DE2011050A1 - Copolyester - Google Patents

Description

The Goodyear Tire & Rubber Company, Akron, Ohio / USA

Copolyester

The invention relates to new copolyester hairs and improved polyester threads, films and other products made from them Oopolyester resins are produced.

Set synthetic threads made of aromatic polyester resins made up of relatively large linear molecules. In order to such threads have appropriate Garaelgenechaften, the resins from which they are made must soak have high molecular weight. It was generally used

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because as the molecular weight of the resin from which a thread is made increases, the physical properties imparted to the threads are improved, , threads made of aromatic polyester resins, such as Polyethylene terephthalate, are generally highly elongated crystalline structures that are more difficult to color than threads or yarns made from natural fibers, regenerated cellulose or protein fibers. She stretched The crystal structure of aromatic polyester fibers is not readily influenced by water or by dye molecules during Imbued with common staining methods,

Were prepared from polyethylene terephthalate fibers, can sswischen 120 and 13O ⁰ G under superatmospheric pressure at elevated temperatures: are colored using disperse dyes. However, these temperatures are too high for certain natural fibers, so that goods made from mixtures of polyester fibers with natural fibers can be destroyed by such temperatures. Polyethylene terephthalate pads can also be colored using a vehicle to swell the fibers and allow the dyes to invade. The use of carriers is impractical because they are difficult to remove from the fibers and plasticize or soften polyester fibers. In addition, they are impaired in their serviceability by such carriers, furthermore carriers swell the fibers and make them resistant to the action of dry cleaning agents _; less resistant. In addition, the use of carriers adds to the cost of dyeing because fibers that are dyed using a carrier must undergo further treatment to remove absorbed carrier. There is therefore a need for polyester fibers, especially when

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these parsers are to be blended with other fibers which are dyeable at temperatures of about 10O ⁰ C or lower without using an Slower.

The aim of the invention is to create new copolyester resins, the Bioh sum are suitable for spinning fibers, which can be dyed using disperse dyes. By The invention provides improved polyester fibers which are dyed at relatively low temperatures can, whereby the staining can be carried out without the use of a carrier for undermining the staining. The new copolyester resins have a decreased Sohmels viscosity. They are particularly used to produce Fibers with a long tear length are suitable. Also falls within the scope of the invention a process for the preparation of these gopolyester resins.

Ba was found in an unexpected way * that fibers that

made from copolyesters, those made from ethylene glycol, terephthalic acid, and azelaic acid, one markedly improved dye affinity possessed such

Fibers can be dyed directly to deep tints without

that this requires the use of a carrier. |

Compared to polyethylene, the copolyester haree

terephthalates have a reduced melt viscosity and can processed into fibers with a long tear length.

It is usually convenient to be at least about 1.0 56 moles of azelaic acid based on the total moles of acid units in the copolyester. Fibers made from copolyesters, which contain up to about 10 M0I-5S azelaic acid, have a good tear length, an improved one Affinity for disperse dyes as well as others desirable

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Properties. The copolyesters contain ethylene terephthalate units in an amount of 99 - 90 # of the sum of the Ethylene terephthalate units and the ethylene azelate units la the copolyester and correspondingly 1 to 10 Kol-jG the Sum of the ethylene azelate units. The preferred copolyesters have ratios of ethylene terephthalate units: Azelate units from 97.5 / 2.5 to 90/10, with the most preferred ratios of xerephthalate-to-aselate units being between 95/5 and 92/8.

Me inventive copolyesters can be prepared in such a way that ethylene glycol, terephthalic acid and Azelaic acid can be reacted with one another, or that ethylene glycol with a mixture of ester-forming Derivatives of terephthalic acid and ester-forming derivatives of azelaic acid, such as the lower alkyl esters or similar derivatives, is implemented.

According to a preferred embodiment of the copolyester according to the invention, Iat and ethylene glycol are used for the reaction at a temperature of 140- $ Q $ ° 0 in the presence of a catalyst, such as, for example, gan diacetate, at atmospheric pressure. The gewüneohte amount of azelaic acid is given anschlieae 'a4'', after which the heating at 200 to 220 ⁰ C is fortjiattjt to distill the formed in the esterification reaction of Azelaiawtar · water. After the theoretical amount of water has been distilled off, ice Tatanun is applied until a pressure of 1.0 torr has been reached. At the same time, the reaction temperature is increased gradually from about 220 to about 275 ° 0. In the case of Atr condensate ion area, the glycol released is distilled off.

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OmöJ INSFECTEO

lates. After the desired viscosity has been reached is, the copolymer melt is removed from the reactor. To carry out the ütaesterungsreaktion you can use different catalysts. Suitable catalysts are, for example, zinc acetate, lead acetate and manganese acetate and black lead. Even though it is not essential, one Catalyst of the reaction solution for carrying out the esterification reaction such an addition is nevertheless expedient, since certain esterification catalysts are used the esterification reaction is favored. Representative examples of such esterification catalysts are soluble metal glycolates, alkylates as well Salts of weak acids, tertiary amines and amphoteric Metals.

The copolyesters can also be prepared by direct esterification of terephthalic acid and azelaic acid with ethylene glycol. This reaction is expedient in the presence of a low molecular weight polyester, such as Poly ^ thylenterephthalatZ-azelat) or a low molecular weight polyethylene terephthalate carried out, with corresponding reactant ratios set to arrive at the desired copolyester. The esterified product is then as long as under a reduced pressure in the presence of a catalyst condenses until the desired solids viscosity is reached has been. \

Various catalysts can be used to carry out the condensation reaction can be used. Representative examples of suitable catalysts are antimony triocide, black lead, Glycol-soluble compounds from Sitan and glycol-1ösliehe Compounds of cobalt.

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To give products good physical properties, it is necessary that the copolyesters have a high molecular weight, ie have an intrinsic visual viscosity of at least 0.3 and preferably at least 0.5; They can be colored with pieper dyes without using a vehicle to promote coloring. Various disperse dyes can be used. Representative examples of such dyes are JDuranol Blue S, Dieperaol Scarlet S, Dispers oil P ₉ Orange B, Duranol Br and Yellow! Er.

The following examples illustrate the invention. example 1

β.4 kg (18.6 pounds) of dimethyl terephthalate, 6.2 kg (13.6 pounds) of ethylene glycol, and 21.3 g (0.75 ounces) of manganese acetate are placed in a reactor and kept at 190 under a nitrogen atmosphere with constant stirring - 210 ° 0 heated until the release of methanol has ended. Then 613 g (1.36 pounds) of azelaic acid are added, whereupon the temperature is increased from 210 to 230 ⁰ C the formed by the reaction of azelaic acid water abzudestil-witches. Then 0.23 g of antimony oxide are added to the reaction mixture. The temperature is slowly increased to 280 ° C while the pressure is decreased to 0.5 mm Hg. After the copolyester has reached the desired melt viscosity, it is withdrawn from the reactor and spun into a yarn using a conventional melt spinning and drawing process. A sample made from the yarn is dyed with disperse oil soarlet disperse dye without a carrier at 85.degree. C. for a period of 1 hour.

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The goods are dyed with a deep tint. A comparative product which iet made from polyethylene terephthalate _v besitst no affinity for the dye.

Example 2

7.4 kg (16.2 pounds) of terephthalic acid, 523 g (1.17 pounds) of aselaic acid and 3.50 kg (7.72 pounds) of ethylene glycol are exposed to 13.6 kg (30 pounds) of a molten low molecular weight polyethylene terephthalate. Pie reaction mixture is absolutely psig ($ 3) kept under a nitrogen pressure of 2.46 kg / cm to 25O ⁰ C after the Freiseteung has stopped of water, 0.48 g of antimony trioxide are added. The reaction mixture is then under a pressure of 0.5 mm Hg at 280 ° 0 der

Polycondensation reaction examined. From this polymer yarns are spun and processed into a product. This commodity becomes one in the same manner as in Example 1 deep hue colored. A comparative product made from polyalkylene terephthalate can only be colored slightly.

It has been found that small amounts of pentaerythritol, exposed to the reactants improve the color of the copolymer resin. Copolyesters up to 0.084 mol- ^ (based on the total moles of glycol units in the copolyester) are whiter than resins that do not contain pentaerythritol.

In the presence of a carrier, ΔtbyI terephthalate / Dye ethylene aeelate gopolyester in deeper tones than

the homopolymer. . '

Sine colored goods made from a 94/6 ethylene terephthalate / ethylene belate copolyester bleeds in tetrachlorobenzene at 46 ° C '

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does not go off for a period of 1/2 hour. The washability of the goods is excellent.

Fibers made from copolymers which have been produced using the free acids as reactants can be used Color slightly deeper tints than pasers, which have been produced using dirnethyl esters as beactants. So is a 94/6 ethylene terephthalate / ethylene azelate copolyester, which has been prepared by esterification of the free acids and condensation, a 93/7 ethylene terephthalate / ethylene azelate CopoIyester equivalent, which by transesterification of Dimethyleater of acids and condensation has been produced, namely with regard to the absorption capacity for disperse dyes.

! Table I.

Comparison of the properties of copolyester with the properties of a polyethylene terephthalate

Homopolymers

Polyester, the duroh Polyester «the Transesterification and condensation and condensation have been established are

* 1OO / O 93/7 100/0 94/6 Intrinsic viscosity * 0.624 0.606 0.628 0.622 Hydrolytic degradation 0.09 0.09 0.09 0.11 (f> broken bin fertilize) density 1,370 1.328 1.361 1.326 Carboxyl content, eq / 10 ⁵ g 40 9 15th 11 Melting point, ⁰ C (DSA) 254 245 254 242

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The table above shows the physical properties of fibers according to the invention with the properties of a polyethylene terephthalate homopolymer are comparable. The copolyester fibers, however, have somewhat lower melting points on. ".- '■■'

Fibers made from the copolyesters according to the invention have a improved dyeability compared to homopolymers, although the physical properties and history of the fibers are the same. This comes from the values which are summarized in Table IX below are.

label II Washfastness Fiber properties 4.137 • 4-5 of ethy- Determined experimentally Dry cleaning fastness - 0.59 5 lenterephthalate / azelate 146/35 Same as 4.1 1O0 / O 27 4.137 Stretch ratio $> 8.9 0.58 Xntrinsic viscosity * 242 144/35 denier 19th 4> 25 Tear length ° 0) middle 32 Elongation, §6. solution 3.8 Shrinkage in boiling water, very deep 255 Melting point, ⁰ C 47 Garboxyl content ^, Iq / 10 g very Color image (no carrier at 99 easy middle Dye uptake (10 # Oarolid at 99 ° ö) 4-5 5

* The intrinsic viscosities are measured at 30 ° 0 in a 60/40 phenol / carbon tetrachloride mixture determined.

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- ίο -

All staining tests shown are made in the Gaston Oounty stainer carried out. Knitted goods made of resin fibers are introduced into the dye solutions at 70 ° 0, whereupon the tempera tor is increased to 99 ° C. The total staining time is 2 hours. You used batches of dye sit as follows:

(A) No carrier

3.5 i »disperse dye

30: 1 liquid: goods

2 drops of Duponol RA (wetting agent)

In all cases, the goods are ^{moistened in water at a temperature of 70 °} C. in order to achieve an optimal flow.

(B) With carrier

(1) Carrier: 10 # Garοlid by weight of the goods. The fabric is treated in the vehicle for approximately 10 minutes prior to dyeing.

(2) Dyeing corresponds to the above-described method without using a carrier, wherein 1 io KaH ₂ PO., Based on the weight of the product is added.

The dyed goods are post-treated for 0.5 hours at 70 ° 0 in the following bath:

0.1 # Triton X-100

0.1 i » anhydrous soda

100 water

Fibers which are produced from the resins according to the invention can be produced by melt extrusion as well as by spinning a solution in a suitable solvent.

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2Ό1Ί050

Such fibers can be drawn. you will be usually stretched by cold drawing. If necessary, can the fibers are fixed by heating them to an elevated temperature are kept under tension during βie in a known manner will. They stretched fixed ones according to the invention Fibers have reduced dyeability, a long travel distance, low elongation and other desirable properties. They are particularly suitable for use on the textile sector. For example, you can use them in the form of staple fiber blends that are about 25 - 65 de- | weight # of the copolyester staple fibers and 75 - 35 weight ^ contain another staple fiber. Mixtures of fibers with a low shrinkage capacity can be used to produce Outerwear is used, for example for the production of costumes and suits, for the production of sports guards, Underwear, sports trousers, sweaters or similar clothing. Other uses are in the manufacture of covers, foils, mattress covers and pouches to see. In the case of the Copolyester fibers to be mixed staple fibers with little Shrinkage capacity can be fibers made of cotton, Silk, rayon, linen, wool, acrylic polymers and copolymers, < Nylon and polyester fibers, such as polyethylene ' terephthalate and poly-1,4-cyclohexylenedimethylene terephthalate, Act. Preferred blends consist of 25-65% by weight of a copolyester according to the invention with 75-35 Weight- ^ cotton and 25-65 weight- ^ one according to the invention Copolyesters with 75 - 35 weight? S wool.

Mixtures of fibers according to the present application with other fibers are particularly suitable for the production of textile objects in which certain patterns are to be achieved.

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Such textile articles can be produced by subjecting the textile to a treatment in a dye bath. This way you can mix the Copolyester fibers with fibers with different dyeability, such as polyethylene terephthalate, all in one Weave an object, for example a carpet, after which such an object in a disperse dye bath in can be colored in a single step. The colored object obtained then has a salt-and-pepper tint fc or a similar pattern. Furthermore, by appropriate interweaving, articles can be produced which, if necessary have checkered coughs or other patterns.

Mixtures of fibers with a low shrinkage capacity with Fibers with a high shrinkability are suitable for the production of buildable and bulky yarns, textured goods and carpets.

Mixtures of the copolyester fibers with fibers that have elastic properties are suitable for the production of streokwaren, sportswear, socks and other articles for the production of which stretchable materials are required. Mixtures with elastic fibers W, such as Iyera, to £ UEX uses where it comes to a Verstreokbarkeit suitable.

In addition, mixtures of endless single threads made from gopolyesters according to the invention with endless single threads made from other materials can be produced. With the mixes can they are also mixtures of staple fibers and mixtures of continuous single filaments and staple fibers. Ser-like mixtures are suitable for the production of buildable composite yarns, bulky yarns, and crimped fibers

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and goods. Mixtures of fibers with different Shrinkage properties are particularly suitable for manufacture permanent, folded garments as well as the production of thermal insulation goods, textured goods,! carpets and the same.

The copolyesters according to the invention are valuable film-forming ones Materials »Films can be produced from these copolyesters by melt extrusion or other suitable methods will. A stretching or coverage improved | the film properties. Films and sheets made from the polyesters are characterized by good clarity and brilliant gloss. They are characterized by high tensile strength and low elongation, good aging resistance as well as characterized by excellent electrical properties * They are particularly suitable for packaging purposes, for the production of magnetic tapes, electrical insulation as well as other applications where high strength clear films are required. Films made from crystallizable gopolyesters, the 2.5-10 mol # ethylene aselate and 97.5-90 Mol-jS containing lifhylene terephthalate can be in an amorphous state by supercooling the hot amorphous film before the ^ Occurrence of crystallization can be produced. Such films can be easily produced by heating and then Pull apart, stretch. They can be fixed by known methods, for example by heating while they are under tension. Is a biaxial If you want stretching, then the films can be made in two sizes Way in two directions that are at a right angle stand to each other, be stretched.

For some uses, it's convenient to watch the movie only to stretch in one direction, for example to

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-u-

8 Division of belts for industrial purposes. A Stretching in only one direction can, for example achieve in such a way that a PiIm is wound from one roll to another, with the second roll sioh with rotates at a higher speed than the first roller. Simultaneously with such an extension, others can well-known, the Veratreckung easier methods used for example, heating the film by any suitable means immediately prior to the actual P stretching the "film.

The ethylene terephthalate / ethylene azelate gopolyeeters according to the invention can contain small amounts, namely up to 5 f> ₉ units of other dicarboxylic acids or glycols. Examples of such other dicarboxylic acids are adipic acid, sebacic acid or dodecanedicarboxylic acid. Examples of other glycols are, for example, tetramethylene glycol, pentamethylene glycol and hexamethylene glycol. Such modified copolyesters should contain a total of at least 85 mole ethylene terephthalate units.

^ Even if the copolyester in general without another Compounding are used, they can nevertheless also be compounded with other materials if necessary. Compatible resins, elastomers, pigments, matting agents, dyes, plasticizers and other compounding ingredients can be added either by mixing the materials together in an appropriate one Mill or other mixing device or by mixing such compounding ingredients in solutions the polyester in a solvent.

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Claims (1)

2Ö11050 - 15 patent claims. 1. Ciopolyester, characterized by itbylene glycol units, terephthalic acid units and eelainic acid units, the terephthalic acid units making up 90.0 - 99.0 j £ the Svatwe der Hole the acid units in the copolyester, and the azelaic acid units 10 - 1 # of this sum. 2. Copolyester naoh claim 1, characterized in that the lerephthalic acid units 90 - 97.5 # of the sum of the colons of the acid units in the oopolyester, while the Aaelic acid units are 10 - 2.5 # of the sum. 3. Copolyester according to claim 2, characterized in that it is in the form of a uae. 4. Dyed fiber according to claim J _9, characterized in that the fiber has been colored with a sieve dye. 5. Copolyester according to claim 1, characterized in that the terephthalic acid units 92 - 95 9 »the sum of the moles | of the acid units in the copolyester, while the aselaic acid units are 8-5 i> this sum. 6. Oopolyeeter after. Claim 1, characterized in that he is fooled in a film in Perm. 7 «mixture of 25-65 weight fibers from a copolyester according to claim 1 and 75-35 weight fibers from one other fibers made from cotton, silk, rayon, linen, Solid, Aory! Compounds, nylon or a polyester. 009841/1915 2-01Ί Ο 5 O »16 8. Dyed goods from a mixture according to claim 7 »thereby characterized as having a patterned appearance. 9. A method for producing a copolyester, characterized in that ethylene glycol with an ester-forming Compound before terephthalic acid and an ester-forming compound Clay azelaic acid is brought into reaction, whereby the terephthalic acid compound used 90 - 99.0 mol- # makes up the total mole of acid compound present, while the aselate is 10-1.0 mole jS of the present acid compound is, wherein in this reaction the glycol esters are formed dor acid, and these glycol esters under Release of glycol with the formation of glycyl ester resins condensed with high molecular weights. 009841/1915