DE1570503A1 - Process for the preparation of polyesters of the dimer of linoleic acid - Google Patents

Description

Dr. W. Cool

Patent attorney

Ttltgrwnm-AdraM ·! Dellner patent Telephone 34 6131

2OOO Hamburg 36, ₉ * _{nr 1Q} ec

opian.de 36 a ^m i » " H ·· «303

Seso Ee8earch, and Eng. Oo. Betohung

BSSO BBSEARCH AHB SHOIHESRIHe COICPANY ₁
Slissabeth, Htw Jersey, V.St.A.

Process for the production of polyesters
of the diaeren of linoleum & ure

for this registration the priority tob April 6, 1964 is set the British patient registration Ho. 14 110/64.

The invention relates to improved Eilusliche Polyaerieates, which are used as additions to hydrocarbon syrup or fuel oils, especially when used in combustion power, soaks up works.

The inventive additives can be hydrocarbon fuels, like Bensin, £ euehtul and D "etill" tül # n aittierer

C8 «eul #»} »sugesetst, including the rereohleiseain-Blgtniohftea aolohtr oils su increase «if you see s.B.

909886/1733

through propellant pumps τοη dieeelaotoren, and • you can also use «1 · Susfttse sa scarf oil, iB Sohiffeiylinderölen, motor vehicle suction pumps, oils for cooling systems, hydraulic oils and sonic oils, xm to increase the anti-icing properties of these oils, if the oils lu in Touching old moving casino parts can be used.

Bit additional geatas of the invention are blocked poliyeeters, the see τοη des Biaeren of idnoleic acid and a «diol the long legs forael

B - C - OH

RO-OH
H

derive, in which R is a Waeeeretoffatoa or an alkyl group old means 1 to 20 Kohlenetoffatoaen and the beds R in jedea Molecules can be the same or different, while a den Has value 0 or 1. This Vorael therefore uafaeet ethylene glycol, Propylene glycol and mono- or poly-alkyl derivatives of the same. BIe 8erppen the polyesters get old one old them reaction afanigettf Non-oil-containing compound, Torsugaweiae an aliphatic alcohol or an aain, uageeetat.

The polyether core according to the invention entepreohen the general forael

SAD ORJGiNAL

909886/1733

HO - C Σ - ^οοσ - ^γ - "J

in the Z the remainder of the mole »Y the remainder of the linoleic acid, E an organic group »preferably the residue of an aliphatic alcohol with 1 to 6 carbon atoms or of a primary or secondary amine, and a is an integer from 1 to 25, preferably from 3 to 6 »means. The upper The limit of η depends on the solubility limits in the hydrocarbon oil to which the additive is to be added.

The linoleur dimer is a well-known compound » obtained by the dimerization of linoleic acid. The usual one The product may contain small amounts of monomeric linoleic acid and trimeric linoleic acid as impurities.

The additives genäse of the invention are simple Esterification of the dimer of linoleic acid Mt dea diol in equivalent molecular weight Quantitative ratios produced «whereby the esterification is continued until more than 1 and have formed less than 2 moles of water of reaction per mole of acid and diol. The polyester thus obtained is then blocking with a effective connection »z„ B. an alcohol or a Amine, with which the acid group reacts be exposed to true polyester formation, as soon as the desired degree of polycondensation is reached. In this way one obtains valuable connections »but through them Polyester formation reaction continues until 1.0 to 1.96 mol of water are split off.

_ 3 ^ BATH

90 9 8 86/1733

The formation of polyester is carried out according to methods known per se carried out, see B. Indiaa da «Piaare dar Linolsiura and daa Biol In an inert soil like heptane, bensol or toluene, susaaaen old an esterification catalyst, see B. concentrated Sohwefelelurt or p-toluenesulphonic acid Return flow temperature will be obtained, see a bestiaate Amount of Baaktionawaasar has formed. Bann will do the Beaktionegeaieoh the blocking compound (alcohol or lain) is sugeaetst and the heating element continues on Btiokfluaataaperatur get, baror daa thinner, daa waaaer and the part not stated is the blooming aittala, see B. by distillation. In this way, high-quality products are obtained from acid grinders τοη 5 to 80 ag KOH / g.

The geaäas the invention hergeetellten blocked polyesters can su hydrocarbon oil in amounts τοη O OOI ₁ to 5 eev.-jt be Bugeeetst, su rerleinen inter alia dan oils Teraohleissaindernde properties. Ingredients can also be prepared which contain the blocked polyester in amounts up to its solubility limit and which are suitable for use.

The blocked polyesters are useful in accordance with the invention especially as additives su hydrocarbon oils, the so-called contain "over-alkaline" additives, such as s.B. organic Salsa, such as alkali or alkaline earth salts τοη öllösliohen Sulphonic acids, salicylates, haphthenates and phenolates, which are more old than the atoichiometric amount of a metal base

been aind. Ια blessing value for over-alkaline compounds the elements of the invention do not constitute any kind of development or songs «

BtUUeI

3.5 moles of dilinoleic acid and 5.5 moles of ethylene glycol are heated in 980 »1 bensol in the presence of 15 g of p-ioluenesulfonic acid under Btlokflues until after 3 hours at a reaction temperature of 95 ° 0 6.6 moles of water have escaped. The reaction ageaoli is cooled to 75 ° C and bit of a liquid τοη 3 g of methanol is evaporated in 75 g of bensol, whereupon “on the reaction ageaiaoh for another 1/2 hour at 83 ° C as the radiator cooler ele“ the lttaet and daa Waeaer removed by aaeotropic distillation. 7.1 moles of waaeer are ventilated off within the concentrated reaction time. The ao produced polyester is under the reward "Polytater B" ⁵ ms. rerwandet the approaching Terauohen.

Ba * sugesetst product is in an amount of 1 wt. -I "a" Sohiffaaylinderul which fön a überalkaliaiertea Oaloiuaaulfonat in an amount containing 7 £. Sa * product is free from dyeing or! Leather sole «.

Sa is a rom legs eAT-SreibetoffpuHpen-PrflfetfindTerauohen durohgefOlirt _y us the Abnutsung the Kurbelaohlene using τοη Leucshtöl as fuel "it and without Zuaats dea erfindungegesSfssta $ oly © i3tere su bestisnesi. The Brgebniaae find aioh in the Salbelle I.

BAO 90988B / 1733

table I.
PAY-Trelbetoffmuroe ^ PrüfetandTerBuehe

Abnutmra the lorbelsofeleno. u »• It, 8td. 100 200 250 300 400

fuel

Leuohi oil 86.4

AutodieeelBl - -22.9

Leuht oil +0.1

l A * 0 12.7 20.3

Luminous oil + 0.1 oev.-jt '
Polyester A * 4-water * 50.8

LeuchWl + 0.1

Polyester A * 4- 0.025 mi
jt "Priaene 81 U ^nK } L
20 ppa "Arqnmd 2 Hf · ¹² '

Leuolrtei + 0.1

Polyester A + 0.025
aew · - * "Prieene 81 B"
+ 20 pp »" ArqiMd 2 Hf "
V ^ - - 63.5

Leuht oil -1-0.1
Polyester Β * »

Luminous oil + 0.1 wt. -J6.
Polyester B · »+ water ' ¹ '

+ Leuohtöl and 10 % Vmeser are visoht well for 1 hour, whereupon the water, which separates as soil acid, is not disturbed.

(1) OberfMolienaktiTes means, produced by Mraa BoIw k Haas.

(2) Oherflichenaktiree means manufactured by Pirea Araour Oheaioals.

* Polyester A is an unglazed polyester made from ethylene glycol and di-linoleic acid.

♦ · Polyester B is a blocked polyester made from ethylene glycol and dilinoleic acid, which is used as a KLockierunggrappe Contains CHj -flruppe and prepared according to the above example is.

909886/1733 ^^, ^

From the above experiments it can be seen that the Zueate the polyester according to the invention to Leu®htöl as fuel prevents wear on the crank rail.

Table II shows the beneficial effects in terms of changing the adjustment of the pump when the inventive Polyester su gasoline can be added »

Table II

The following results show the beneficial effects of polyester B in reducing wear the pump when using different types of benches Comparison «u a turbo-jet fuel. You wear verte are not fixed with the four-ball device.

Sole test with the animal ball device

(Critical Wear and tear, kg) 0 OA-201, 1000 ppm 2000 Boiling range _p Soft
drmok
after
Reid
at 42 500 66 1500 82 fabric ⁰ O 100 ° C 42 57 54 * 74 59 A (MVH) 41 to (59 0.46 20th 47 46 59 52 B (HVN) 146 "185 '0.06 37 39 64 52 68 C (LVH) 25 "153 1.2 56 49 - 68 - D (LVN) 45 " 0.62 - - Turbo jet
fuel * YlerkU device according to Shell

"Manual for the Pour Ball E.P. Lubricant Testing Machine",

issued by Shell Petroleum Company Limited,

P.D. & B. Department, Technical Division, Reference No. 29/52.

-'- 909886/173 ^ ° * ^

KraftfahrBeug- Kurbkaatenaohinierttle additive B is evaluated in crankcase oil for gasoline engines, primarily about the "possible replacement of wear reducing agents τοη the type of zinc dialkyldithiophoephate by a more permanent additive to examine, which does not cause deposits in the engine, for example the piston crown, contributes. The following basic approach is used and compared with the same approach under Zueats τοη "Polyester S" or zinc dialkyldithiophosphate in the "Ford Zephyr Brand III engine test" (Ford Testing Schedule for Approval of Lubricating Oils, Ford Motor Coupany Liaited, England).

Basic gusajnpensetzun " Paraffin base crude oil, Saybolt viscosity

at 37.θ ° C 140 to 160 sec. 86.22

Viekoaitätsindezveresserer \ Misohpolynerisat from Tinylacetat, H-Vinylpyrrolidon and Fuaareäureeetern 6.0

Detergent; sulfurized barium phenolate 4.2 Detergent calibrated sulfonate 2.08 Non-organic detergent; Addition connection off Polyisobutylene and succinic acid 1.5

SAD - 8 -

909886/1733

oil 1 2 1570503 Yereohleiaemimin-
the addition, wt .- ^ Zinc dialkyl
dlthiophoe-
phat (1 »O) Poly
ester B
(0.5) .5 Wear and tear of the
Yentilvpitzes Table III Mean value, μ
Area, μ 12.7
5-25.4 19.3
10-35.6 3 StBseel * 4 SpL, 1 SpA unconcerned
eohamaged 0 Ring bonding
(Kaxinua »10) Ford Zephyr Brand III engine enteat cold
hot 88 5.95
9.15 8.0
10.0 29.2
15.2-45.7 Piston (waxinsua = 10) 2 SpA, 1 A ₁
2 sat Aussenlaok on
Kolbemaantel
Aufnahoe on AussenaeJ
dee KolbeniBantele
Paint under piston
floor
Coal deposition under
Piston crown 8.0
Lte
10.0
Completely
old
money
bedeokt 8.1
8.3
2.40
10.0 7.6
10.0 9.1
10.0
2.70
10.0

Piston Bolsenlaok (MaxiBua «10)

3.7

3.0

3.0

♦ SpL SpA

SA

Spurealoohfraas trace abrasion abrasion
strong abrasion

bath

9 0 9886/1733

With regard to the ram wear, all six show stUasel no abrasion when using polyester B; when using zinc dialkyldithiophoephate as additive, eight sioh however, at five Loohfraee and beginning of eeohe Stöeeeln beginning abrasion noticeable.

With regard to the? Est gluing of the piston rings and the Purity below the piston head, the results are significantly improved by using polyester B.

Ud to bestlaaen the wetness, to dea these results maybe influenced by other additions in dea Geaisoh a third verse will be made using the basic composition carried out, but no wear-binding Addition includes “As expected, this results a considerable increase in the wear and tear of the valve drives; however, the purity of the flask is the same as that obtained with dee Ul 2. These engine tests show that "polyester B "to a considerably lower wear of the ram and to A higher purity of the engine leads than additives on the basis of zinc dialkyldithiophoephaten.

The three oils are also examined in the Petter W-i engine. The »it dea oil Ir. 2, which contains the "polyester B *, experiment carried out, with dea the piston remains so pure, ale if it were new, the oil 3 will confirm the repeat bit. In both cases the bearing weight loss is satisfactory.

OfUGiNAL

- 10 -

909886/1733

Storage weight loss, mg

Paint on piston skirt (10 = pure)

Inner of the piston skirt

Under the piston crown

oil ring lining

Table IY

Petter W ~ 1 engine tests 1

2.6

9.0

2 pounds, light

red discoloration

exercise

12.3
10.0
pure

75 f> pure black paint
20 1 » redder
Laok

12.5 10.0 pure

pure

completely free completely free completely free

These two series of tests show that the additive B provides good protection against Yeraohleiss without forming of deposits in the engine.

Marine diesel fuel tank Bohmier oils

Polyester B is investigated as an additive to marine diesel engine ohms and compared with other compositions. The tests are carried out according to the "Abingdon Petter Hk. I" and "Mk. II ⁿ -Yerfahren, which in" Laboratory Engine Testing of Marine Diesel Cylinder Lubricants ¹ⁿ (Baker and Daviee), Journal of the Institute of Petroleum, Volume 50, Mr. 484, April 1964, are

oil 4 - 79 + oil base, 21 * overbased Gaiciumsulfonat *

oil 5-78 i * ölbasie, 21 * tiberslkalieiertes Calciumeulfonat, unblocked polyester of ethylene glycol and Mlinolsäure

- 11 -

909886 / U

oil 6 - 78 * oil plant, 21 t overalkali egg tea oaloixuieulfonate, polyester IT.

Fat Mk. I χ 10 ⁴ ) Petter Mk. II oil Medium flow of Fe
VOB expiry (g / BHP / hr. SohlitB-
Teretopung 4th 20th 40 5 16 28 6th 12th 21

* Ie GeaiBoh Bit naphthenbaeieohen oils, SAE 50.

BAD ORiQINAL

- 12 -

9098 86/17 33

Claims (1)

Εββο Research and Bng Co.
Claims Fat en t an sprüoh e ₇ ) polyester made from dimers of linoleum 1 acid and a diol of the
general Jorael H
RO-OH r " R-O-OH in which R is a hydrogen atom or an alkyl group sit 1 to
20 carbon atoms and the groups R in each molecule can be the same or different, while a is the value
0 or 1, the polyester having the general formula HO - / Tt - 000 - T - 000 J _n R in which X is the remainder of the diol, 7 is the remainder of the diserene of linoleic acid, R is an organic group, preferably the remainder an aliphatic alcohol sit 1 to 6 carbon atoms or a primary or secondary amine, and η a perfect number ron 4, BAD ORIQtMWL "* 909886/1733 1 to 25 », preferably from 3 to 6, means. 2. Polyester according to claim 1, characterized in that the diol is ethylene glycol. 3 · polyester according to claim 1 or 2, characterized in that * that R means a methyl group. 4. Process for the production of polyesters according to claim 1 to 3 »daduroh characterized in that the diaere of linoleic acid old equiaolecular amounts of the diol is reesterified until aehr than 1 and less than 2 MbI of water per mole of diacid and the diol are formed, whereupon the polyester is an aliphatic alcohol with 1 to 6 carbon atoms per molecule or if a primary or secondary AaIn is uageaetst. 5 »Method according to claim 4, characterized in that as diol ethylene glycol and as alcohol ait I bie 6 carbon atoms Methanol is used. 6. HydrocarbonUl, characterized in that it a polyester according to claims 1 to 3 contains. 7. Hydrocarbon oil naoh claim 6, characterized in that that it contains the polyester in amounts of 0.001 to 5.0 wt contains. SAD OfVGiNAL 909886/1733