wt. Of polyalkyl methacrylate, molecular weight 50,000 wt. From a product mixture made from 1 mole of a mixture of C 10-19 alcohols, 0.04 mole of phosphoric acid, 0.5 mole of acetic acid and 0.1 mole of diethanolarninoleic acid ester in a three-step reaction; this product mixture contains the individual components in the following ratio: 45 wt. From a mixture of aliphatic alcohols with 10-19 carbon atoms, 48 wt. From a mixture of C10-C19 aliphatic n-alcohols esterified with acetic acid, 7 wt. Of the mixed diethanolamine ester with oleic acid and dialkyl phosphate of 10-19 carbon atoms, wt. Of oleic acid.

Example 1 a d 4

The following ingredients were mixed together:

wt. Base oil; viscosity at 20 ° C 5.13. 10 “6 m ² / s; distillation range 250-340 ° C; flash point 127 ° C; pour point -5 ° C; sulfur content 0.05 wt.%; an acid number of 0.08 mg KOH / g; iodo-bromo number 6.7 g J / 100 g, wt. Of polyisobutylene, molecular weight 1000, wt. From a mixture of aliphatic n-alcohols with 10-18 carbon atoms, wt. From a mixture of aliphatic n-alcohols with 10-18 carbon atoms esterified with acetic acid,

0.5 wt. From a compound of formula II wherein x - 2,

R ₂ = R 3 = - / CH _2/2 O-oleyl,

R = -SO ₂ O / CH _2/12 ^_CH 3>

0.5 wt. Of oleic acid.

Example 5

The following ingredients were mixed together:

wt. Base oil; viscosity at 20 ° C 2. 1G ”6 m ² / s; boiling point 200 degrees C; flash point 100 ° C; pour point -12 ° C; sulfur content 0.03 wt. OF; an acid number of 0.02 mg KOH / g; iodo-bromo number 5 g J / 100 g;

wt. From a product mixture, made from 1 mole of a mixture of C 10-18 alcohols, 0.06 mole of phosphoric acid, 0.6 mole of acetic acid, and 0.2 mole of triethanolaminstearic diester, in a three-step reaction; the product mixture contains the individual components in the following ratio: 40 wt. From a mixture of aliphatic n-alcohols with 10-18 carbon atoms, 45 wt. From a mixture of aliphatic n-alcohols having from 10 to 18 carbon atoms with tertiary fraction, acetic acid, 5 wt.

wt. Of polyacrylic methacrylate, molecular weight 10 000, wt. From octadecenic acid.

Example 6

The following ingredients were mixed together:

wt. Base oil; viscosity at 20 ° C 30. 10 “6 m ² / s; boiling point

350 ° C, flash point 140 ° C, pour point 0 ° C, sulfur content 0.1 wt. Z, acid number 0.1 mg KOH / g; iodo-bromo number 10 g J / 100 g, wt. Of polyisobutylene, molecular weight 5 000,

0.9 wt. Of lauryl alcohol, wt. Of lauryl alcohol butyric ester, wt. Of the compounds of formula II where R ₂ = - / CH _2/2 0H, R 3 = - / CH _2/2 0 steary1-R; = -SO ₂ -O- / CH ₂ /17-CH 3,

0.1 wt. From palmitic acid.

Compositions of the invention and various known comparative compositions were compared. In comparative experiments, aluminum with a purity of 99.5 was rolled on a roller mill at a belt speed of 10 g / min. The results are shown in the table below:

Ί

Κο ^ ομϊοι Formation of brown spots before aging after aging ⁺ / According to Example 1 none none According to Example 2 none none According to Example 3 none none According to Example 4 none none According to case 5 none none According to Example 6 none none BL3A Gerove / with content weak. medium polymer produced in GDR / staining staining A 65/4 / manufacturer: БИШ, medium s i lný contains ethers / Genrex 24 / manufacturer Moobl, staining staining contains esters, ethers, esters of phosphoric acid strong weak and polymer / staining staining БовоШг P 44 / manufacturer Esso contains ether and polymer / strong strong staining staining + / Aging is done by that is certain mono substance · in open glass container in an oven at 110 ° C to half of his volume.

SUBJECT V

Claims (1)

An oil-based machining composition useful for cold rolling aluminum containing 80 to 96 hmoo. Of the orthotreated oil raffinate with a viscosity of 2 to ³⁰ . 1 ° C ⁶ m 2 / s ( ² ° C), o (test range 200 to 350 ° C, flash point above 100 ° C, pour point below 0 ° C, with sulfur content less than 0.1% by weight Having an acid number below 0.1 mg KOH / g and having a number of less than 10 g J / 100 g, furthermore 0.5 to 15 wt.% Of an adhesion promoting polymer, characterized in that it contains as additive 1 to 10% by weight. a) from 10 to 75 hmoo, from an aliphatic alcohol having from 9 to 19 carbon atoms or a mixture of such alcohols, b) from 20 to 60 hmoo. % of an ester of one or more aliphatic alcohols having 9 to 19 carbon atoms and an aliphatic carboxylic acid having 1 to 6 carbon atoms; A straight or saturated saturated or unsaturated carboxylic acid having from 8 to 20 carbon atoms, d / 1 to 30; H R2-N- (CH2) X-ORJ * 3 R @ ₂ -N @ ⁺ - (CH2) _x @ 10 OH R3 / 1 / / 11 / wherein x is an integer between 1 and 5, R 1 is a group of the formula (O- / CH 2) y -CH 3 -SO 2 -O- (CH 2) _y -CH 3 or -PO ² О- / СН2 / _г -СНз where the values for y and z independently are integers between 4 and 20, R 2 denotes hydrogen, a (C 1 -C 5) hydroxyalkyl or - (CH 2) _x OEEt group, wherein the value for x is an integer between 1 and 5 and the Est group forming an ester separable from a saturated or unsaturated carboxylic acid having 1 up to 20 straight chain carbon atoms, R3 represents a group of formula ^- / ^{CH2 /} _X o ^ ^ st, ^kt era of ^d ^ i (^ \ ^ i s ^{to be} in a ^p in'ě - / CH2 / x0E8t mentioned in R2.