DE2224255A1 - SOUR MODIFIED POLYTEREPHTHALIC ACID ESTER - Google Patents

Description

TBRIKE BAYER AG LEVERKUS EN-Bayerwerk ·) J μ π. . Central area Patents, trademarks and licenses

Sdt / MH

Acid modified polyterephthalic acid. Ster

The invention "relates to modified and sulfonate groups polyterephthalic acid esters that can be dyed with basic dyes, by melt condensation of terephthalic acid or its derivatives with a glycol and a salt of 2-sulfonatomethyl-propanediol- (1,3) or its derivatives are produced.

It is known, by gocondensation of, for example, sodium 3,5-di- (carbomethoxy) -benzene-sulfona't or 1- ^ 3 ', 5'-di- (carbomethoxy) -phenoxvj-propanesulfonate- (3) - Incorporate sodium with dimethyl terephthalate and ethylene glycol sulfonate groups in polyethylene terephthalate. The disadvantage of these comonomers containing sulfonate groups is, on the one hand, that they are technically difficult to obtain. In the first case isophthalic acid must be sulfonated at temperatures above 200 ⁰ C and sulfuric acid reuchender namely, in the second case, the complex can be produced 5-hydroxy-isophthalic acid is contacted with the physiologically dangerous propane sultone to the reaction. On the other hand, both sulfonates have molecular weights of around 300, so that relatively large amounts of co-condensation have to be used for dyeing with basic dyes, as a result of which the textile-technological data of threads produced from such co-condensates can be significantly impaired.

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The invention relates to high molecular weight linear terephthalic acid copolyesters containing sulfonate groups, consisting of recurring structural elements of the general formula

0 0

Il Il

-C-Ar-C-O-X-

wherein Ar is a phenylene radical and

X to 99-70 mol- # a straight-chain or branched one Alkylene radical with 2-20 carbon atoms, a cycloalkylene radical, the radical of the general formula

wherein R is a straight-chain or branched alkylene radical with 1-10 carbon atoms, and a sulfonate group-containing radical of the general formula for 1 to 30 mol

- Cn — Cn »- ·} -

. , ti

CH ₂
SO ₃ M

is where M is the meaning of a. Has metal,

wherein the relative solution viscosities Terephthalsäurecopolyester ^ _rel in the range from 1.1 to 4.0 (measured on a solution of 1 g of substance in 100 ml m-cresol at 25 ⁰ C).

The preferred representatives of this class consist of 99 - 70 - # of recurring structural elements of the formula

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-OX ₁ -0 *

wherein X. the radical -CHg-CHp- and / or

means the radical -GH ₂ -ZhYcH ₂ - ,

and 1 - 50 mol # from structural elements of the general formula

0 0

-C-Ar-CO-CH ₉ -CH-CIL ,. CH ₂ SO, M

■ where Ar and M have the meaning given above. Preferred metals are the alkali metals.

For the production of such polyterephthalates modified by sulfonate groups,! Carboxylic acid derivatives of the general formula

0
11

R ₁ -OC-Ar-COR ₁

wherein Ar is phenylene and

R-J is hydrogen or a straight or branched chain Denotes alkylene radical with 1 - 10 carbon atoms,

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with a diol derivative of the general formula

R ₂ -OXOR ₂

wherein X is a straight-chain or branched alkylene radical with 2-20 carbon atoms, a cycloalkylene radical, the rest of the general formula

wherein R is a straight-chain or branched alkylene radical having 1-10 carbon atoms, and
Rp hydrogen, aliphatic or aromatic

Is acyl radical
and a diol derivative of the general formula

R ₉ -O-CH ₉ -CH-GH ₀ -OR

CH ₂

wherein M has the meaning of a metal and R _{0 has} the meaning given above.

in such quantitative ratios with one another in the melt at temperatures of 150-300 ⁰ C with exclusion of moisture and oxygen in an inert gas atmosphere at pressures between normal pressure and 0.001 Torr using known catalysts that the condensed amount of the salt of 2-sulfonatomethyl- propanediol- (1,3) is in the range between 1-30 mol- #, based on the amount of condensed glycols.

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A dicarboxylic acid derivative of the general formula

0 0
η r
R ₁ -OC- / '

wherein R _{1 is} hydrogen or a straight-chain or branched alkyl radical having 1-10 carbon atoms. ",

and a mixture of 99-70 mol of a diol

HO-CH ₂ -CH ₂ -OH and / or

HO-CH ₂ _ / _H V-CH ₂ -OH

and 1 to 30 mol $ of a sulfonate group-containing diol derivative the general formula

R ₂ -O-CH ₂ -CH-CH ₂ -OR ₂ CH ₉

where S ₂ ^{un (} i ^ have ^the meaning given, polycondensed with one another.

The modified polyterephthalates thus obtained Can be processed excellently from the melt into shaped structures, especially into threads and foils.

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The salts of 2-sulfonatomethyl-propanediols (i, 3) or its derivatives used to modify the new polyesters are prepared in such a way that bisulfites of 2-methylenepanediol- (1,3) or its acyl derivatives are preferably in aqueous solution with the aid of a catalyst such as oxygen in a pH range of 3-9 kept constant by the addition of acid in the temperature range of -10 to 10O ⁰ C are added. It is advantageous to introduce the 2-methylene-propanediol- (1,3) in portions into the bisulfite solution, whereby the molar ratio between bisulfite and diol can be in the range from 1: 1 to 5: Ί:

MHSO, + HO-CH ₀ -CH-CH ₀ -OH > HO-CH ₀ -CH-CH ₀ -OH

CH ₀ CH ₀

^ t ^c

SO ₃ M

Dicarboxylic acids or derivatives are used for the polycondensation in addition to the free terephthalic acid, their esters, such as. B. dimethyl terephthalate or bis-ß-hydroxyethyl terephthalate, and proportions of isophthalic acid, which should not exceed 10 mol # if possible, or their esters are used.

Alkylene glycols with 2-20 are primarily used as diols Carbon atoms, quinite or glycols of the general structure

H0-R-4-H-HR-OH

in question, where R has the meaning given above. Ethylene glycol and bis-1,4-hydroxymethylcyclohexane are particularly preferred.

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To produce the polyterephthalates, customary esterification or condensation catalysts, such as. B. alkali and alkaline earth metals, zinc, cadmium, manganese, iron, nickel, cobalt, tin, lanthanum, lead, bismuth, or combinations of such metals, salts such as calcium, manganese, cobalt, zinc acetate, lithium hydride, sodium alcoholates, zinc succinate , Zinc acetylacetonate, oxides such as lead oxide (PbO), antimony oxide (SbpO · *) »germanium dioxide (GeOp) and combinations such as antimony trioxide / manganese acetate or antimony trioxide / titanium dioxide are used. Based on the monomers, the amount of catalyst is in the range of O ₁ X) Q ?. to 0.2 wt .- $ added.

To carry out the polycondensation, in a preferred embodiment of the process according to the invention, the reaction mixture consisting of, for example, a dialkyl terephthalate such as dimethyl terephthalate, ethylene glycol, a salt of 2-sulfonatomethyl-propanediols (1,3) and a catalyst or catalyst mixture, the ethylene glycol for Transesterification is used in excess, 1-4 hours in the presence of an inert gas, such as. Heated 280 ⁰ C - as nitrogen, hydrogen or helium, with stirring at 130-200 ⁰ C and then 1-3 hours to 225th Then the pressure is reduced, generally below 15 Torr, preferably below 1 Torr, the temperature in the range of 250 - ⁰ 29o C is maintained. Condensation is carried out under these conditions for 1 to 18 hours until the desired viscosity of the melt is reached. After the reaction has ended, the resulting polyester can immediately be processed from the melt into shaped articles such as threads, foils or other shaped bodies.

Additives such as pigments, matting agents, discoloration stabilizers and optical brighteners can be added to the polyester melts etc. are admixed without impairing the properties.

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The new products are characterized by excellent raw clay, good dyeability with basic dyes, and good mechanical properties and thermal properties as well as good processability.

The relative solution viscosities r) given in the following examples were at 25 ^° C. on solutions of 1 g of Sub- * rex

punch measured in 100 ml m-cresol.

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example 1

194.0 parts by weight of dimethyl terephthalate, 186.0 parts by weight of ethylene glycol, 7.7 parts by weight of sodium-2-sulfonatomethyl are placed in a reaction vessel equipped with an anchor blade stirrer, gas inlet tube, distillation attachment, condenser, vacuum inlet and receiver -propanediol- (i, 3) added as a mixture with 0.5 part by weight of zinc acetate and 0.6 part by weight of antimony trioxide. The mixture is heated under a stream of nitrogen at 165 ⁰ C and 2 Stunden'umgeestert. The temperature is then ^{increased to 280 °} C. over the course of 2 hours. After interrupting the supply of nitrogen, the pressure is slowly reduced to 0.03 torr over the course of one hour. The stirring speed must then be reduced from approx. 150 to approx. 20 revolutions per minute because of the constant increase in the viscosity of the melt. The polycondensation is ended after a further 3.5 hours. The colorless, homogeneous, highly viscous melt can be processed into shaped bodies, especially threads. The drawn threads can be dyed with a basic dye in a dark, blue shade. The coloring is washable.

The polyester shows a softening point of 252 - 264- ⁰ C and a relative solution viscosity of ^ = 1.98.

Production of sodium-2-sulfonato-propanediol- (1,3)

390 parts by weight of a technical, 40 ^ strength ITatriumbisulfitlauge are brought to pH 7.05 with concentrated NaOH solution. Air is blown in and the mixture is stirred so vigorously that the reaction solution looks cloudy due to the finely divided air bubbles. Then 88 parts by weight of 2-methylenepropanediol-1,3 in 38 ml of H ₂ O are added dropwise at room temperature within 3/4 to 1 hour, with simultaneous dropping

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of dilute sulfuric acid the pH between 7.0 and 7.1 is held. The reaction is allowed to continue until no more change in the pH can be detected. Then sour the pH is adjusted to approximately 3 with dilute sulfuric acid and the excess SOp is stirred out. After neutralizing with NaOH it is concentrated to about half the volume and, after standing for several hours in the refrigerator, the precipitated Glauber's salt is filtered off. The Piltrat is left to dryness evaporated and the residue boiled up with 90 tiger methanol. It is filtered, the piltrate is evaporated and crystallized the residue from alcohol.

Yield: 142 parts by weight

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Claims (1)

Claims 1) High molecular weight, linear, sulfonate groups containing Terephthalic acid copolyester, consisting of recurring structural elements of the general formula, 0 0
n · n -C-Ar-C-O-X- wherein Ar is a phenylene radical and X to 99-70 mol- # a straight-chain or branched one Alkylene radical with 2 - 20 carbon atoms, a cycloalkylene radical, the remainder of general formula ■ H.- · wherein R is a straight-chain or branched alkylene radical with 1-10 carbon atoms ", and 1 to 30 mol- # contains a sulfonate group ger remainder of the general formula —OH “—GH— A- ι CH ₂
S. is where M has the meaning of a hetaiie, the terephthalic acid copolyesters having relative solution viscosities Tp _ - in the range from 1.1 to 4.0 (measured on a solution of 1 g of substance in 100 ml of m-cresol at 25 ^° C.).
Le A 14 422 - 11 - 3 0 8/1004 2) High molecular weight, linear terephthalic acid copolyester containing sulfonate groups according to claim 1, consisting 99 - 70 mol- $ of recurring structural elements the IOrmel wherein X _{1 is} the radical -CH ₂ -GH ₂ - and / or the rest - CH ₂ - means and to 1
formula - 30 mol- $ from structural elements of the general Il -Ar-CO-CH ₉ -CH-CH CH ₂
SO, M where Ar is a phenylene radical and M is a metal, the terephthalic acid copolyesters having relative solution viscosities η , in the range from 1.1 to 4.0 (measured on a solution of 1 g of substance in 100 ml of m-cresol at 25 ^° C.). 3j Process for the production of high molecular weight, linear terephthalic acid copolyesters modified by sulfonate groups by melt condensation of ester-forming components containing sulfonate groups together with a terephthalic acid Le A U 422 - 12 - C) ü S 0 · -; ■ -J j ί U 'J- - >> acid derivative and a glycol, acid derivatives and Glycols are used in approximately equivalent amounts, characterized in that dicarboxylic acid derivatives are used the general formula 0 0. . R ₁ -OS-Ar-COR ₁ wherein Ar is phenylene and ] L · hydrogen or a straight or branched chain Alkyl radical with 1-10 carbon atoms means, with a diol derivative of the general formula - R ₂ -OXOR ₂ wherein X is a straight-chain or branched alkylene radical with 2-20 carbon atoms, a cycloalkylene radical ,. the rest of the general formula wherein R is a straight-chain or branched alkylene radical having 1-10 carbon atoms, and
Rp hydrogen «an aliphatic or aromatic one Is acyl radical, and a diol derivative of the general formula R ₂ -O-CH ₂ -CH-CH ₂ -OR ₂ CH ₂
SO, M Le AU 422 - 13 - 309848/1064 wherein M has the meaning of a metal and R _{2 has} the meaning given above, in such proportions with each other in the melt "at temperatures of 150-300 ⁰ C with exclusion of moisture and oxygen in an inert gas atmosphere at pressures between normal pressure and 0.001 Torr using known catalysts polycondensed that the condensed amount of the salt of 2-sulfonatomethyl -propanediols- (1,3) is in the range between 1-30 mol- $, based on the amount of condensed glycols. 4) Process according to claim 3, characterized in that one dicarboxylic acid derivatives of the general formula wherein R _{1 is} hydrogen or a straight-chain or branched alkyl radical 'with 1 - 10 carbon atoms, with diols of the formula HO-X ₁ -OH wherein X _{1 has} the meaning given in claim 2, and of the formula R ₂ -O-CH ₂ -CH-CH ₂ -OR ₂ CH ₂ Le A 14 422 -H- 309348/1064 where Rg is hydrogen, aliphatic or aromatic Is acyl radical and
M stands for a metal, polycondensed. \. . ■ ^{: ::} - ' ^ ^; 5) Fibers and threads, consisting of high molecular weight, linear terephthalic acid copolyesters containing sulfonate groups according to claim 1, " Le A 14 422 - 15 - 309848/1064 fNSPECTßÖ