DE1435549A1 - Process for the production of synthetic linear fibers or threads, especially acrylic fibers with high shrinkage - Google Patents

Description

Y /. 11287/65 13 / Ko

Monsanto Chemical Company St. "Louis, Missouri (V ₀ St ₀ A

Process for the production of iron synthetic linear strands or threads, in particular acrylic fibers

with high shrinkage

The invention relates to a method for producing synthetic linear fibers with high shrinkage. More particularly, the invention shall look to a method for the preparation of Acrylfusern or filaments with high shrinkage, wherein at least du fi of the fiber consists of acrylonitrile "

The fibers or threads which are produced after the process dimensions of the invention are produced have a number of uses, among which mainly the use as short hair in artificial furs call is, v / obei the fibers or threads with a proportionate non-shrinking fibers are connected and the guard hair or the upright hair

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Pile or pile portion of the fabric, form,. f-enn also; those produced by the method according to the invention. Fibers with holier. Shrinkage ■ with relatively non-shrinking fibers or threads are stiffened or connected (platted) and then this. Sara is treated with moist heat, there is an excellent bulking effect, if furthermore an erect louse is desired on a piece of fabric, this area is composed of relatively non-shrinking fibers, with the low or deep section being composed the fibers produced by the process according to the invention consists of _β The fibers or threads produced by the process according to the invention can also be used for the production of unbound felt, since fine binding agent is required by the shrinkage of this fiber in the materials pulled together to form a felt or bound,

The purpose of the invention is to provide a method of making synthetic linear fibers or filaments "which shrink when treated with heat." Another purpose of the invention is to provide a method of making acrylic fibers or filaments with high shrinkage, which when treated: Shrink with heat. Another purpose of the invention is a process for the production of acrylic fibers consisting of at least 80 fo acrylonitrile, with high shrinkage, which

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shrink when treated with heat «Another purpose of the Invention is to provide a method of manufacture of acrylonitrile fibers or threads with high shrinkage, which when treated with moist or dry heat shrink »Other purposes of the invention are -from the following Description visible.

In general, the purposes of the invention are thereby achieves that one first determines the extent or ratio of stretching in the usual stretching stage, which is based on the spinning operation the acrylic fiber follows, diminished «. This leads to a low molecular orientation of the so produced "The laser or the load is then exposed to steam under pressure" Itaeh this stage becomes the fiber The fiber or the load is stretched in a hot water bath under a regulated temperature. The cable is then pulled out of the hot water bath removed, cooled, curled »moistened, dried, cut into stacks and then ready, around with a laser or shop rope or cord that has relatively no shrinkage for any desired Purpose to be mixed *

In particular, the "purposes of the invention are thereby achieved by putting the acrylic fibers or threads into one The usual spinning bath spins, then the lasers pass through boiling water while the lasers are in a ratio or Extent stretched from 1.5 to 2.5 and preferably 1.3

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be, the polymer is given a low molecularö orientation. The fibers or filaments are then passed through a finishing bath to add any desired finishing or additives, whereupon, generally, the fibers or tow (or hede-tow) are dried and curled, either operation being common: the fiber or the tow are then 'of steam under a pressure in the range of about 2.46 to 5.8? atmospheres (35 - 55 psig), preferably exposed to about 3.16 psig (45) atmospheres, "were to all the fibers engaged with the vapor in contact" Kach the pressure and steam treatment is the cable around ein'Ausmaß of at least 1, 7 but not more than 3.0, stretched in a hot water bath at a temperature of 70 ° to 95 ° 0, the preferred temperature being 85 ° C. The stretched cable is cooled under tension, crimped and at a temperature below 70 ° C ⁰ C dried und'dann in stacking · fibers cut * the stack is then by conventional working steps of the textile industry to G-arnmaterialien od. like verarbeifeto When these are G-arnmaterlalien exposed to boiling water *, they shrink by 57 $> to 50 ^ of their original length. The amount of shrinkage depends on the particular usual stretching and spinning conditions used in the manufacture of the fibers or threads

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same parsers are shrink of 32 ° ß> to about 4-5 ° f its original length when exposed to dry heat 145-155 ⁰ G "The time duration during which the cable remains in the second hot drawing zone is not important. It remains herein only as long as it is necessary for the lasers to reach the required temperature. The method according to the invention can also be used to produce fibers with high shrinkage with widely different denier values, the desired denier being depends on the required end product »The shrinkage produced in the lasers produced according to the method of the invention is considerably greater than in typical commercially available synthetic lasers when treated with heat

The polymeric materials that can be used in the practical implementation of the method according to the invention are polyacrylonitrile, copolymers, including binary and ternary polymers, which contain at least 80.Sew .- ^ acrylonitrile in the polymer molecule, or a mixture of polyacrylonitrile or copolymers, which acrylonitrile with 2 to 50 fa include one other polymeric material, wherein the mixture has a G-esamtgehalt of polymerized acrylonitrile content of at least 80 wt. -fo has. Although the in the present invention

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r polymers used are those which 'contain least 80 <fa acrylonitrile, which are generally recognized as a fiber-forming acrylonitrile polymers,' min- which it is apparent that the invention is equally applicable .on. -. Polymers with a lower acrylonitrile content than 80 $> can be used. The acrylonitrile polymers with a content of less than 80 fo acrylonitrile are .: -... for the formation of films, coating compounds, compounds for molding and pressing operations and paints useful "■ '

The polymer can Z ₀ = B, is interpolymerizable of a copolymer with 80 to 98 fo acrylonitrile and 2 to 20 io -one other monomers containing the / C = C bond and with acrylonitrile exist. Suitable monoolefinic monomers include acrylic acid, X-chloro- acrylic acid and methacrylic acid, acrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methoxymethyl methacrylate, beta-Chloräthylmethacrylat and the corresponding esters of acrylic and ⁰ ^ chloroacrylic acid, Tinylchlorid, vinyl fluoride, vinyl bromide, vinylidene chloride, 1-chloro-i-bromo- · ethylene, kethacrylonitrile, acrylamide and liethacrylamide, << -Chloracrylamide or monoalkyl substitution products thereof, methyl vinyl ketone, vinyl carboxylates, such as. Vinyl acetate, vinyl chloroacetate, vinyl propionate and Vinyls te ar at, ΙΓ-vinyl imides, such as ¥ imid-vinylphinyl and E- Vinyl sue cinimid,

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ffiethylenmalonsäureester, Itaeonsäure and Itaeonsäureester, 'IT-vinyl carbazole, vinyl furan, alkyl vinyl ester, vinyl sulfonic acid, ethylene ^ ^0, ß-dicarToansäuren or their anhydrides or derivatives, such as Diäthylcitraeonat, Diäthylmesaeonat, styrene, Viny! .naphthalin, vinyl substituted tertiary heterocyclic amines, such as the Vinylpyridines and alkylsubstituted vinylpyridines _t z, E _t 2-yinylpyridine, 4- "vinylpyridine, 2-methyl-5 ~ 'vinylpyridine, or the like. 1-vinylimidazo! And alkyl-substituted 1-yinylimidazoles, such as 2-, 4- or 5- Polymerisierlaare Ivimaterialien _o

The polymer can consist of a ternary or higher copolymer, for example products obtained by copolymerizing acrylonitrile and two or more of any of the monomers except acrylonitrile, as listed above -Vinylpyridine "The ternary polymer contains preferably 80" to 98 <fo acrylonitrile ,, 1 bis 10% of a vinylpyridine or 1-vinylimidazole and 1 Ms 18 io any other substance, such as methacrylonitrile or vinyl chloride.

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The polymers can also consist of a mixture of a polyacrylonitrile or a binary copolymer of 80 to 98 fo acrylonitrile and 1 to 20 f> of at least one other ^ C = C <fenthaltenden substance having 2 to 50 Qewo-fof based on the mixture, of a Copolymer of 10 to 70 f> acrylonitrile and 30 to 90 f> of at least one other polymerizable monomer containing ^ C = C <f If the polymeric material consists of a mixture, this preferably comprises a mixture of a mixed polymer of 90 to 98 - fo acrylonitrile and 2 to 10 fo of another mono-olefinic monomers such .as vinyl acetate, which is not receptive to the dye, with a sufficient amount of a copolymer, 10 to 10 fo acrylonitrile and 30 to 90 f ° of a vinyl-substituted tertiary heterocyclic amine " such as vinyl pyridine or 1-vinyl imidazole to give a dyeable mixture having a total content of vinyl substituted tertiary heterocyclic amine from 2 to 10 fo _t based on the weight of the mixture, has β. ·

The invention is explained in more detail below with reference to the examples, in which the stated percentages are based on weight, unless otherwise stated. is ο --- "- ..

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example 1

A mixture consisting of 94 $> acrylonitrile and 6 «£ ■ vinyl acetate existing polymer was dissolved in a common solvent and spun into an aqueous spinning bath" The spun filaments or! Fibers were then then passed into a water bath at 100 ⁰ C over rollers and. The threads or fibers were stretched 1.94 times their original length during their passage through the bath. In addition, the fibers or threads were heated over drying rollers which were heated with steam at a pressure of about 2.11 atmospheres (50 psig) They were then exposed to steam at about 3.16 atmospheres (45 psig) pressure until all of the fibers or filaments were in full contact with the steam, at which point the fibers were 1.83 times of their original length in a hot water bath at 87 C, removed from the bath and cooled while still under chipboard. were voltage "the fibers were then crimped moist and dried at a temperature of 4O ⁰ C. the in the foregoing manner, The tow or rope made was placed in a boiling water bath and the fibers or filaments were found to have a boiling water shrinkage of $ 38 when the original fiber length was compared with the length of the fiber after the boiling water treatment step. Another cable

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Sample, which had been prepared in the above manner, was exposed to dry V / arm in a hot air oven "at a temperature of 145 ° C for a period of 6 minutes." Under these conditions, a shrinkage of the fiber or thread of 34 $> found

Example 2 ■

The procedure of Example 1 was repeated except that the initial stretching degree T, was 06- and the second stretching to a degree of 1.67 at a temperature of 85 ⁰ C was carried out. " The boiling water shrinkage was determined to be $ 38. Another cable sample prepared in the above manner was exposed to dry heat in a hot air oven at a temperature of 145 ° G for a period of 6 minutes. The fiber was found to have a dry heat shrinkage of 32% under these conditions ? ' on how s.

Example 3

The procedure of Example 2 was repeated except that the amount of second stretching was 2.0 and the temperature of the hot water was 86 ^° G ". It was determined that the shrinkage in boiling water was 4 * 4- fold Another cable sample made in the above manner was exposed to dry heat in a hot

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exposed to an air oven at a temperature of 149 ° C for a period of 6 minutes. It was found that the fiber had a shrinkage under these conditions, under a dry Wärme.von 40 fo,

Example 4

There was repeated the procedure of Example 1 except that the second stretching at a water temperature of about 85 ° was 0 and the Streekungsausmaß was 2.0 "The boiling water shrinkage was 39j6 fi, as observed"

Example 5

Kin polymer which ^c from a mixture of a copolymer in an amount of 98.5? ° from 94 fo fo 6 acrylonitrile and vinyl acetate and 1,5 consisted i ° cellulose acetate, was dissolved in a common solvent and spun into an aqueous spinning bath. The spun threads or fibers were passed over Y / alzen and then into a hot Y / water bath at a low boil. The filaments or fibers were stretched 1.6 times their original length as they passed through the hot water bath. In addition, the filaments or fibers were dried over drying rollers with steam at a pressure of about 2.11 atm (30 psig). They were then exposed to water vapor under a pressure iron about 3.30 atmospheres

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(47 psig.) Exposed "until all of the pasers or threads were woolly in contact with the steam. The pasers were then 1.9 times their original length ^: in a second hot water bath" at 85 ° G stretched j removed from the bath and cooled while they were still under tension. The fibers or threads were then curled. and at

¹ N ¹ * - '; - V ^ - ^x ".'.- rv ■.-'-'■■■; ■■ ··.; -" .. a temperature of about 63 ° Cf (145 ⁰ P) ^ for 10 minutes ··.

dried. A heygestellte in dieöer manner Paser was hot air while suspended six minutes in an oven at about 149 ^G E (300 ⁰ P) around and then cooled. In determining the original fiber length .Length Paser im'Vergleich with after the Paser the dry vifäriae was exposed, it was found that a shrinkage τοιι 40 was obtained fö "

With the process according to the invention, pasers or threads of high shrinkage are produced which, when exposed to pasers of relatively low shrinkage and exposed to moist heat, shrinkage with the production of beautiful and in the Hancril acceptable Ijausehigen or voluminous, G-ewet) s ene been with erect odo pattern like. he go en "Pur ixewe" be two or plore Hopp-beJaen (two level pile fabrics), or for artificial or synthetic furs, .If dry heat preferred for developing shrinkage, and preferred dry heat shrinkage is in the range of 35 ° and above. *

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Claims (1)

1435548 Claims 1.Werfahreii for the production of synthetic linear ! Fibers or threads, especially acrylic fibers, with high Shrinkage, characterized in that the fibers or threads are stretched two times in a low degree or ratio subjected to moist heat, whereby the fibers or threads are cooled under tension » 2. Yerfahren according to claim 1, characterized in that the fibers or threads after spinning a first Low-stretch stretching treatment exposes the low-stretched fibers or filaments of a Subjected to steam and pressure treatment, then .the fibers or subjecting filaments to a second low-draw stretching treatment in hot water, the fibers or Cooling threads under tension and drying them 3. The method according to claim 1 or 2, characterized in that fibers with high shrinkage with a content of at least .80 * $> acrylonitrile are produced » 4ο The method according to claim 3, characterized in that one produces fibers with high shrinkage, which from 94 fo acrylonitrile and '6 ° ß> vinyl acetate or a mixture of 88 fo a copolymer of 94 5 & acrylonitrile and 143554S 6 ^c fo vinyl acetate and 12 fa of a second io_schpolymerisats of 50 fo acrylonitrile and 50 ψ> methyl vinyl pyridine consist, 5. The method according to any one of claims 1 to 4, characterized in that fibers of at least ,, 80- ° / o acrylonitrile and Ms to 20 fö another misehpolymerisierbaren mono olefinic monomers a first ötreckbehand.-lung at low Streekungsausmaß in the range of 1 .5 to 2.5 below, the stretched fibers ¥ ate it steam under a pressure in the range of about 2.46 Ms 3.8? atm (35 · 55 psig) exposes, the parsers are subjected to a second stretching treatment at a low stretching amount in the range from 1.7 to 3.0 in a hot water bath at a temperature between 70 and 95 ⁰ C, then the fibers Tension cools and finally dries the fibers at a temperature below 70 ° G * 6. ο Method according to one of claims 1 * to 5, characterized in that fibers made from 94 % acrylonitrile and 6% vinyl acetate are stretched in the first stretching treatment stage to an extent of 1.9; Subjected> 16 atmospheres (45 psig), stretching to an extent of 1.8 in the second drawing treatment, with the hot water bath at a temperature of 87 ° C. BATH ORIGINAL 809812/0653 7. The method according to any one of claims 1 Ms 5 »characterized · characterized in that fibers from a mixture of 88 fo one. Interpolymer clay 94 P acrylonitrile vaiä 6 fo vinyl acetate and Λ2 io of another interpolymer of 50 <fa • acrylonitrile and 50 $ iviethylvinylpyridine in the first ■ stretching treatment stage to an extent "of 1.9, she the steam treatment under a pressure clay Subjected to about 3.16 at.u (45 psig), in the second stretching treatment to an extent of 2.0, where the hot water la ad has a temperature of 85 ⁰ C _a 809812/0653