DE1568980A1 - Process for the preparation of glycol esters of carboxylic acids - Google Patents

Description

W. 12451/66 13 / Ko

Mitsui Petrochemical Industries, Ltd. Tokyo (Japan)

Process for the production of glycol esters of carboxylic acids

The invention relates to a process for the preparation of glycol esters of organic carboxylic acids in good yield if " ¹ neither discoloration of the resulting esters nor of the products obtained therefrom occurs during processing of the esters. The invention also relates to those used in such a process In particular, the invention relates to a process for the preparation of glycol esters of organic carboxylic acids from the group of aromatic, aliphatic and alicyclic carboxylic acids, which may optionally carry substituents, by reacting an alkylene oxide having 2 to 4 carbon atoms with such an acid in one organic solvent in the presence of a catalyst.

009814/1977

£ 8 It is known that an organic carboxylic acid z. B. an aromatic, allphatlsche or alioyclische Carboxylic acid, which may optionally have a substituent, with an alkylene oxide in an organic one Solvent in the presence of a catalyst for the preparation of the corresponding organic carboxylic acid glycol ester can implement and obtain useful polymers by polycondensation of such esters.

Xn of British Patent 623,669 is a method for carrying out the reaction described above described in water as the reaction medium, in which amines or alkalis are used as a catalyst. In addition, British patent specification 906 722 (US patent specification 2 932 662 ;: German patent specification 1 138 030) a process described in which the reaction in an aqueous medium using amines as a catalyst is performed. However, there is the method in which an organic solvent is used as a reactive medium becomes, the procedure in which water is used as the reaction medium, in terms of yield and purity of the product, proposals were made to carry out the reaction in organic solvents

0098U / 1977

8ο 1st sub example in British Patent Specification 915 β91 (US Patent 3,037,049; German Patent 1 155 11 ¹ I-) proposed · 1η methods in which bis- (B-aroxy "thyl) terephthalate in a high yield when executed the leaktion «between terephthalic acid and ethylene oxide in methyl ethyl ketone in the presence of a tertiary amine as a catalyst, z. B. Tri-n-propylamine, 1 £ § | §ί81 *% will.

Although excellent results in terms of yield and purity of the product with this procedure are obtained, this often occurs a discoloration of the resulting organic carboxylic acid glycol ester, Or the particularly disturbing phenomenon is observed that the material produced from this ester as a starting material The polymer product is discolored, although the ester appears to be of high purity and not discolored 1st.

The cause of this discoloration is not yet complete clarified * In addition, if this is prevented discoloration is to be, co-ordinated procedures are required to eliminate the cause of the discoloration, and it is therefore evident that this is a significant technical disadvantage represents.

Investigations have been carried out, including one > '<eg to prevent the occurrence of the cause of the hardly foreseeable and difficult to avoid discoloration to be found,

009814/1977

BATH ORIGINAL

it was found that the organic carboxylic acid glycol esters can be obtained in good yield without the risk of discoloration can be produced by carrying out the reaction using a catalyst that has hitherto been used for this type of τοη Esterification reaction has never been proposed Further research showed that the "bindings that the tert. Photphinen, tert. Arsines and tert · stibines

catalytic / belong, have an advantageous / activity and no ·

Cause discoloration.

The object of the invention is to create a method for the production of high quality organic carboxylic acid glycol esters by converting an organic carboxylic acid old an alkylene oxide in an organic solvent in the presence of a catalyst, the conversion being carried out in the presence of a catalyst from compounds which have never been proposed for this purpose, in order to prevent the cause of the discoloration of the ester and of the polymers produced from it, which has been the case with the previously known procedures could not be avoided, and in addition, there are no disadvantages in terms of yield or the like. Another object of the invention is to provide catalysts which can be used in such advantageous manufacturing processes can be used.

00981A / 1977

The method according to the invention is characterized in that that the reaction between the carboxylic acid and the - ^ lkylenoxyd using a catalyst of at least one tert. Phosphine, tert. Arsine and / or tert. Stibine of the formula R * X executes, in which R is a phenyl or represents an alkyl radical having 1 to 5 carbon atoms, where the radicals R can be identical or different, and X Means phosphorus, arsenic or antimony.

The organic carboxylic acids and alkylene oxides to be used as the starting material are all common ones known combinations useful. The carboxylic acids include aromatic, aliphatic and al! cyclic carboxylic acids, which can optionally carry substituents, Ie with regard to their catalytic activity and ability to Preventing the occurrence of the cause of discoloration is particularly advantageous in the method according to the invention Acids, the benzene mono- or polycarboxylic acids, which may have substituents, the naphthalene mono- or polycarboxylic acids, the cycloalkane mono- or polycarboxylic acids and the aliphatic mono- or polycarboxylic acids having 1 to 20 carbon atoms.

0098U / 1977

With regard to the catalytic activity and ability To prevent the occurrence of discoloration, benzene monooarboxylic acid, Benzene dicarboxylic acids, monosubstituted benzene monoarboxylic acids, cyclohexanecarboxylic acids and the lower aliphatic ones Carboxylic acids are particularly preferred. As substituents of the monosubstituted benzene monocarboxylic acids mentioned above, z. B. methyl, nitro, chlorine and the lower Alkylreete be present.

The organic carboxylic acids to be used as the starting material include naphtholic acid, naphthalenediearboxylic acid, Naphthenic acid, benzoic acid, nitrobenzoic acid, chlorobenzoic acid, toluic acid, tert-butybenzoic acid, phthalic acid, Isophthalic acid, terephthalic acid, benzenetricarboxylic acid, benzene tetracarboxylic acid, adipic acid, cyclohexanedicarboxylic acid, Acetic acid, chloropropionic acid, nitrobutyric acid and cyanocapric acid *

They succeeded as the starting materials for use lkylenoxyde ^A containing 2 to 4 carbon atoms in the molecule, and z comprise. B. ethylene oxide, propylene oxide and butylene oxide.

As indicated above * the implementation according to the Invention carried out in an organic solvent »With regard to this organic solvent there is no ·

0098U / 1977

special provisions, as long as it is inert to the reactants under the reaction conditions and can dissolve at least one of the reactants. For this purpose, e.g. B, the following in solvent svr application gelsngent hydrocarbons, halogenated throats Vtaeerstoffe, nitro hydrocarbons, ethers, ketones, organic esters, nitriles and laetones, ι. B. flexan, cyclohexane, toluene. Chloroform, ethylenedl chloride, chlorobensol, hydrolyzate ether ₉ dioxin, tetrahydrofuran, acetone, methyl ethyl ketone, acetophenone, ithylaoetate, ethyl acetate, acetonitrile, lenionite film and f-butyrclectone. AIa catalysts will »in the case of the process according to the invention. Phosphine, tert · Areine and "tort. Stibine of the formula R ^ X used, in which 1 a phenyl radical and / or alkyl radical with 1 to 9 carbon atoms and X means phosphorus, arsenic or antimony« These compounds can be used alone or as (taaison το »» ihreren connections methodology is used. in addition, eii both the phenyl as AUOH ^a lkylreste la molecule contain or may consist of a compound in which only one or the other of the best. from 1st contain technical aspects are Trlphenylphosih £ n , Triphenylarsin and tryphenylstibine.

0098U / 1S77

BATH ORIGINAL

fell according to the practical execution of the procedure of the invention, the organic carboxylic acid and the organic solvent in a ratio of 0.5 to 20 parts by weight and preferably 1 to 10 parts by weight of the latter are used per part by weight of the former. If the carboxylic acid is difficult to dissolve in the organic solvent, an appropriate amount of the will technically be used Solvent sur transferring the mixture in the form of a Sohlammes preferred, with a three- to ten-fold amount of solvent being used here in general. Furthermore, the molar ratio of the organic carboxylic acid to the alkylene oxide is expediently in a molar amount

the from / 0.8 to 1.5 times the stoehiometric amount used.

Although products of high purity below this range can be obtained, this is not practically advantageous because there is an increase in the amount of unreacted organic carboxylic acid. On the other hand occur Fiixo m \ f, in which the alkylene oxide is discarded if this area wlra exceeded, that a polymer Bilauue! Satsxtigen material takes place α the purity of the desired product is lowered.

The amount of catalyst used is preferably 0.1 to 10 parts by weight per 100 parts by weight of organic carboxylic acid. If the amount of catalyst is large, the

0098U / 1977

BAD OFHGiNAL

Reaction temperature can be decreased; however, since the Formation of a polymer-like material is promoted, not only the purity of the product is lowered, but the separation of the desired product from the reaction mixture is also made more difficult. ϊίΓβηη, on the other hand, the amount of catalyst is insufficient, the reaction temperature must be increased. There are cases in which the The results obtained are undesirable by making the product a polymeric material depending on the used organic carboxylic acid can result.

Those used in the method according to the invention reaching polymerization temperature is in the range between 50 ° and 200 ° 0 and preferably between 80 ° and 180 ° 0. The method can bie under an overpressure of 0

50 kg / cm. Usually it is preferred to carry out the reaction between the organic carboxylic acid and the alkylene oxide under a Uber atmosphere pressure, the latter being in a liquid state. The use of an inert gas is desirable for this purpose « However, the reaction can also be carried out with the addition of the alkylene oxide to the reaction system under atmospheric pressure. The method according to the invention can be carried out both batchwise and continuously

0098U / 1977

τ "5RlGSNAL

- ίο -

The vast majority of the after the procedure Products made according to the invention can be any brewable and valuable intermediate for making clay Plasticizers, resins and paints without any further Cleaning can be used. The olympic esters of terephthalic acid can, for. B. when heated to form a substance of high molecular weight polycondensed «ground ·

The invention is hereinafter referred to as "η >>" ™ < explained in more detail by examples.

example 1

A 500 ml autoclave equipped with a stirring device Stainless steel was made with 50 g of terephthalic acid, 26.7 8 g of liquid ethylene oxide, 3 g of triphenylphosphine and 150 g Methyl ethyl ketone is charged, whereupon the reaction takes place after the air in the autoclave has been displaced by nitrogen two hours at 130 ° C under a nitrogen pressure of 20 atm. After the end of the reaction, the reaction mixture was filtered hot, with 2 g not « reacted terephthalic acid were separated. The JiItrat

was * cooled to 5 ° G and 64.3 g of deposited biB- (I-5ydroxy) terephthalate were separated off by filtration

0098U / 1977

- li -

ethyl The melting point of this biB- (B-Hydrojtir) terephthalate was 109 ° 0 · When dissolving 2 g of the organic ester · in 20 ml of βineβ L solvent mixtures of 20 parts of water and 80 parts of Itmsnol, the optical density at a wavelength Toa was 180 Μψ. 0.051 and the saponification feel was 439 · This material was made from. Methyl ethyl ketone was recrystallized and was subjected to the polymerisation reaction for animal hours at 270 ° 0 under a nitrogen pressure of 0.4 Hg ^ in the presence of antimony trioxide, a colorless polyethylene terephthalate being obtained.

Example 2 and Verielchsveruch 1 The "Autokle.Y described in Example 1 vurde with 50 s terephthalic acid (rabbit number 100), 26.7 g liquid" ethylene oxide, 3.7 g (0.014 mol) trisshenylphoephine and ISO g methyl ethyl ketone besGhiokt, whereupon the reaction during swel Stunlenbei 110 ° 0 under a Sticketoffdruck τοη was carried out 15 atmospheres "Dannsh the fieaktionsmiachung was treated as in example 1, 64.5 g wcbti terephthalate, melting point 109 ° O ^ ₉ were obtained in example 1, the NaOH beschneibenen Yerfahre "Determined optisab * value was 0.050 \ mA the saponification level ar 4443, With polymerization" this E "t? ··:, · naob Uxücristallisation

As in βΐ 1 ma de eie colorless fol7ätäylent «rephthalat

0098U / 1977

BATH ORIGINAL

For comparison, 2 g (0.014 mol) of tri-n-propylamine were used instead of the aforementioned tri-phenylphosphine and, using the same procedure as described above, 63-8 g of As- (B-ltydroxyethyl) terephthalate were obtained (comparison 1) · This bis (ß-hydroxyethyl) terephthalate had a Melting point of 109 ° C, an optical density of 0.060 and a saponification number of 439 · Si «color of the after The polyethylene terephthalate obtained from crystallization and polymerization of this ester was brown.

Example 3

The beschreibene in Example 2 procedure was carried out using 50 g of terephthalic acid, 26.7 g ,, liquid "Äthyltnoxyd, 2 g of triphenylphosphine and 150 g of acetonitrile, and 67» 3 g bending (ß-h _y droxyäthyl) terephthalate, Schmfilspunkt 109 ° 0, Saponification Steel 440.

Examples 4 to 8

The procedure of Example 3 was repeated except that it was used in place of that used therein Triphenylphoephins as shown in Table I below Catalysts indicated were used and the respective results set forth therein were obtained.

0098U / 1977

! Table I Catalyst and yield of BiB- (B- »hydro3gräthyl) terephthalate

example catalyst Catalyst-
amount (κ) Yield of bia-
(ß-hydroxyethyl) «- terephthalate (κ) 4th Trimethylphosphine 0.8 65.0 '5 Triethylarsine 1.5 61.8 6th Tributylstibine 2.5 57.6 7th Triamylph.ospb.in 2.0 5 *, 1 8th Diphenylethyl
phosphine 1.8 66.8 Example 9

The working cycle of Example 1 was modified with the modification repeats that instead of 3 g of triphenyl phosphine 1.0 g Triphenylphosphine and 2.3 g triphenylarsine were used, 65 g Bii>. (ß-hydroxyethyl) terephthalate were obtained

Example 10

50 g terephthalic acid, 26.7 g liquid ethylene oxide, 3.5 g triphenylarsine and 150 g acetone were in denin Example 1 described autoclave, whereupon the ßeaktion was carried out for two hours at 125 ° C under a nitrogen pressure of 30 atm. Bas reaction - product was filtered hot under superatmospheric pressure, with 2.2 g of unreacted terephthalic acid being separated off. Then * was cooled to 0 ° C and 64 g of BIe- (B-. HydroxyethyD-terephthatt separated "tie optically · Diohte of the Bie-Cβ-hydroxyethyl & erephthalate thus obtained was 0.050.

Example 11

The procedure described in Example 10 was used using the reaction given in Example 1 · - »participant with the modification that instead of τοη Methyl ethyl ketone 220 g of ethylene dichloride were used. 67.3 g of bis (β-hydroxyethyl) terephthalate were obtained.

Example 12

The procedure described in Example 10 was carried out using the reaction given in Example 1 - with the amendment that instead of the Methyl ethyl ketone 500 g of ethyl acetate were used 57 g of Bi8- (ß-hydroxyethyl) terephthalate were obtained Upon further concentration of the filtrate, 8 g of bis (β-hydroxyethyl) terephthalate were separated off. *

Example 13

The procedure described in Example 1 was Repeated with the modification that 120 g of dioxane were used instead of the methyl ethyl ketone. 55 g of BIe (e-hydroxyl) terephthalate were obtained.

0098U / 1977

Example 14

50 g isophthalic acid, 26.7 β liquid JLth / lenoxyd, 3 g friphenjrlphosphia and 100 g Äthylendlehlorid were in dta Ia example 1 described in the autoclave and 41 «reaction was taking place during 2 hours at 110 ° C • Inta nitrogen pressure of 15 »tti carried out · The reaction tpiBeH» mrdt then filtered at 70 ° 0, whereby 0.5 β I · © - phthalsittrt were transferred. F * ah cooling was 60.2 β Bii «(Ä * tayaM7lthyl) -> Uopüthe.lat received.

BeliPltl IS

In .Btlipltl 1 ae autoclave was old 50 g oyelohexandloarbozic acid "" 26.7 g flow if # "3 β Xripatnylphospoin and 150 g ütttgrlieobutyUcetoa be * ■ fthtki" whereupon the reaction for two hours at 115 * 0 below? "Int * nitrogen pressure of 15 atmospheres was carried out. The reaction money was then carried out with a sufficient amount of irerdLUazite» Auaoniftkwaeser to remove setsttr 8 £ vixe, then with water and * in «r little dilution of salic acid» for removal of the catalyst and • 6hii «aiieh Washed with water and with hatriussulfat g * ~ Bae I ^ suaesmittdX v was removed under reduced ", whereby 62.8 g Bl" - (. ^>! 37d) at esrh & ltte. «» Rdtn «0098U / 1977

BATH ORIGINAL

Example 16

The autoclave described in Example 1 was Bit 50 g of benzoic acid, 26.7 g of liquid ethylene oxide, 2 g of triphenylphosphine and 150 g of benzene besohiokt, whereupon the

Air in the AutoHaven replaced with nitrogen and a

2 «1t nitrogen / pressure up to 150 g / cm overpressure / was sucked» Di « Reaction mixture was then reacted for two hours while maintaining the temperature at 110 ° C. After completion of the reaction, the reaction product was washed with a 5% aqueous sodium carbonate solution to remove the unreacted benzoic acid by extraction into the aqueous solution, whereupon it was de-diluted. The yield of benzoic acid glycol ester clay was 93.4%. The boiling point of this estera was up to 156 ° C / 11 µHg ₁ even when it was heated

No discoloration of the material was observed for 10 hours at 150 ° C. The most unreacted benzoic acid Extraction liquid containing hydrochloric acid acidified, but no benzoic acid was cooled at all. Accordingly, the conversion of the benzoic acid was in this reaction 100%.

0098U / 1 977

- 17 - Example 17

50 g of benzoic acid, 28.6 g of propylene oxide, 2 g of triphenylarsine and 150 g of xylene were used and under Using the procedure described in Example 16, propylene glycol benzoate was obtained in one yield obtained by 88.4%.

Example 18

Nitro 50 g p-benzoic acid, 13.5 g liquid ethylene oxide,

1.5g triphenylphosphine and 150facetonitrile were used and using the procedure described in Example 14, there was obtained 62.2 g of glycol p-nitrobenoate.

Example 19

50 g of acetic acid, 58 g of propylene oxide, 4 g of tripheaylstibine and 200 g of acetonitrile were used in the in Example 1 autoclave described and the reaction was carried out for two hours at 140 ° 0 under a cloth pressure run from 20 atm. To. Termination of the action was by distillation of acetic acid propylene glycol ether in one 87.7% yield obtained

0098U / 1977

Example 20

30 g of acetic acid, 150 g of benzotonitrile and 3 g of triphenylarsine were introduced into a three-necked flask equipped with a stirrer, a reflux condenser and a gas inlet nozzle, followed by gaseous ethylene oxide for four hours from the bottom of the flask with a circulating pump, while the reaction mixture was fed to 120 ° The reaction mixture was distilled until the acetic acid was completely consumed, 49 »5 g of acetic acid glycol ester distillate were obtained. The distillate amounted to 82 % of the converted acetic acid.

In Table II below are those obtained in Examples 1-20 and Comparative Experiment 1 Results summarized.

0098U / 1977

ORIGINAL INSPECTED

(G)

(β)

middle

Catalyst (S)

Tfmp., DTUCJt ₉ ZtIt

( ⁸ C) On / « ² ) (BM *.)

Yield

Cf)

Terephthalic Ethylene- - Methy Iith7l-50

See 1

3 ο

* S

00

2

■ acid

10 11

50 50 50

50

50 50 50 50 50

50

50

26.7 ketone 26 · 7 ^{Η Λ} 26.7 "26.7 acetonitrile

26.7

150

26.7 " 150 26.7 " 150 26.7 " 150 26.7 - 150

26.7 methyl ethyl ketone

26.7 acetone

26.7 ethane dichloride 220 Trlphenylphosphblm 3

2.7

Tri-n-propjlamin 2.0 Triphenylphosphine 2.0

Triaethylphosphine 0.8

Triethylarsine

130 HO HO

110

110 HO HO

t Tributjlstibla

• 2.5 triaeylphonphine

2.0

Diphenylethylphosphine 1.8 Triphenylphoephine 1.0 triphenylarsine

Triphenylarein

3.5

Tripheny! Phosphine 3

20 15 15

15th

15 15

15 15 15 20

30 30

2 2 2

2 2 2 2 2

2 2

64.3

64.5 63.8 +)

67.3

65.0 61.8 57.6 58.6 66.8 65.0

64.0

67.3

+) reddened polymer

co 'co

Table II fFortaet

example No,

Seed

ure (β)

• rial Alkyl

[IkyTenöxyd solvent (S) (β)

Catalyst (S)

g ^{nT | g} e; it

Temp pressure _o time ( ^ö c5 (kg / cm ² ) (hrs.)

yield
(β) 0 65, 0 55, 2 60, 8th 62, 4 « 93, · * 88 2 62, 7% 87 5 ♦♦) ♦ 9,

Terephthalic ethylene oxide, ethyl acetate

acid

50 50

Isophthalic acid 50

26.7 500 26.7 dioxane 120

O
(O
00

26.7 dicalorethane 100

26.7 methyl isobutyl ketone

26.7 benzene

Cyclohexane " dicarboic acid 50

Benzoic acid ⁿ 50

"50 propyleno-xylene xyd 28.6

p-nitrobene »ethylene oxide acetonitrile acid 50 13.5 150

Acetic acid propylenozide " 50 58

30 ethylene oxide bensonitrile (Gas) 150

Triphenylphoe-
phln 3 125 30th 3 130 20th 3.0 110 15th 3.0 115 15th 3.0 110 15th Tripheny larsine
2.0 110 15th Triphenylphoa-
phln 1.5 110 15th TrIphenyIstibine
4 » 140 20th Triphenylarsine 120 at

2 2

2 2

++) glass reactor

Claims (3)

- 21 claims 1. Process for the preparation of glycol esters of carboxylic acids by reacting an optionally substituent having aromatic, aliphatic or alicyclic carboxylic acid with an alkylene oxide with 2 to Carbon atoms in an organic solvent in the presence of a catalyst, characterized in that the catalyst used is at least one tert.phosphine, tert.arsine and / or tert. Stibine's formula used in which R is the same or different and in each case a phenyl radical or alkyl radicals having 1 to 5 carbon atoms and X is phosphorus, arsenic or antimony. 2. The method according to claim 1, characterized in gekennaeicb.net, that the solvent used is nitriles, ketones, hydrocarbons, halogenated hydrocarbons, organic acid esters or ether used. 3. The method according to claim 1 or 2, characterized in that a benzene mono- or polycarboxylic acid, naphthalene mono- or polycarboxylic acid, glycloalkonemono- or polycarboxylic acid or an aliphatic ^ mono- οά * ν polycarboxylic acid with 1 to 20 carbon atoms in the alkylene molecule is used implements. 003814/1977 ORIGIMAL. 4- · Process according to one of the precedents 1 to 1 ₁ characterized by the fact that "an tin" Bensolaono "afto & ~ acid, bensol dioarboxylic acid, simply anbetituiett · Jenaol * ■ onocarboxylic acid," has in particular a »methyl or hitroreate as a subitituent, a OyclohexanearboMÄure _t tin · OvOlohexanedioarbonaäure or a lower aliphatic carboxylic acid »it de» Alkylenelylieioxyd u »etst. 9 · Proceedings according to a »der Aneprilehe 1 bii V ^ characterized by the fact that "tertphthalic acid, laophthalic" acid or acid »it de» alkylene oxide uaeetit · 0098U / 1977 BATH ORIGINAL