DE2921572A1 - PHOSPHORIC ACID ESTER OF POLY (2-10) - AETHYLENOXY-N-BUTANE-1,4-DIOL - Google Patents

Description

Phosphoric acid ester of poly (2-10) -ethyleneoxy-n-butane

The use of synthetic, flowable cutting preparations is constantly increasing. The oil-free preparations are designed to provide lubrication impart at high temperatures, inhibit rust, reduce surface tension, produce little foam and be compatible with concentrated electrolyte solutions for hard water.

Synthetic, flowable metalworking compounds that can be both oil and water soluble are being made from conventional, nonionic, surface-active agents formed, which consist of a polyoxyethylated hydrophobe. These nonionic surfactants are provided with a phosphate radical which is various of those desired Properties improved including an increase in the hydrophilic character of these surfactants. Examples of such flowable metalworking materials are e.g. the ANTARA ^ lubricant preparations from GAF. These flowable metalworking preparations are based on aliphatic and aromatic, hydrophobic parts that are further alkoxylated and phosphated.

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The present invention provides compounds that see especially for the formulation of synthetic, flowable metalworking preparations water-based. The connection

■> fertilizers are polyethoxylated (2 to 10 EO) n-butane-1,4-diols, which are completely hydrophilic and do not contain any hydrophobic part. The particularly novelty of the present invention consists in the phosphoric acid ester of the condensation products of 1 mole of butane-1,4-diol with 2 to 10 moles of ethylene oxide. These

! "Esters are suitable for a variety of uses, e.g. as synthetic metalworking fluids on an aqueous basis. Other uses are as lubricating additives, Corrosion inhibitors, hydraulic fluids, flame retardant additives, Plasticizers, etc. The phosphate esters

π-of the present invention are very likely straight-chain compounds, meaning that they do not contain any branched chains.

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This is what distinguishes the compounds according to the invention of the generally available compounds based on combinations of hydrophobic and hydrophilic parts »The straight * chain nature of the present compounds is another ίο special desirable trait, namely that it is biodegradable are. The compounds according to the invention can by formation of ammonium, substituted ammonium, AlkalineOaIl or Alkaline earth metal salts are further modified.

Process for the preparation of the rather complex, according to the invention Compounds and their mixtures follow known synthetic procedures. The ethoxylation takes place by addition a predetermined number of moles of ethylene oxide to the terminal hydroxyl groups of the butanediol. Of course

'''This addition gives a known, random distribution of oxyethylene groups on each side of Butandiolteils. The phosphating by known processes. As phosphating is achieved according to polyphosphoric bev'> rz _U gt, although P2O5 can be used. The choice

^ between the two phosphating agents depends on whether you mainly want the diester or monoester. Polyphosphoric acid provides more of the monoester, while P ^ O ₁ - more strongly provides the diester.

Typical manufacturing methods according to the invention are like follows:

n-Butanediol is placed in a pressure vessel, for example an autoclave, and 0.05 % NaOH catalyst, based on the diol, is added. In a cylinder, which by means of a valve

³ -> provided pipe is connected to the pressure vessel, a predetermined amount of ethylene oxide is given. The valve is opened to allow the reaction to take place at a pressure of 2.1 to 2.31. atü with a temperature regulated to 130 to 140 C to continue. The reaction continues until the pressure drop

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case indicates that no unreacted ethylene oxide remains.

The phosphating of the ethoxylated n-butanediol can be carried out with PpO ₁ - or polyphoposphoric acid (PPA) 115 ~% strength; it is carried out in a four-necked flask provided inlet (or CaCIp pipe) and vent tube (or cooler) with methanischem stirrer, Therometer, N ^. Before Phos _m phosphatizing the Dioläthoxylat, a Färbstahilisator in amounts of from 0.5 g to be added to the first The stabilizer is hypophosphorous acid when using P2O5 ^and * sodium hypophosphire when using polyphosphoric acid.

ι! P ^ Oc is added in portions, the temperature being maintained at about 50 to 6O ⁰ C. After the addition has ended, the reactants are heated to 90 to 95 ° C. for about 5 hours.

Polyphosphoric acid in a predetermined amount is placed in a stone dropping funnel connected to a neck of the flask and added dropwise while maintaining the temperature at 40 to 45 ° C. After the addition has ended, the reactants are heated ^{to 95 to 100 ° C. for about 2 hours.}

The products from each phosphating can be bleached using 1 to 3 ecm 30- ^ HgO _2.

Typical preparations be bought in the following table ^{■! I} shows.

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Temp.wanr;

Diol Phosphat.-Mittea addition Reakt.-Temp »Yield,

No. g., mol g., mol (addition time j · (reaction time.V - g ■ % monoester *.

—— r ———, « /

° -60 ° C 90 ° -95 ° (

133, 0.5 55 / o, 37 (30 min.) (5 hrs.) 188 44.5 65.4

BID.4EO P ₂ O ₅ 50 ° -60 ° C 90 ° -95 ° C

BID.6EO P ₂ O ₅ 60 ° -65 ° C 90 ° -95 ° C

177, 0.5 55, 0.37 (30 min.) (5 hrs.) 232 41.0 50.0

cd 3 BID.6EO PPA 50 ° -55 ° C 95 ° -100 ° C

354, 1. 340, 2.0 (25 min.) (2 hrs.) 694 71.9 13.4 '

. VJl

4 BID.6EO PPA 40 ° -45 ° C 95 ° -100 ° C l

5 "354, 1. 170, 1.0 (30 min.) (2 hrs.) 524 47.8 Xl ₁ I ^ ο T *

BID.6EO PPA 40 ° -45 ° C 95 ° -100 ° C

354, 1. 127, 0.75 (20 min.) (2 hrs.) 481 49.0 0.0

BID.6EO PPA 40 ° -45 ° C 95 ° -100 ° C

354, 1. 85, 0.5 (20 min.) (2 hrs.) 439 35.6 3.1

: 7 BID. 6EO P ₃ O ₅ 6.0 ° -65 ° C 90 ° -95 ° C ^ ₀

₃₅
177, 0.5 26, 0.185 (20 min.) (5 hrs.) 232 45 _f 4 45.7

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The compounds according to the invention are all based on butanediol. The number of moles of ethylene oxide which is ethoxylated with one mole of butane diol is given as the number of EO, and that

:> Phosphating agent is called PpOc, or PPA for polyphosphoric acid specified. The ratio shown following the butanediol, ethylene oxide and phosphating agent is this Ratio between 1 mole of ethoxylated butanediol and the number of moles of phosphating agent with which it is

H) has been set.

The compounds according to the invention are all based on butane _: diol. The degree of ethoxylation varies between 2 to 10 EO, and the phosphating can vary with PPA or PpOj-.

ib The compounds falling under these conditions are all in synthetic flowable metalworking materials, sometimes called coolants, suitable. When the compounds are diluted with water, they form true solutions. The connections continue to form little or no foam and any foam that forms breaks quickly. The invention further impart Compounds most metals corrosion protection and withstand extreme pressure and elevated temperature very well the end.

The desirable properties of the ethoxylated, phosphated butanediols of the invention are shown by a comparison with two commercially available compounds used in the manufacture of flowable metalworking preparations. ANTARA ^ Lp-700 is a phosphate ester of phenol plus 6 EO, reacted with 1 mol of P ₂ 0 _t ; per 2.7 moles of the ethoxylated phenol. ANTARA ^ LK-500 is the phosphate ester of nC ^ H ^ OH + 3.4 EO and using 1 mole P ₂ O ^ per 2.7 moles of the ethoxylated alcohol is phos- ^;

as phated. ;

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The following tests show the foam properties of the he ^; inventive compounds as well as the two compounds used in commercially available metalworking fluids

b bindings. A typical concentration of a flowable metalworking compound water-based is as follows:

concentrate

Parts by weight of phosphate ester 10

ίο triethanolamine 20

Water 70

The triethanolarain is used in the preparation, xrm acidic; To adjust phosphate esters alkaline. Commercially available, flowable

Ib metalworking preparations are also stored alkaline in the concentrate of the same composition as the compounds according to the invention. In each experiment shown in Table I, 15 g of concentrate were diluted to 250 ecm with dist. Diluted with water, which results in an approximately 0.6% concentration of the phosphate

20 ester compound.

A mixer, for example a Waring mixer, was used with a measuring strip in mm on the side of the mixing bowl. The measuring strip was adjusted so that the marking 0 with the ^? ■:? B Height of the unstirred, diluted preparation of the metal ^; machining fluid matched. The solutions were stirred at high speed for 1 minute and the foam height read when stirring was stopped and every minute thereafter for a total of 5 minutes.

In the following Table I, BID stands for butanediol.

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Table I.

Foaming test in the mixer
(15 g concentrate, diluted to 250 ecm with distilled water; 0.6% phosphate ester)

PHOSPHATE ESTER
(neutralized like
. in concentrate) 0 me, 1 min Foam height
2 min 3 in mm
Min 4 min 5 min Antara LP-700
. (not biodegradable) 70 58 50 48 46 45 LC
O
CiD Antara LK-500
(biodegradable) 112 105 90 85 68 58 OO
CO BID.2EOrP ₂ O ₅ (1: 0.74) 73 38 25th 15th 10 7th O BID.4EOrP ₂ O ₅ (1: 0.74) 70 40 26th 18th 15th 8th 'Tl' BID.6EOrP ₂ O ₅ (1: 0.74) 78 32 16 8th 3 0 BLD-OEOrP ₉ Oc- (1: 0.37)
/ L Zj * 83 53 35 21st 13th 8th B1D.4EO: PPA * (ArI) 52 24 9 7th 6th 5 BID.6EOrPPA * (1: 0.5) 72 23 7th 0 0 0 BID.6EOrPPA * (IrO, 75) 71 25th 1 0 0 0 : BID.6EOrPPA * (IrI) 70 24 9 0 0 0 BID.6EOrPPA * (IrI, 5) 63 26th 7th 0 0 0 BID.6EOrPPA * (1: 2) 52 12th 1 0 0 0

* 115 % PPA (= polyphosphoric acid)

ro cn κ:

As can be seen, all of the above flowable metalworking preparations with the exception of ANTARA®LP-700 are biozer-? settable. The biodegradability is one of the most desirable features of such metalworking products, particularly in view of the increased environmental protection against unauthorized \ needed contaminated wastewater.

Of course, all form flowable metalworking preparations based on ethoxylated, phosphated butanediols less foam than decomposable, alkoxylated, phosphated alcohols, whereby the foam breaks faster than with any other commercial product. The diminished Foaming and the relatively quick breakage of a gebilib deten foam increase with the degree of ethoxylation. ■ The preparations are further improved when the phosphating agent Is polyphosphoric acid which predominantly forms the monoester. An extraordinary connection regarding low foam is BID.6EOjPPA (1: 1). This was; j 20 in different proportions with respect to triethanolamine; j and water incorporated into preparations and the pH value established. The preparations are shown in Table I, wherein

all parts are parts by weight. \

Table II;

Preparation A (B C-

; BID.6EO: PPA (1: 1) 10 parts 10 parts

Triethanolamine 20 "33.5»

Water 70 "56.5 ·»

pH 8j 25 8.6

The preparations were diluted in water to a concentration of 0.6% phosphate ester. As a result, formulation C \ had to be added twice as much as A and B at 250 ecm. {The results of the foam test are shown in Table III.!

^: j

■ 35 ^:

5 Parts 20th ti 75 8.5

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Table III

Foam test in the mixer (preparations from Table II, with dist. Water to a concentration of 0.6 Yo Phosphatester diluted) foam height in min

preparation 0 min 1 min 2 min 3 min 4 min 5 min A. 70 25th 8th 0 0 0 B. 70 35 14th 0 0 0 C. 70 27 3 0 0 0

The results show that the phosphate esters according to the invention are quick regardless of their degree of neutralization have breaking foam. As can be seen, no foam remained after 3 minutes.

A further reduction in foam and an increase in the rate of its breaking is obtained by adding 1 % by weight of Surfynol 104E (tetramethyldecynediol in ethylene glycol; 50 % concentration) to 99% by weight of preparation C. Preparations C and C plus Surfynol 104E were stirred in the mixer at a phosphate ester concentration of 0.6% with the following results:

Table IV

Foam test in the mixer (preparations diluted to 2i? 0 ecm and 0.6% with distilled water)

^2b foam height in mm

Preparation Ο min 1 min 2 min 3 min 4 min 5__M_in_

0 0 0 0

The lubricating properties of the compounds according to the invention were determined in aqueous solution as protection against wear by means of a standard four-ball test and by the lubricating properties measured according to the Falex test under extreme pressure. ^;

C. 70 27 3 0 C. plus Surfynol 25th 1 0 0 30th 104E

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The four-ball test was carried out with a test load of! 100 kg at 1500 rpm and an initial temperature of 38 ° C \ for 5 minutes. There were steel balls from a chrome alloy; 1.25 cm diameter was used. Three balls abutting one another were held stationary under a fourth, which, with the given load against the others, spinning balls was pressed. The balls were placed in the various liquid metalworking machines to be tested.

immersed in water-based exercise preparations. The test i followed five minutes, after which the bullets came out |

gutted and examined for wear and tear. The smaller: the groove, the more effective the tested compound.

iö The metalworking preparation for performing the four-ball test was prepared by adding 12.5 g of the basic; Dilute the preparations in sufficient water to a 250 ccm solution. The preparation obtained had one concentration
of the phosphoate ester compound of 0.5 %. The in the test

The total amount of triethanolamine present in the solution was adjusted so that the pH of each sample was 8.3 + 0.1. the
Test results are shown in Table V. As can be seen
the compounds according to the invention provide results that
are comparable to the leading commercial product that

jh is not biodegradable.

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Table V

Four-ball wear test (0.1>% phosphate stone "; with TEA to pH 8.3 + 0.1)

^!> Diameter of

Phosphate ester wear groove

water only, with TEA to pH 8.3 failure (T)

Antara LP-700 0.77

B1D.2EO: P ₂ O ₅ (1: 0.74) 0.74

B3D.2EO ^ Oc (1: 0.74) 0.79

B1D.4EO: P ₉ O, - (1: 0.74) 0.85

B2D.4EO: P ^ O ^ (1: 0.74) 0.76

B3D.4EO ₁ P ^ O ;? (1: 0.74) 0.79

B1D.6EO: P ₉ O, - (1: 0.74) 0.78

B2D.6EO: per ^ (1: 0.74) 0.76

,,, B3D.6EO ^ Og (1: 0.74) 0.74

B1D.6EO: PPA (2) (1: 0.5) 0.77

B1D.6EO: PPA (2) (1: 2) 0.76;

(1) Failure means the rpm could not be maintained, ₀ , and the test had to be performed before the necessary

Minutes to be canceled. A typical groove diameter ^; on failure (in less than 5 minutes) is well over 3: mm *

(2) 115 % polyphosphoric acid ]

The four-ball wear test was done with comparisons
the preferred compound B1D.6EO: PPA (1: 1) according to the invention with a 0.1% strength triethanolamine solution and the leading,
commercial product ANTARA ^ LP-7OO. The other variable in this test was diluting each preparation in half to see when to do that
The preparation was no longer effective enough to prevent excessive wear and tear. The results of this test are
listed in Table VI. ;

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Table VI
Four-ball A ^v D usage test (pH of test solution 8.3 + 0.1)

Groove diameter ((mm)

concentration 1.0% 0.5% 0.25% . 0.125% 0.062% 0.031% Water alone
(pH 8.3 with TEA) Failure (1) 0.5% -% TEA solution
(pH - 10.1) Failure (i) Antara LP-700 0.75 0.77 0.80 1.42 failure (i) Failure (1 BID.6EO: PPA (2) (1;) 0 _s 77 0.77 0.76 0.86 0.92 2.46

(1) see Table V

(2) 115 % polyphosphoric acid

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Some of the preparations described in Table I were diluted to 0.15% of the phosphate ester compound in the test solution. After that no adjustment of the pH value was superiors'> taken. The load bearing capacity results are shown in Table VII below.

Table VII

Falex test of load-bearing capacity (preparations based on 0.15 % phosphoric ester compound

diluted)

Test connection
(0.15 % concentr.) (1: 0, max.
pressure on failure
kg 998 Torque
kg / cm Water alone
Antara LP-700 (1: 0,
(1: 0,
(1: 0, 862 11.8 B1D.2EO: P ₂ O ₅ (1: 0,
(1: 0,
(1: 0, 74) 907
Il
816 12.5 BID. 4EO: PpO, -
B2D. 4EO ^ Og
B3D.4EO: Ρ ₂ Ος (1: 0,
(1: 1) 74)
74)
74) 907
816
Il dd
ti
It BID.6EO: P ₂ O ₅
B2D. 6EO: P-jOj-
B3D.6EO: P ₂ O ₅ 74)
74)
74) 862
1134 12.9
It
It B1D.6EO: PPA *
BID.6EO: PPA 5) 13.2
It

* 115 % polyphosphoric acid

A second series of tests of the load-bearing capacity was carried out by comparing the connection preferred according to the invention, B1D.6EO: PPA (1: 1), with the leading, commercially available Connection ANTAfIA. © LP-700. The comparison was made on three different concentrations of the flowable metalworking compound. The results are shown in Table VIII.

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Table VIII

Falex test of load-bearing capacity (pH of the test solutions 8.3 +0.1)

., Concentration d. Max. Backenbeiet.- Dr-eluuoment b iddruck in verse. kg l-c '/ ^rm

Antara LP-700 1089 ¹¹ > 3

B1D.6EO: PPA * (1: 1) 1134 13.0

0.07 5% !

Antara LP-700 630 10.7.

BlD.6EO: PPA * (1: 1) ^Ö16 11.6

0.037%

Antara LP-700 363 ~~ _;

BID.6EO: PPA (1: 1) ⁸ ^ ^{6 11} » ^&:

* 115 % polyphosphoric acid

The comparison results of the commercially available product with the preferred compound according to the invention show almost an equivalent at 0.15% concentration, but a longer-lasting effectiveness with decreasing concentrations of the compound according to the invention.

The same two compounds, namely the preferred one according to the invention / 3 Phosphate ester, and ANTARA LP-700, were based on

_{? ö} Rust inhibition tested. The materials were applied to GuJ3 iron blocks dex * Mai3e 63.5 x 127 χ 19 mm. These were freshly polished with 2AO grit alumina paper to remove any oxides from the surface; then the blocks were further cleaned with mineral spirits or hexane

j ₍₎ and rubbed with a clean cloth until no more black oxide was visible on it.

The test solutions were applied as relatively uniform drops, usually in a series of five, over the block area _{; i>)} . Then, the test was blocke at 2k ^hours room temperature allowed to stand. During this time, all of the water will evaporate from the metalworking fluid. The blocks were then examined for rust. The Kon- ^; doors of the dried solution were visible, and the rust;

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inhibition was estimated by taking the average

the area of each rust-showing stain. .

ij ANTARA (r) lP-700 was made with water alone and that according to the invention preferred connection. The test solutions ■ were with triethanolamine to a pH of 8.3 + 0.1 set. The results were rated from A to E, where A means no rust; B means that less than

ίο 10% of the area on which the specimens were allowed to dry was covered with rust; C means that between 10 to 50 % was covered with rust; D stands for 50 to 99 % rust, and E stands for 100% coverage with rust.

The preparations were examined in concentrations of 0.1 or 0.3%. In one test series, 0.02 % sodium nitrite and another 0.06% sodium nitrite was used as an additional rust inhibitor. The results are shown in Table IX.

Table IX _;

Rust inhibition test (test solution with TEA on

pH 8.3 +, 0.1 adjusted) \

D. concentration σ ο in test solution avg
Rust rating
tion D. % Connection 0.3
0.3 % NaNO ₂ E. Water alone D. - 0.1
0.1 none B.
B. Antara LP-700
BID.6EO: PPA (1: D. 0.1
0.1 It
M. A.
A. Antara LP-700
B1D.6E0-.PPA (1: 11
It A.
A. Antara LP-700
BlD.ÖEOrPPA (1: 0.02
0.02 A.
A. Antara LP-700
B1D.6EO: PPA (1: 0.06
0.06

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As can be seen, the compound preferred according to the invention exhibits rust-inhibiting properties by itself
Adding an additional rust inhibitor be \ improved ".

In addition to the rust-inhibiting properties, the inventions \ compounds according are also compatible with the Elektrolytkorrosionsimhibitoren, the flowable metal working; Preparations are usually added, such as sodium nitrite. Load-bearing tests were carried out comparing the compound preferred according to the invention and the commercially available product ANTARA®LP-700, in preparations containing _{NaNO 2.} The results are shown in Table X.

In both cases there is a certain loss of the load-bearing Capacity, however, when the invention

Connection is less than that of the commercial product. ;

Table X

Falex Load Carrying Test; in the presence of NaNOp ^; pH of the test solution = 8.3 +0.1:

link

Concentrate.

% NaNO,

max. jaw pressure in case of failure .; kg

Antara LP-700
BID.6EO: PPA * (1: 1) 0 _r 15
0jl5 0.03
0.03 590
862 Antara LP-700
BID.6EO: PPA * (1: 1) 0.075
0.075 0.015
0.015 544
726 Beginning: ara LP-700
BID.6EO: PPA * (1: 1) 0.037
0.037 0.0075
0.0075 386
454

* 115 % polyphosphoric acid

I _1n general, the novel compounds or mixtures thereof in a concentration of 0.1 to 1.2 parts by weight Ji in a
aqueous, alkaline solution used.

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Claims (1)

' Patent claims •. "1. ■ ** 'Phosphoric acid ester of poly (2-10) -ethyleneoxy-n-butane- ; 1,4-diol. : 2.- Compounds according to claim 1 in the form of the mono-, di-
\ or Trieste. J 3.- Compounds according to claim 1 and 2, in the form of their
: io mixes. 4.- mixture according to claim 3 _t, characterized in that
i (larger; ΐ the monoester is present in a substantial amount. f j I is 5 · mixtures according to claim 3%. characterized in that! (larger) j i the diester is present in a substantial amount. j ι 6.- compounds or mixtures according to claim 1 to 5 in ■ their salt form with organic or inorganic bases. ■ i ? 7 · - Process for making connections and mixing f ; gene according to claim 1 to 5, characterized in that one i about 1 mole of n-1,4-butanediol with about 2 to 10 moles, preferred j i wise 6 moles, ethylene oxide converts, the so produced, ; 25 ethoxylated n-1,4-butanediol with polyphosphoric acid and / or ι ^P 2 ° 5 phosphated and optionally then with a
organic or inorganic base. J ί 0.- Metalworking concentrates, consisting of or containing compounds or mixtures according to claims 1 to 6
'' in the form of aqueous solutions with an alkaline pH value. ! : 9.- Concentrates according to claim 8, characterized in that f ". That the pH value is adjusted to at least 7.5. J 35 I. \ 10.- Concentrates according to claim 8 and 9, characterized in that j; draws that they are compounds or mixtures according to
J claim 6 included. 09849/0750 ORIGINAL INSPECTED 11. Concentrates according to claim 10, characterized in that that the salt is composed of ammonium, substituted ammonium, an alkali or alkaline earth metal, e.g. triethanolamine, derives. 12.- concentrate according to claim 8, characterized in that there is also an antifoam agent and / or a rust inhibitor contains. j 10 The patent attorney: 15th 20th ^: 30 ^: 3b 9098A9 / 0750