DE1919782A1 - Process for the preparation of bis-hydroxyalkyl esters of benzene dicarboxylic acids - Google Patents

Description

Process for the preparation of bis-hydroxyalkyl-eatern of benaol dicarboxylic acids

The present invention relates to the production of bis-hydroxyalkyl esters of receipts © 1-diarboxylic acid. She concerns in particular the preparation of bis-'hydroxyalkyl esters of Benzene-nüiearhonsäuren by reacting a Bensol ^ dicarboxylic acid, such as terephthalic acid, with an alleylenoside, such as ethylene oxide, in the presence of a new catalyst,

The production of bie-hydroxyalkyl esters of benzene-diacid boric acids, such as bis'-> C2 ^ Hydroxyätayl) = - terephthalate, has attained considerable technical importance in the last few years, because these are diesters with the formation of linear super polyesters can be polymerized. These polyesters, such as polyethylene terephthalate, are used to a considerable extent for textiles or tires . 3> The most well-known and widely used method for the preparation of the bis-hyraxyalfeyleater consists in suspending the eenaol-di-carbonic acid in an inert liquid medium and treating the diacid with

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an alkylene oxide in the presence of a catalyst. Various catalysts and reaction media are in the literature door for carrying out such an implementation been. In US Pat. No. 3,037,049, the British Patent specifications 999 242 and 1 029 669, the Dutch patent specifications 6 506 220 and 6 602 077 »of the German patent font 1 157 623, French patents 1 430 842 "and 1 415 134", Belgian patents 660 257 and 666 527 and Japanese Patent 26 341/65 is the Use of such reactants as water »cyclic ethers, such as dioxane, ketones, hydrocarbons, halogenated hydrocarbons, nitriles, alcohols, esters, such as butyl acetate, and Mixtures of dimethylformamide and water are described. The catalysts used in these patents are benzyl tz * - ethyl-ammonium chloride, triethyl-amine, trimethyl-phoapMn, Tri ™ ethyl arsine, tributyl stibine and the chlorides. Sulfates or Hitrate of alkali metals described. From the foregoing it can be seen that many catalysts for the implementation of a Benzene «aicarboxylic acid with alkylene oxides are known, however is the Porachung because of the economic importance of Polyester is always on the lookout for new catalysts.

The present invention provides a method for the manufacture! treatment of bis-hydroxyalkyl esters of bensol dicarboxylic acids Available * The present invention also provides a new one Catalyst available for a process in which a bensol dicarboxylic acid is reacted with an alkylene oxide under Formation of a bis ^ hydroxyalkyl ester of a benzene aicarbon " acid, especially bis (2-hydroxyethyl) ~ terephthalate. Further Features are evident from the following description ..

909845/1697

In particular, the present invention relates to a method for advising bis-hydroxyalkyl-ethers of benzene! carboxylic acids by adding a benzene-dioarboxylic acid, which in suspended in an inert liquid reaction medium an alkylene oxide in the presence of an insoluble, organic, quatern & ren ammonium dew resin in the hydroxide form or in the form of the half salt of the benzene dicarboxylic acid mentioned as Catalyst converts.

The catalysts used in the present invention are known organic quaternary ammonium anion exchange resins in the hydroxide form or in the benzene dicarboxylate form. These resins, which are generally available in the form of holiday or granules, represent insoluble, three-dimensionally crosslinked organic polymers with quaternary monolumines attached to them ₍ such as

OBT. or -VT IF

The total capacity of an anion exchange resin corresponds to the number of ions or fractional groups (such as of the above-mentioned quaternary ammonium groups) per unit weight or per unit volume of the resin and this capacity is generally expressed in mi / equivalents or per equivalents Expressed in unit volume or per weight of resin. Sin quaternary ammonium aniönmustau raw resin with a capacity of 3.0 mi-equivalents per gram would be the same number have quaternary ammonium groups per gram of resin. The template to which the functional groups are bound can vary widely but it is general

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a styrene polymer which is known as diviny benzene "Other resins that can act as matrices of an ion-exchange resin" are phenol-formaldehyde resins, - "chloro-treated; *. Styrene-tivinylbenzene copolymers and the like "The Teroaren ATnmonium" Anionenaustausehliarsie ₉ di® can be used for the invention., Kttanen. The (! remain gel-like resins, which have a relatively low porosity, or e can m & kroretiimlare resins (replacement resins with a network-like confused structure), which have a relatively bone porosity -tebe » _s , the macroreticular resins ie preferably tferiem <j - because a better one Ensure contact of the Umsetefflägaköjagoneatea with äes lysator. As the Lehmann "b@kB.nnt" is »this easily accessible qnat@rpJS.Ten
Use exchange resins to a large extent for the removal of the most common ions from solutions or for other purposes. «det. Some commercially available resins like those for the present ©. "Suitable for the invention are those" as sold by the Messenger Haas Company under the trade names Ämberlite XBA ~ 9Q4, Ämberlite IRA-91O, Araberlite XRA-42 or such as βIe. from the Dow Chemical Company under the trade names Bowex 1 and Dowex 2 are sold. The commercially available quaternary ammonium anion exchange resins are generally in the. Supplied in chloride form and in such cases it is necessary to convert the resins into the hyd ^ oxide form by treating them with sodium hydroxide or they are converted into fluent half-salts of bensol-dioarbanaic acid by mixing the resin with an aqueous solution of an alkali half salt of the Benaol ~ di ^. carboxylic acid, for example with monosodium terephthalate. These alkali half salts can be prepared by adding 1 mol of the diacid to an aqueous solution which contains 1 mol

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one contains alkali hydroxide · You preferred Hanse for the present invention are those making the following quaternary Ammonium groups bound to the matrix contain:

* A "oäer -H. A"

where E is an alkyl group with 1 to 4 carbon atoms, special methyl or ethyl, and R 'is an alkylene reed with 1 to 4 carbon atoms, in particular ethylene or Kethylene, and A "* is a HydroxylioE or a Benaol ^ di carboxy la t-

ion, that is

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means"

An alkylene best is understood to mean radicals of the formula -C_ -CH ₂ ^ or -OH ₂ CE ₂ - When using the anion exchange resins as catalysts, it is generally desirable to use them in amounts such that about 0.001 to 0.13 "Preferably 0.005 to 0.15 equivalents per mole of benzene" dicarboxylic acid can be used.

The method according to the invention can be carried out in various ways and be carried out discontinuously or continuously. Since the benzene-dicar-

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Bone acids In general, very insoluble substances are used when carrying out the process, preferably in a finely divided form, by moving in the 1.0 to 15 _{tons of} oil, preferably 2.5 to 10.0 colors the reaction aediw "" pending and then old of the alkylene oxide in the equivalent of the new catalyst according to the invention uneaten. On the basis of the "valuable build-up systems", there is a solution in the reaction medium under the reaction conditions, and therefore generally completely in the reaction medium if sufficient amounts of the leakage medium are used. The temperatures "which can be used for the present invention can vary in the range from about 80 to 200 ° 0", they are preferably in the range from about 115 to 160 ° 0. The pressures can vary superatraospheric and subatmospheric drills ^ with the "! tend Yorrausseteung" that the Hwuuk auisreicb, t ₉ in the liquid Reaktionemedium- in the liquid Aase to h & ltmir Ia general, the pressure jedocstl t> el about 1 to 30 'Atnoe-. pbftren ". the Terweilseit the reactants in the leaktionszoa® is generally about 2 to 180 minutes.

The alkylene oxides should be present in amounts of about 1 »7 Ms 3 molar mol of the carboxylic acid» where »at amounts of 2 to 4 mol per mole of the diacid are preferred» Ethylenoxlsä is the alkylene oxide preferred for the present process and the one to be avoided Silicon & ure 1st Tarephthalic Acid, Me invention, however, does not refer to these compounds. The suitable alkylene oxides include vioinal epoxides with 2 to € carbon atoms such as 1,2 - »: propylene oxide and 1,2-butylene oxide, while other benEol di-carbonic acids such as phthalic acid and isophthalic acid can be used. Ss is too

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possible mixtures of alkylene oxides and / or mixtures of the Use dicarboxylic acids for the present invention.

The respective method for separating the bie ~ bydroryalkyl ester from the reaction medium does not form part of the invention and numerous methods are available to those skilled in the art. After completion of the esterification reaction in a continuous process, the reactor contents probably consist of unreacted alkylene oxide. unreacted, solid bicarhonic acid ₉ the liquid reaction mixture used, the soluble Eiester product and the insoluble aalonette Austmusehhar as a catalyst. worked up by first evaporating the alkylene oxide, subsequently separating the solid acidic acid and the catalyst by filtering and possibly cooling the remaining solution of the beast, whereby the diester product crystallizes out. The crystallized beast can then be removed by filtration with or without vaechen. In a continuous process, the effluent from the reaction can be removed from the reactor through a filter * so that the solid dieöure and the solid anion exchange resin catalyst remain in the reactor, and the effluent only essentially consists of a solution of the blester product in the liquid reaction medium and some alkylene oxide. Zn this case you can simply relax the Abflieseende to the alkylene eu remove and then cool "to the product zn kristal" taping. When crystallizing a solution of a bis * hydroxy «alkyl ester of a BenBcl-dicarboxylic acid in a liquid medium, one can easily determine the respective temperature up to which the solution has to be cooled in order to bring about the crystallization, whereby the temperature depends on the type of

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respective siesters and on the type of each used liquid medium depends on «One crystallizes, for example bie «(2-Hydroxyätbyl) terephthalate from xylene, ep it is advantageous to keep the solution below 40 ° C and preferably below Cool to 25 ° C BU in order to obtain the best possible diestera. Yield to ensure Hacb of the extraction of the beasts can they are used to remove residual impurities treat in a variety of ways. You can E.B. from a Recrystallize aqueous solution to remove nitrogen-containing impurities BU.

Inert reaction media as used in the present invention are generally known and it only needs to be noted that the reaction medium nisfat with the Reactants are allowed to react and that it must not settle under the reaction conditions Reaction medium from an organic compound, that is an organic compound or a mixture of an organic compound with water. As mentioned before, For example, cyclic ethers, ketones, hydrocarbons, water, halocarbons, alkyl esters of alkanoic acids, and the like have been described in the literature as reaction media. 2-alkyldioxolane and 2.2 ° »dialkyldioxolane are also suitable, as well as nitrobeneol and nitrotoluene as reaction media · Preferred reaction media for the present invention are hydrocarbons and halogenated hydrocarbons. Most will Of the hydrocarbons, the alkylbenzenes having 6 to 10 carbon atoms, such as xylene, ethylbenzene, toluene and cumene, are preferred. From the chlorinated hydrocarbons]! are the chloroalkanes and chloroaromatics, which are not ethylenic and acetylenic double bonds contain, such as 1,1,2

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ethane, chlorobenzene, ρ-chlorotolu oil, dichlorobenzene and 1,1,1 Trichloroethane preferred.

Be lBtle'l. . 1

Amberlyst A-26 is made in the chloride form in a catalyst by converting it to the hydroxide form. Amberlyst A-26 is the trade name of the Rohm and Haas Company and represents a biacroreticular, quaternary ammonium anion exchangeable with the functional groups -N (CH,), (chloride form) on a styrene-egg vinylbenzene matrix. The resin is converted into the hydroxide form by placing it in a column, treating it with 1 volume volume of 5 volume sodium hydroxide solution, washing it with 5 volume volumes of distilled water, mixing the resin with cyclohexane and then the mixture in a container, which is provided with a Dean ~ Stark ~] all, heated until the water is azeotroped off. The resin in the hydroxide form has a capacity of 0.45 milliequivalents per milliliter *

Example

A 5-Lite3v Stirauto: klav is prepared with 600 g (3.6 mol) of serephthalic acid (in a purity as it is used for the production of fibers), 1600 ml of butyl acetate and an amount of a catalyst prepared according to Example 1, the sufficient to deliver about 0.11 equivalents, filled and then flushed with stick «=. 473 g fltiseiges ethylene oxide (10.75 mole) are added to the reactor and this is heated to 130 ° C, passing internally Barapf by internal heating coils. The tempera-

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The door is held for 60 minutes at 130 ° C with a bridge of about 10.5 kg / cm ² . After the 60 minutes have elapsed, the reaction is ended by pressing the contents of the autoclave into a vessel in which the ethylene oxide is blown off and the unconverted terephthalic acid and the solid catalyst are separated off by filtration. When the filtrate is cooled to about 25 ° C., about 90 g of bis (2r-hydroxyethyl) terephthalate (dry) are obtained. The conversion of the fed terephthalic acid into the diester product is about 10 mol ~ #. Although the reaction temperature of 130 ° C is above the manufacturer's recommended maximum temperature for Amberlyst A-26, only little decomposition of the anion exchange chiaarsea was observed. As can be seen from small amounts of nitrogen impurities in the product, but a slight decomposition has taken place »

B e i s ρ i e 1 3

The procedure of Example 2 is repeated using; of the catalyst separated off in Example 2, but 1600 ml of xylene are used instead of butyl acetate. Hau receives about 110 g to ~ (2 ^ Hydro2yäthyl ^ terephthalate

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Claims (1)

r * r t * r r 0-4551 T8. April 1969 P a t β a t a η β ρ r ü ehe 1. Process for the preparation of bie-hydroxyalkyl-ethers of Sensol dicarboxylic acids by reacting a Benssol dicarboxylic acid suspended in an inert liquid reaction medium with an alkylene oxide in the presence of a catalyst, characterized by »that nan as a catalyst an insoluble« organic, quateraäres ammonia, anionic acid in the hydroxide * or «or in the form of the half-shell of the named Beneol-dioartionic acid used S. The method according to claim 1 »characterized in that eur Production of bi- {2-hydroryethyl) terephthalate, terephthalate, xthylenozide is set 3 · The method according to claim t, characterized in that the * inert liquid reaction medium a hydrocarbon or is a halogenated hydrocarbon 4. The method according to claim 1, characterized in that «the quaternary Aomoniua groups attached to the die of Harses are bound to the formula -H- (R-) * A * or -H in which R is methyl or ethyl, R * is methylene or ethylene, A ^{- is} a hydroxyl ion or a Bettsol dicarboxylate ion and in which the said catalyst is present in an amount sufficient to about 0.001 to 0.3 equivalents per time Bentsol diacid available «u provide · BAD ORlGSHAL "1t - 90 984 5/1697 5 · The method according to claim 4 »characterized in that the temperature is about 115 to 160 ° C and the pressure is about 1 bie
30. Atmospheres and the alkylene oxide present
is present in an amount of about 2 to 4 moles per mole of Bensol * <dicarboxylic acid. 6. Method according to Arm ρ ru eh f? » characterized in that then inert liquid «; ItoRktionsmittel an alkylbenzene or a Halogenl'ohlenwai? RKiretof.f, which is free from ethylene and
acetylene:! ¹ · eggien Un # esa.ttix £ tbaJton represents. 7. The method according Annnmeii 6, characterized in that the catalyst in & Uw, r Volume is present which is sufficient to provide su about 0.005 to ¹ J ₁ 'ff equivalents per Koi Benssol-dicarboxylic acid sur available. 8. The method according to claim 7 _S, characterized in that on the preparation of back C2-Hyärosyäthyl) terephthalate ethylene ■ oxide is reacted with ferephthr] acid * 9. Method rea «h claim 8, characterized in that the ilatrise «es quaternf'ii'esi ammonium ion exchange hareses a Oapolymerlsat is " Process according to AKspTnek 8, marked as aflur «h, the © the quaternary« ΑίΜίοϊΐίΐξΚ · FuiionenausstauBchharz in the hydroxide- '
shape 1. Procedure na-'h ArrF-priirih 8, characterized in that the quaternary © Amnsoniuui-p.uilonenaiis exchange resin in the form do a
Halbsalssealer (perephthalic acid is present. - 12 ~ ■. BATH ORIGINAL 90984 5/169 7