DE2229755A1 - Process for the preparation of compounds and polyesters substituted by one or more alkoxysulfonate groups - Google Patents

Description

FhC Corporation, 1617 Pennsylvania Boulevard, Pennsylvania / USA

Process for the preparation of substituted by one or more alkoxysulfonate groups Compounds and polyesters

The invention relates to a process for the preparation of compounds formed by one or more alkoxysulfonate groups are substituted, as well as by polyester or mixed polyester resins, which an alkoxysulfonatubstituierte Compound or from the alkoxysulfonate-substituted monomer, contain derived segments. The final polyester product obtained in this way is particularly suitable for manufacture of threads and films and can easily be colored with basic dyes; it has a sufficiently high Intrinsic viscosity., So that it is a

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Is fiber former and it should preferably have a carboxyl content of less than about 5C equivalents per willion Grams (i ^ q. / 10 g or rrL.q./kg).

The present invention relates to a process for the preparation of a compound substituted by a 1-letallalkoxysulfonatgruppe by reaction of an alkali or alkaline earth metal salt or a derivative of a compound (A) from group (a) a phenol, (b) one by one or more phenolic Group-substituted organic compound and (c) U ₁ OOC-CH-COOR ₁ , in which R ₁ denotes a lower alkyl radical with 1 to 4 carbon atoms and h " denotes a hydrogen atom ₍ a phenyl radical, a tolyl radical or a lower alkyl radical with 1 to 4 carbon atoms, with an alkane sultone in a reaction medium consisting of a molten lower alkyl (C, -C,) dicarboxylate.

The salt or derivative can be prepared by reacting the compound (A) with an alkali or alkaline earth metal or a compound thereof to form the corresponding MetalisaL it ^v or the corresponding derivative of the compound (A) and dispersing the metal salt obtained or the derivative in the reaction medium be prepared, sufficient alkane sultone being added for the reaction with the metal salt or the derivative.

When an organic compound containing one or more phenolic groups with an alkali or alkaline earth metal or a compound thereof is reacted, a salt of the organic compound is formed, while when a of the above-mentioned compounds (c) (dialkyl malonate) with the

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the same alkali or alkaline earth metal or a compound thereof is reacted, the product formed is not a salt, but hereinafter referred to as "metal derivative".

A preferred compound (A) is selected from the group of compounds of the formulas

(a)
(R ₁ OOC)

OH (c) 0R ₀

R _n OO

, -0-0 ^

COOR ₁

(d) OH

0OR, Z-OH

(COOR,) Ix

OH

(e)

O (CI-I ₂ ) _n OH

and (f) R
I ^J

R ₁ OOC-CH-COOR ₁

where mean:

"fi" is a lower alkyl radical with 1 to 4 carbon atoms, t,;: and γ is the number 0 or 1,
η is an integer from 2 to 4,
Q and P are each alkyl radicals with 1 to 6 carbon atoms,

Alkoicy radicals with 1 to 6 carbon atoms or halogen atoms and
Z is an unsubstituted radical "

Dei dc: Production of a polyester resin is the reaction

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Mixture of the above process, sufficient glycol is added to the transesterification of all polyester-forming reactants to achieve, wherein a transesterification reaction is carried out with the formation of a prepolymer and then the prepolymer polycondensed wirci.

The following equations are intended to provide some of the preferred embodiments of the invention with regard to the "in situ" preparation of compounds substituted by alcoholsulfonate groups in a melted aliphatic or aromatic Explain the dicarboxylate reaction medium in more detail:

(1) X-OI + ROM> X-OM + RAW

(Metal salt)

Melted dicarboxyiate

(2) X-OM + alkanesultone) X-O (CH ₉ ) SO-M

rf - LL «3

where mean:

R is a lower alkyl radical with 1 to 3 carbon atoms, X is an organic radical or a substituted organic Rest,

Ii is an alkali metal and
η is a positive integer corresponding to the number of carbon atoms in the alkane sultone reactant used.

If a dialkyl malonate is used as the starting reactant, the reaction can be represented as follows:

^ 3 C- or C ₂ -alkanol jf3 (1) R 0OC-C-COOR ₁ + ROM - = ^ R.OOC-C-COOI ^ + llOII

H, Vi ■

(Metal derivative)

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BAD CR; &; \ AL

222975b

- "Melted

^ 3 DicarbQxylate \ 3

(2) H ₁ OuC-CQOIt ₁ + alkanesultone - _: - £ RjOOOC-GOOR.,

what mean!

R- a lower alkyl radical with 1 to 4 carbon atoms, R_ is a hydrogen atom, a phenyl radical, a tolyl radical or

an IJiedrigalkylrest with 1 to 4 carbon atoms, Pv, M and η have the same meanings as above ,.

In order to complete the desired implementation, a ver ^ ratio of alkane sultone to metal salt or metal derivative of about 1: 1 or, if indicated, a slight excess of that Alkanesultone used.

The metal alkoxysulfonate substituted compounds are selected from the lower alkyl dicarboxylate reaction medium, e.g. dimethyl terephthalate, by the following extroction method extracted or isolated:

The reaction product containing the metal alkoxy sulfonate substituted Dimethyl terephthalate melt is left at room temperature cooling down. The white solid obtained is comminuted (granulated). Then the dimethyl terephthalate is made from the crushed white solid by extraction with diethyl ether in a Soxhlet apparatus or the like over a period of time of 4C hours away, with the desired MetaHalkoxysulfonatverbindungen receives.

Examples of some of the particularly preferred compounds (A), that can be used are the following:

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Ethyl o-hydroxybenzoate, methyl-m-hydroxybenzone Methyl p-hydroxybenzoate 1-hydroxy-2,4-dicarbomethoxybenzene Dimethyl 5-hydroxy isophthalate Methyl 3,5-di-butyl-4-hydroxybenzoate Dibutyl 5-hydroxy isophthalate Methyl salicylate

Methyl 3,5-dimethyl-4-hydroxybenzoate Methyl 3-methoxy-4-hydroxybenzoate diethyl malonate

Diethyl 2-methyl malonate Dimethyl malonate

Dibutyl 2-tolyl malonate

Dibutyl 2-propyl malonate dimethyl 2-phenyl malonate o-phenylpheno1

p-phenylpheno1

3-hydroxyethoxypheno1

3-hydroxybutoxypheno1

3,5-diisopropylphenol

Dibutyl 2-hydroxy-5-butoxy-isophthalate Dimethyl 1-2-hydroxy-5-methoxy-isophthalate Dimethyl 4,6-di-t-butyl ~ 5-hydroxyisophthalate Dimethyl 4,6-dimethyl-5-hydroxyisophthalate Dimethyl 4,6-dichloro-5-hydrox) ^ isophthalate Diethyl 3-tert-butyl-4-hydroxybenzoate Methyl 3,5-dichloro-4-hydroxybenzoate, methyl 3-methoxy-4-hydroxybenzoate and Ethyl 3,5-dibutoxy-4-hydroxybenzoate.

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The various esters (mono- and diesters) falling under the above compound (Λ) can easily be prepared from their corresponding acid products using a conventional esterification process. For example, a C 1 -C, -dialkyl-5-hydroxyisophthalate, such as dimethyl-5-hydroxyisophthalate, can be prepared by adding 5-hydroxyisophthalic acid to a C 1 -C 4 alkanol solution, for example ethanol, which is a catalytic Contains amount (about 1 to 3 %) concentrated sulfuric acid, boils under reflux. Any combination of the compounds (A) given here can also be used, so that one or more sulfonate derivatives can be formed simultaneously in the "in situ" process of the invention.

In the case of the alkali metal used in the process according to the invention, The alkaline earth metal or a compound thereof can be any suitable substance such as them in particular is described here. Line 13, metallic sodium, potassium or calcium can be used. But it can also additionally C, -C, -alkylates of alkali or alkaline earth metals, such as iiatrium methylate, lithium ethylate, lithium propylate, Calcium ethylate, sodium butylate, potassium t-butylate and Potassium butylate, can be used.

In the alkane sultone reactant used in the process according to the invention it can be any straight or branched chain compound that interacts with the metal salt or with the metal derivative of the compound (A) under the conditions of the method according to the invention reacts. Preferred Alkane sultones are e.g. 1,3-propane sultone, 2-methyl-1,3-propane sultone and 1,4-butane sultone, as a molten reaction medium

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can be any suitable aliphatic or aromatic Illower alkyl dicarboxylate can be used as the molten dispersing medium for the desired reaction serves. The temperature during the reaction according to the invention varies depending on the melting point of the dicarboxylate used as the reaction medium. Examples of some of the preferred lower dialkyl dicarboxylates, which are available as molten Reaction medium which can be used are dimethyl adipate, dimethyl azelate, dimethyl terephthalate, and dimethyl isophthalate and combinations thereof.

Suitable glycols for the preparation of the polyester or wiped polyester resins can be aliphatic or cycloaliphatic. Such glycols that can be used include the glycols of the formula HO (CH ₉ ) OM, in which ζ is a positive integer from 2 to 10. Cycloaliphatic glycols such as 1,4-cyclohexanedimethanol can also be used. Examples of alkylene glycols that can be used are ethylene glycol, butylene glycol and hexylene glycol. In addition, if indicated, the glyco component can also contain a common alkyl glycol, such as 2,2-dimethyl-1,3-propanediol or 2,2-diethyl-1,3-propanediol. Any combination of the abovementioned glycols can also be used to produce the polyester resins according to the invention.

with the GlykoIreaktanten must for the preparation of Polyester or mixed polyester according to the process according to the invention there should also be sufficient lower alkyl dicarboxylate to form a high polymer polyester or high polyester resin to enable. In the method according to the invention may be all or all of the lower alkyl dicarboxylate reactant

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Mixtures thereof may be present in the initial molten reaction medium to form the desired polyester resin or some of it can be added at a later stage, if desired. The dicarboxylate reaction medium can consist of one or more suitable dicarboxylates, depending on the specific polyester or mixed polyester resin desired. Examples of other dicarboxylates in addition to those listed above can be used in the production of the homo- and mixed polyesters according to the invention, are diethyl 4,4'-bibenzoate, dibutyl 4,4'-sulfonyl dibenzoate, Dimethyl 2,6-naphthalenedicarboxylate, sodium 3,5-di (carbomethoxy) benzenesulfonate and dimethyl glutarate or any combination thereof. In the method according to the invention can but also many other dicarboxylates are used which are suitable for use in the production of homo- and mixed polyesters are already known from the literature.

The inventive method, the use of a molten reaction medium for the production of mixed polyester resins is used in conjunction with a transesterification process to make these resins. As is well known can be used in an ester exchange or transesterification process Manufacture of high polymer, thread-forming resins in a molar ratio of glycol to the appropriate diester from about 1: 1 to about 15: 1, preferably from about. 1.5: 1 to about 2.6: 1, be applied. In general, but this depends on the reactants, the transesterification reaction will take place at atmospheric pressure in an inert atmosphere such as nitrogen initially at a temperature within the range of about 125 to about 250, preferably from about 150 to about 200 ° C. in the presence of a transesterification catalyst. Included if a dialkyl ester of the dicarboxylic acid used is derived

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Talking alkyl alcohol developed and continuously removed by distillation. After a reaction time of 1 to 2 hours, the temperature of the reaction mixture is increased from about 200 to about 230 ° C. over a period of about 1 hour to complete the reaction, to form the desired polyester prepolymer and to distill off some of the diol present. Any known and suitable transesterification or ester interchange catalyst can be used, for example lithium amide, lithium hydride or sodium methylate can be used to catalyze the transesterification reaction according to the invention. In most cases, the transesterification catalyst will be used in concentrations within the range of 0.01 to about 0.20 percent based on the weight of the dialkyl ester of the dicarboxylic acid used in the starting reaction mixture.

The polycondensation of the prepolymers is achieved by adding a suitable polycondensation catalyst the polyester prepolymer or the polyester prepolymers, as defined above, and by heating the Mix them under reduced pressure within the range of about 0.05 to about 0.20 mm of mercury below Stir at a temperature of about 260 to about 325 C for a period of 2 to 4 hours. It can be any suitable Polycondensation catalyst can be used, for example antimony oxalate, antimony trioxide or disodium lead ethylenediamine tetraacetate.

Within the limits of the transesterification process described above the process according to the invention comprises the production of a homo- or mixed polymer resin and is thereby characterized

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shows that one or more of the alkoxysulfonate-substituted compounds according to the invention are formed directly in a molten aliphatic or aromatic lower alkyl (G ₁ -C,) dicarboxylate reaction medium. The temperature of the reaction medium must of course be varied depending on the melting point of the particular aliphatic or aromatic dicarboxylate used as the reaction medium. It is not necessary that all of the dicarboxylate reaction medium be in a molten state when the metal salt or metal derivative of the compound (A) as described above and the alkane sultone are added, but a sufficient amount of the dicarboxylate in the molten state is required so that there is a liquid (ie, molten) or semi-liquid dispersion medium for the desired reaction. Then the other reactants or additives, for example a suitable amount of glycol as described above, a heat stabilizer such as tritoIy! Phosphate, and a suitable transesterification catalyst are introduced into the molten reaction medium and a transesterification reaction is carried out to form a prepolymer. This prepolymer is then polycondensed in the presence of a suitable polyester polycondensation catalyst, such as one such as is listed above, with the formation of the desired homo- or mixed polyester resin product.

The following examples are intended to explain the invention in more detail. but without limiting it to that. The mixed polyester resins prepared in these examples are Uandom ethylene terephthalate resin resins which contain minor amounts of ester units derived from other monomers such as dimethyl carbonate and an organic sulfonate as indicated in the examples. The mole percentages of these

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Modifying monomers contained in the following examples are based on dimethyl terephthalate content the reaction mixture. All of the reactions reported in the following examples were, unless otherwise is indicated, carried out with mechanical stirring and essentially at atmospheric pressure.

example 1
feed

4.2.41 kg of dimethyl terephthalate

1500 g (4 mol%) dimethyl glutarate

312 g (0.45 mol%) sodium 3,5-di (carbomethoxy) benzenesulfonate 810 g sodium salt of methyl p-hydroxybenzoate.

The above feed was made under a nitrogen atmosphere

of 140.6 g / cm ⁴ "and melted. After 57 minutes, the temperature was 160 G. Then 560 g of propane sultone were added. After 28 minutes, the temperature was 174 G. Then, over a period of about 47 minutes, the A reaction mixture of 30.4 kg / ethylene glycol containing 18.2 g of lithium hydride was added in dosed form, heating was continued and 90 minutes later the temperature was about 227 G and all of the by-product methanol was distilled off 27.2 g of antimony trioxide and 430 g of trityllium phosphate were added. 45 minutes later the temperature was 249 C and a vacuum was applied. 1 3/4 hours later the temperature was 277 G and the vacuum was less than 1, For 110 minutes the temperature was 282 C and the resulting resin product was extruded and converted into chips (cubes) The fiber-forming ethylene terephthalate mixed polyester resin product contained about 2 mol% of ester segments derived from the sodium salt of Met ethyl 4- (3-sulfopropoxy) benzoate

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which was formed in situ in addition to the segments from the other enumerated monomers. The educated Resin would have an intrinsic viscosity of 0.48, a carboxyl content of 44 meq / kg and a sulfur content of 0.34% by weight.

Example 2
feed

42.18 kg of dimethyl terephthalate

312 g (0.45 Mo 1/0 sodium 3,5-di (carbomethoxy) benzenesulfonate

The above charge was heated to a melt and after 35 minutes the temperature was 160 C. Then the metered addition of a solution of the sodium salt of methyl hydroxybenzoate started to melt in methanol. (This solution was made by dissolving 107 g of metallic Sodium in 1500 ml of methanol and subsequent addition of 710 g Methyl p-hydroxybenzoate). The addition of the sodium salt of Methyl p-hydroxybenzoate in methanol was added within 10 minutes ended, after which the temperature was 161 C. After 30 minutes, the distillation of methanol had ceased and it 560 g of propane sultone were added at 180 g. Then after 18 minutes over 45 minutes became the reaction ^ mixture 16.8 kg ethylene glycol and 1688 g (4.5 mol%) Dimethyl glutarate was added, after which the temperature was 182 C. The reaction mixture was then added over a period of time 48 minutes a catalyst solution (65.7 g of metallic sodium in 1500 ml of methanol, then mixed into 13.6 kg Ethylene glycol) added, then the temperature was 178 G. An hour later the temperature was 227 C and the whole By-product methanol was distilled off. Then 27.2 g

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Antimony trioxide and 430 g of tritolyl phosphate were added and a vacuum was applied 45 minutes later at 254.degree. 1 1/2 Hours later the vacuum was less than 1 mm of mercury and the temperature was 278 G. 75 minutes later was the Temperature 282 C at which time the resin product was extruded. The obtained ethylene terephthalate mixed polyoxyethylene fiber-forming resin contained about 2 mole percent ester segments derived from the sodium salt of 4- (3-sulfopropoxy) benzoate which had formed in situ alongside the segments from the other listed monomers. The resin product had an intrinsic viscosity of 0.46, a carboxy content of 16 meq / kg and a sulfur content of 0.34% by weight.

Example 3

1013 g of a 25% strength by weight solution of sodium methylate in methyl alcohol and 2 liters of methyl alcohol were mixed together. 983 g of dimethyl 5-hydroxyisophthalate were added to the solution obtained added with formation of the sodium salt of dimethyl 5-hydroxyisophthalate in methyl alcohol. This methyl alcohol sodium salt solution and 44.45 kg of dimethyl terephthalate were charged to a 75.7 liter reactor. The reaction mixture was heated and the methanol was distilled off over a period of 75 minutes, after which the temperature was 128 C. Then 570 g of propane sultone were added to the reaction mixture. After 25 minutes the temperature was 132 ° C. and within one Over a period of 35 minutes, 16.8 kg of ethylene glycol were added in dosed form, after which the temperature was 127 G. Then a catalyst solution (170 g of a 25 wt .-% solution of sodium methylate in methyl alcohol + 13.6 kg of Ätl ^ lenglykol) added over a period of 30 minutes to the reaction mixture, after which the temperature was 166 C, 37 minutes

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th later, practically all of the methanol was removed and the temperature was 213 C. Because 13.6 g / mtimontrioxide and 215 g of tritolyl phosphate were added. 45 minutes later than that Temperature was 243 ° C, a vacuum was applied and two hours later the vacuum in the reactor was 0.5 ram of mercury at 264 G. 42 minutes later the temperature was 265 G, at which point the resin product was extruded and was converted into schnitzel or cubes. The thread-forming mixed polyester resin obtained contained about 2 mol% of ester segments, that of sodium 3- (3,5-dicarbomethoxyphenoxy) propanesulfonate formed in situ. The resin product had an intrinsic viscosity of 0.49, a carboxyl content of 10 mXq / kg and a sulfur content of 0.28% by weight.

Example 4

886 g of a 25% strength by weight solution of sodium methylate in methyl alcohol and 2 liters of methyl alcohol were mixed with one another. To the resulting solution, 860 g of dimethyl S-hydroxy isophthalate was added to form the sodium salt of dimethyl 5-hydroxy isophthalate in methyl alcohol. This methyl alcohol-sodium salt solution and 42.75 kg of dimethyl terephthalate were charged into a 75.7 liter reactor. The reaction mixture was heated and the methanol was distilled off over a period of 104 minutes, after which the temperature was 116 G. Then 499 g of propane sultone were added to the reaction mixture. Then 16 minutes later, 16.8 kg of ethylene glycol and 1500 g (4 mol%) of dimethyl glutarate were added. The addition was complete within 33 minutes, after which the temperature was 126 ° C. Then wwcde over a period of 53 min to the reaction mixture a catalyst solution (150 g of a wt .-% solution of Katriummethylat in methyl alcohol plus

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13.6 kg of ethylene glycol) were added, after which the temperature was 149 C. 73 minutes later, practically all of the methanol was removed and the temperature was 213 G. Then 13.6 g of antimony trioxide and 215 g of tritoIy / phosphate were added. 53 minutes later when the temperature was 243 ° C a vacuum was applied and 107 minutes later the vacuum was in that Reactor 0.6 mm of mercury at 260 G. 64 minutes later the temperature was 264 C, at which point the resin product was extruded and converted into schnitzel or cubes. The obtained thread-forming ethylene terephthalate copolymer resin contained about 1.75 mole percent ester segments derived from Sodium 3- (3,5-dicarbomethoxyphenoxy) propanesulfonate derived that had formed in situ. The resin product had a basic viscosity of 0.54 and a sulfur content of 0.25 wt%.

Example 5

1013 g of a 25% strength by weight solution of sodium methylate in methyl alcohol and 2 liters of methyl alcohol were mixed together. 614 g of dimethyl 5-hydroxyisophthalate were added to the resulting solution and 267 grams of methyl p-hydroxybenzoate was added to form the sodium salt of the two esters in methyl alcohol. The methyl alcohol sodium salt solution thus obtained and 44.45 kg of dimethyl terephthalate were placed in a 75.7 liter reactor. introduced. The reaction mixture was heated and the methanol was distilled off over a period of 107 minutes. then 570 g of propane sultone were added at a temperature of 127 G added to the reaction mixture. After 20 minutes, when the temperature was about 135 ° C., the addition of 16.5 kg Ethylene glycol started. This addition was within 15 minutes

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Nuts ended, after which the temperature was 126 C. A catalyst solution (140 g of a 25% strength solution of sodium methylate in i-Ie thy alcohol plus 13.6 kg of ethylene glycol) was then added to the reaction mixture over a period of 30 minutes , then the temperature was about 127 C. After a further 66 minutes, the temperature was about 204 G and practically all of the! -! ethanol was distilled off. Then 13.6 g of antimony trioxide and 215 g of tritolyl phosphate were added. A vacuum was applied 54 minutes later when the temperature was 241 ° C. 84 minutes later the vacuum was in the reactor of 0.6 mm of mercury at 259 C ₀ 97 minutes later, when the temperature was 266 g, the resin product was extruüert and converted to chips. The resulting filamentary high polyester resin contained about 1.25% by mol of segments derived from sodium 3- (3,5-dicarbomethoxyphynoxy) propanesulfonate and 0.76% by mole of units derived from the sodium salt of methyl ~ 4- ( 3-sulfopropoxy) benzoate, both of which had formed in situ. The resin product had an intrinsic viscosity of 0.45 and a sulfur content of 0.28% by weight.

Example 6

1013 g of a 25% strength by weight solution of sodium methylate in methyl alcohol and 2 liters of methyl alcohol were mixed together. 614 g of dimethyl 5-hydroxyisophthalate were added to the resulting solution and 267 g of Methylsalicyla.t added to form the 1, 'atrium salt of the two esters. This methyl alcohol-sodium salt solution and 44.45 kg of dimethyl terephthalate were placed in a 75.7 liter reactor introduced. The reaction mixture was heated and the methanol was removed over a period of 69 minutes; Lillicrt, thereafter the temperature was 132 ° C. 570 g of propane sultone were then added to the reaction mixture, thereafter

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the temperature was 138 ° C. 12 minutes later they were then over add 16.8 kg of ethylene glycol to the reaction mixture over a period of 14 minutes admitted. A catalyst solution (130 g of a 25% strength by weight solution of sodium methylate in methyl alcohol and 13.6 kg of ethylene glycol) added, then the temperature was 126 ° C. 105 minutes later at about 204 ° C. 13.6 g of antimony trioxide and 215 g of tritolyl phosphate admitted. A vacuum was applied 76 minutes later when the temperature was about 236 C and 80 minutes later the vacuum in the reactor was 0.6 mm of mercury at 254 ° C. 115 minutes later, at about 266 ° C., the resin product was extruded and converted into schnitzel. The obtained thread-forming ethylene terephthalate copolymer resin contained about 1.25 mol% Segments made by sodium 3- (3,5-dicarbomethoxyphenoxy) propanesulfonate and 0.75 mole% segments derived from the iiatrium salt derived from MeL: hyl 2- (3-sulfopropo;: y) benzoate, both of which had formed in situ.

Example 7

1.42 g of sodium were dissolved in 65 ml of methyl alcohol with the formation of sodium methylate. 16.4 grams of methyl 3,5-di-t-butyl-4-hydroxybenzoate and 85 ml of methanol were stirred into the sodium methylate-methanol solution with slight warming to form the Sodium salt of methyl 3,5-di-t-butyl-4-hydroxybenzoate in methanol. 589 g of dirnetyl terephthalate were placed in a 1 liter resin kettle reactor melted. The methanolic solution of the sodium salt of methyl 3,5-di-t-butyl-4-hydroxybenzoate, prepared above, was at 162.5 ° C. introduced into the molten dimethyl terephthalate in metered form. This addition was within one Hour and 15 minutes ended, after which the temperature was 151.5 ° C. Then 7.55 g of propane sultone were added. 30 minutes

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later, at about 180.5 C, with the addition of 250 ml of ethylene glycol began. This addition took 16 minutes, then the temperature was 171.5 C. Then 50 ml of ethylene glycol, containing 0.24 g of lithium hydride was added, after which the Temperature 159 G. A further 100 ml of ethylene glycol were added. The methanol was distilled off and the temperature was allowed to rise to 231 ° C. over the next two hours, which led to the formation of a mixed polyester prepolymer.

150 g of the prepolymer prepared as above, 0.09 g of antimony trioxide and 0.5 ml TritoIy! phosphate were in a reactor introduced and over a period of 2 hours under a vacuum of about 0.6 to 0.1 mm of mercury at a temperature polycondensed from about 280 C. The obtained fiber-forming ilth3 ^ 1eiiterephthalate mixed polyester resin contained about 2 mol% Segments derived from ethyl-3,5-di-t-butyl-4- (3-sodium sulfopropoxy) benzoate, which had formed in situ. A 70 denier fiber made from the moath polyester resin so produced had been spun had an intrinsic viscosity of 0.42, a carboxyl content of 18 mAq / kg and a sulfur content of 0.28 wt%.

Example 8

1.42 g of metallic sodium were dissolved in 40 ml of methyl alcohol to form sodium methylate. 9.9 g of diethyl malonate were to the diethyl alcohol 1-liatrium methylate solution added below Formation of the sodium salt of diethyl malonate. In a 1 liter resin kettle reactor 589 g of dimethyl terephthalate were melted. The methyl alcohol solution of the sodium salt of Diethyl malonate was dosed into the melted di-

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methyl terephthalate introduced. This addition was complete within 31 minutes, after which the temperature was 133 ° C. 17 minutes later, at 157 ° C., 7.55 g of propane sultone were added. 16 minutes later, at about 157.5 C, the addition of 350 ml of ethylene glycol started. Then over a period of 24 minutes 50 ml of ethylene glycol, the 0.69 g of metallic Sodium was added, after which the temperature was 155.5 C. The temperature rose within the next 106 minutes Allowed to rise to 232 C to form a mixed polyester prepolymer.

50 g of the prepolymer prepared above, 0.02 antimony trioxide and 0.32 ml tritoIy / phosphate were introduced into a reactor and under a vacuum of about 0.6 to 0.1 mm of mercury at a temperature of about 280 ° C. for 2 hours polycondensed. The obtained ethylene terephthalate mixed polyester resin contained approximately 2 mole percent segments derived from diethyl 2- (3-sodium sulfopropyl) malonate that had formed in situ. The resin product had an intrinsic viscosity of 0.67, a carboxyl number of 6 meq / kg and a sulfur content of 0.27% by weight.

Example 9

3.14 g of metallic sodium was dissolved in 75 ml of methanol to form a sodium methylate solution. To the alcoholic Solution of the sodium methylate, 9.42 g of methyl p-hydroxybenzoate and 5.27 g of o-phenylphenol were added to form the Sodium salts of methyl p-hydroxybenzoate and o-phenylphenol. In a 1 liter resin kettle reactor, 565 grams of dimethyl terephthalate was melted. At about 149 C the above was made .methanol! See solution of the sodium salt of methyl-p-hydroxy-

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benzoate and the sodium salt of ο-pheny! phenol introduced in dosed form into the molten dimethyl terephthalate. This addition was complete within about 20 minutes, after which the temperature was 162 G. 11.34 g of propane sultone were then added to the reaction mixture. 15 minutes later, 350 ml of ethylene glycol plus 19.8 g (4 mol%) of dimethyl glutarate were added at 160 ° C. over a period of 29 minutes. Then 50 ml of ethylene glycol containing 0.69 g of metallic sodium were added. Within the next 104 minutes, the temperature was left to 23O ° C,
ester prepolymer.

Increase the temperature to 230 C to form a mixed poly-

50 g of the prepolymer prepared above, 0.02 g of antimony trioxide and 0.32 ml of tritolyl phosphate were placed in a reactor and kept under a vacuum of about 0.6 to 0.1 mm of mercury polycondensed at a temperature of about 280 C. The obtained thread-forming mixed polyester resin contained 2 mole percent segments derived from the sodium salt of methyl 4- (3-sulfopropoxy) benzoate, and 1 mole percent of units derived from 2- (3-sodium sulfoprop.oxy) biphenyl, both of which were formed in situ. That The resin obtained had an intrinsic viscosity of 0.43, a carboxyl content of 8 meq / kg and a sulfur content of 0.41 Weight%,

Example 10

1.78 g of metallic sodium was dissolved in 50 ml of methanol to form a sodium methylate solution. To the alcoholic Liatriummethylatlösung were 9.42 g of methyl p-hydroxybenzoate and 2.5 g of diethyl malonate were added to form the sodium salts of methyl p-hydroxybenzoate and diethyl malonate. In one

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1 liter resin kettle reactor was melted 561.6 g of dimethyl terephthalate. At about 150 g, the above prepared methanolic solution of the sodium salt of methyl p-hydroxybenzoate and the sodium salt of diethyl malonate was introduced in metered form into the molten dimethyl terephthalate. This addition was complete within about 10 minutes, after which the temperature was 159 ° C. 9.44 g of propane sultone were then added to the reaction mixture. 15 minutes later, 350 ml of ethylene glycol and 19.8 g (4 mol%) of Dime thy Ig Iu tar at were added at 167 C. Then 50 ml of ethylene glycol containing 0.24 g of lithium hydride were added. The temperature was allowed to rise to 23 over the next 95 minutes
Mixed polyester prepolymer.

the temperature was allowed to rise to 232 ° C. to form a

50 g of the prepolymer prepared above, 0.02 g of antimony trioxide and 0.32 ml of tritolyl phosphate were introduced into a reactor and kept under a vacuum of about 0.6 to 0.1 mm of mercury polycondensed at a temperature of about 280 C. The obtained ethylene terephthalate mixed polyes terharz contained about 2 mole percent segments derived from the sodium salt of methyl 4- (3-sulfopropoxy) benzoate, and about 0.5 mole percent of segments derived from diethyl 2- (3-sodium sulfopropyl) malonate. The resin obtained had an intrinsic viscosity of 0.46, a carboxyl content of 9 meq / kg and a sulfur content of 0.35% by weight

Example 11

13.4 g of a 25% strength by weight solution of sodium methylate in Methanol and 40 ml of methanol were combined with each other. 9.56 g were added to the sodium methylate-methanol solution obtained 3-Hydroxyäthoxyphenol added to the production of the sodium salt this connection. In a 1 liter resin kettle reactor

209853/1221

600 g of dimethyl terephthalate were melted. At about 156 ° C., the methanol solution of the sodium salt of 3-hydroxyethoxyphenol prepared above was introduced in metered form into the molten diethyl terephthalate. This addition was completed within about 50 minutes, after which the temperature was 150 ° C. 7.56 g of propane sultone were then added to the reaction mixture. 15 minutes later, 350 ml of ethylene glycol were added at 155 ° C over a period of 15 minutes, after which the temperature was 137 G. Then a
Catalyst solution prepared by combining 50 ml of ethylene glycol with 0.69 g of metallic sodium was added. 172 minutes after the start of the addition of the catalyst, the temperature reached 230 ° C. and a mixed polyester prepolymer was obtained.

50 g of the prepolymer prepared above, 0.02 g of antimony trioxide and 0.32 ml of tritolyl phosphate were placed in a reactor and placed under a vacuum of about two hours
0.6 to 0.1 mm of mercury at a temperature of about
Polycondensed at 280 C. The thread-forming mixed polyester resin obtained contained about 2 mol% of segments which were derived from hydroxyethoxy-3-sodium sulfopropoxybenzene, which had formed in situ. The resin had an intrinsic viscosity
of about 0.45 and a sulfur content of 0.26% by weight.

Example 12

13.4 g of a 25% strength by weight solution of sodium methylate in
Methanol and 40 ml of methanol were combined with each other.
To the obtained sodium methylate-methanol solution were
11.04 g of 3,5-diisopropylphenol were added to prepare the
Sodium salt of phenol. In a 1 liter resin kettle reactor

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600 g of dimethyl terephthalate were melted. At about 171 ° G the solution of the sodium salt of 3,5-diisopropylphenol in methanol prepared above in metered form in the melted Dimethyl terephthalate introduced. This addition was complete within about 33 minutes, after which the temperature was 155 C. Then were added to the reaction mixture at a temperature of 156 C, which was maintained for about 15 minutes, 7.56 g of propane sultone were added. Then 350 ml of ethylene glycol was added over a period of 28 minutes, after which it was the temperature 135 C. Then a catalyst solution, prepared by combining 50 ml of ethylene glycol with 0.69 g of metallic sodium was added. 171 minutes, After all of the catalyst solution had been added, the temperature reached 230 ° C. and a mixed polyester prepolymer was formed obtain.

50 g of the prepolymer prepared above, 0.02 g of antimony trioxide and 0.32 ml TritoIy! phosphate 'were in a reactor and placed under a vacuum of about 0.6 to 0.1 mm of mercury at a temperature of about 280 C for two hours polycondensed. The obtained polyethylene terephthalate copolymer resin contained about 2 mol% 1,3-diisopropyl-5- (3-sodium sulfopropoxy) benzene, that had formed in situ. The resin product had an intrinsic viscosity of 0.53 and one Sulfur content of 0.62% by weight.

Example 13

6.7 g of a 25% strength by weight solution of sodium methylate in methanol and 80 ml of methanol were combined with each other. To the sodium methylate-methanol solution obtained, 7.45 g of dimethyl

2 0 9 8 5 3/12 2 1

2-hydroxy-5-methoxyisophthalate was added to form the sodium salt of the isophthalate compound. In a reaction kettle, 294.3 g of dimethyl terephthalate were melted and the methanolic solution of the sodium salt of dimethyl 2-hydroxy-5-methoxyisophthalate prepared above and another 40 ml of methanol were added to the melted dimethyl terephthalate. After about 60 minutes the temperature was 161.5 G and about 98 % of the added methanol had distilled off. Then 3.78 g of propane sultone was added to the reaction mixture. After about half an hour at a temperature of 175 ° C., 175 ml of ethylene glycol were added. A catalyst solution consisting of 1.6 g of a 25% strength by weight solution of sodium methylate in methanol and 25 ml of ethylene glycol was then added. About 140 minutes later the temperature reached 238 ° C. and a mixed polyester prepolymer was obtained.

50 g of the prepolymer prepared above, 0.02 g of antimony trioxide and 0.32 ml Tritoly! Phosphate were introduced into a reactor and Γ 1/2 hours under a vacuum of Oj6 to 0.1 mm of mercury at a temperature of about 28O ⁰ G polycondensed. The obtained ethylene terephthalate mixed polyester filament-forming resin contained about 2 mol% of segments derived from dimethyl 2- (3-sodium sulfopropoxy) -5-methoxyisophthalate which was formed in situ.

Example 14

1.42 g of metallic sodium were dissolved in 65 ml of methyl alcohol to form sodium methylate. To this solution were 9.4 g of methyl salicylate were added. The solution obtained, consisting from the sodium salt of methyl salicylate in methanol, was placed in a reaction vessel containing 589 g of molten dimethyl »

2 09 8 53/122 1

contained terephthalate. The reaction kettle was with a Nitrogen inlet pipe, a distillation arm, a heater and a stirrer. the The pot temperature during the addition of the sodium salt of methyl salicylate in methyl alcohol was between 167 and 185 ° C and the reaction kettle was under atmospheric pressure. The addition of this solution to the molten dimethyl terephthalate took about 53 minutes. Thereafter, when the reaction mixture was at a temperature of about 164 ° C., there was 7.55 g of propane sultone added to the reaction mixture. The appearance of the reaction mixture immediately changed from a cloudy yellow to a very clear lemon yellow. About 8 minutes after the addition of the propane sultone, 150 ml of ethylene glycol was added to the reaction mixture and this was continued over a period of 1 hour. Then were over a period of 45 minutes, during which time the temperature was about 154 G, a further 160 ml of ethylene glycol, containing 0.24 g of lithium hydride was added. A further 100 ml of ethylene glycol were added, after which the temperature was of the reaction mixture 146 C. The temperature was then left the reaction mixture under a nitrogen protective gas atmosphere at atmospheric pressure rise to 230 C over a period of about 2 hours, during which time practically all of the by-product methanol was distilled off from the reaction mixture. The prepolymer seed formed was then cooled under a nitrogen atmosphere.

Example 15

1.42 g of metallic sodium were dissolved in 65 ml of methyl alcohol. 9.4 g of methyl p-hydroxybenzoate were added to this solution admitted. The solution obtained, consisting of the sodium salt

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of methyl p-hydroxybenzoate in methanol, was then poured into a Added reaction kettle containing 600 g of molten dimethyl terephthalate. The reaction kettle was equipped with a nitrogen inlet tube, a distillation arm, a heater and a stirrer. The pot temperature during the addition of the above sodium salt solution was between about 145 and 170 g and the kettle was at atmospheric pressure held. The addition of this solution to the molten dimethyl terephthalate took about 30 minutes. Thereafter, when the reaction mixture had a temperature of about 157 G, were 7.55 g propane sultone was added to the reaction mixture. The appearance of the reaction mixture changed from a cloudy yellow an almost colorless solution. Then, after about 15 minutes, 200 ml of ethylene glycol were added over a period of 20 minutes admitted. Subsequently, 0.24 g of lithium hydride, dispersed in ethylene glycol, was added to the reaction mixture, then the temperature of the reaction mixture was about 147 C. Es another 50 ml of ethylene glycol were added. Then the temperature of the reaction mixture was left at atmospheric pressure rise to 230 C over a period of about 2 hours, where during this time practically all of the by-product> -methanol was distilled off from the reaction mixture. The prepolymer product formed was under a nitrogen atmosphere cooled down.

The prepolymer products formed in Examples 14 and 15 above were separately polycondensed as indicated below with the formation of thread-forming copolymer resins:

150 g prepolymer, 0.09 g antimony trioxide and 0.5 ml tritolyl

2 09853/1221

phosphate was placed in a reaction vessel. The reaction mixture was heated to about 240 ° C over a period of about 45 minutes. Heating was continued and vacuum was applied over the next 45 minutes. Thereafter, the pressure in the reaction vessel was about 10 mm of mercury and the temperature was about 260 C. The temperature was then increased to about 280 C and the pressure was increased to about 0.6 mm Mercury lowered. The reaction mixture then became mercury under a vacuum of about 0.6 to 0.1 mm Held at about 280 ° C. for two hours to complete the polycondensation of the prepolymer product to complete. the formed from the prepolymer products of Examples 14 and 15 fiber-forming / »ethylene terephthalate mixed polyester resins contained terminal units of the monofunctional sulfonate compounds indicated below in the also below specified mole percentages:

Example 14: 2 Hol-% of the sodium salt of 2- (3-5ulfopropoxy) -

benzoate and
Example 15: 2 mol% of the sodium salt of methyl 4- (3-sulfo-

propoxy) benzoate.

In the mixed polyester resins prepared in the above examples In all cases it was a matter of thread-forming resins and fibers made from them could be mixed with basic dyes to be stained.

20 98537 122 1

Claims (13)

Claims experienced in making one through a metal alkoxysulfonate group substituted compound, characterized in that an alkali or alkaline earth metal salt or a derivative of a Compound (A) from group (a) is a phenol (b) is substituted by one or more phenolic groups ¥ 3 organic compound and (c) 11,0OC-CII-COOR ₁ , in which R. is a lower alkyl group with 1 to 4 carbon atoms and R_ is a hydrogen atom, a phenyl group, a tolyl group or a lower alkyl group with 1 to 4 carbon atoms, in one Reaction medium of a molten lower alkyl (C, -C,) - dicarboxylate is reacted with an alkane sultone. 2. The method according to claim 1, characterized in that the salt or the derivative thereof by reacting the compound (A) with the alkali or alkaline earth metal or a compound thereof that the salt or derivative obtained dispersed in the reaction medium and sufficient to form the reaction medium for the reaction with the metal salt or derivative Alkanesultone is added. 3. The method according to claim 1 or 2, characterized in that the compound (A) from the group OH OH 2 0 9853/1221 (c) R ₁ OOC Jt (d) COOR. Z-OH OH , ν 0 (CH ₀ ) OH,, -ν (e) / ^ν 2 ^y n and (f) ί ³ R ₁ OOC-CIi-COOR ₁ OH and the salt or derivative is appropriately selected from the group will (a) (R ₁ OOC) - K - ^{- C00R} i J. from left I J- (c) OM OR, (d) R 0OC -U -4- COOR ₁ OM Z-OM (e) (CH ₂ ) _n OH and (f) f R _n OOC-C-COOR ¹ I. OM 209853/1221 where mean: R "is a lower alkyl radical with 1 to 4 carbon atoms, t, χ and y the number 0 or 1, η is an integer from 2 to 4, Q and P are alkyl radicals with 1 to 6 carbon atoms, alkoxy radicals with 1 to 6 carbon atoms or halogen atoms and Z is an unsubstituted aryl radical. 4. The method according to any one of claims 1 to 3, characterized in that that the compound (A) from the group methyl hydroxybenzoate, Dimethyl 5-hydroxyisophthalate, methyl salicylate, Methyl-3,5-di-t-butyl-4-hydroxybeiizoet, diethyl malonate, o-phenylphenol, 3-hydroxyethoxyphenol, 3,5-diisopropylphenol and dimethyl-2-hydro: xy-5-methoxyisophthalate is selected. 5. The method according to any one of claims 1 to 4, characterized in that that an aromatic dicarboxylate is used as the molten dicarboxylate. 6. The method according to claim 5, characterized in that dimethyl terephthalate is used as the dicarboxylate » 7. The method according to any one of claims 1 to 6, characterized in that that propane sultone is used as the sultone. 8. The method according to any one of claims 1 to 7, characterized in that that sodium methylate is used as the alkali metal compound will. 20985 3/1221 9. A method for producing a polyester resin from the reaction mixture according to any one of the preceding claims, characterized in that sufficient glycol is added to the reaction mixture to effect the transesterification of all polyester-forming Reactants to be \ d.r that a transesterification reaction is carried out to produce a prepolymer and then the prepolymer is polycondensed. 10. The method according to claim 9, characterized in that ethylene glycol is used as the glycol. 11. Hydroxyethoxy-3-sodium: lumsulfopropox3'-benzene. 12. 1,3-Diisopropyl-5-sodium sulfopropoxybenzo1. 13. Dimethyl 2-sodium sulfopropoxy-5-methoxyisophthalate. 2 09853/1221