DE1494641A1 - Process for the production of synthetic fiber mixtures - Google Patents

Description

Process for the production of artificial fiber mixtures Priority: Japan January 16, 1963

The invention relates to a process for the production of synthetic fiber mixtures which have excellent crimp and have a woolly "handle", have a high elasticity and buckling resistance or flexibility and through LIisohverspinnen a viscose and a nitrile-substituted Protein derivative can be obtained. The protein derivative is substituted by further chemical conversion of a nitrile Protein derivative with which a monomeric compound bearing an unsaturated ethylene group is graft polymerized has been·

Bs is already known to have fibers that feel woolly or have a woolly "handle", obtained by spinning a viscose together with a protein · The products rot and decompose so easily, however, that uniform and satisfactory fibers are difficult to obtain

• 09144/1531

U94641

was. In addition, the buckling strength is the one generated in this way fibers very little and also their tear resistance moderate. Although they come close to wool in some properties, they are therefore of little use and are rarely used.

Picara pairs (products of Virginia Carolina Chemical Company, U.S.A.) are made by spinning grain protein as a raw material and treating the fibers produced with formalin obtain. The strength of these fibers is 1.0 to 1.5 g / d. Because it will feel like cashmere wool » recommended to mix them with other fibers »to improve the" feel "of the products ·

If a protein is added to the viscose without risk of decomposition can be and the fiber mixtures formed can be processed into stable products, so leave man-made fibers with excellent "grip" and industrial uses are produced.

Be was a process for the joint weaving of a Synthetic resin emulsion of a protein graft polymer with viscose suggested to elasticity and water resistance to improve the viscose fibers

As a result of systematic studies of the relationship between two Molecular structure and colloid character of protein

9008U / 1636

derivatives and about the influence of such protein derivatives on Kunatfaeergemisohe for the purpose of preventing rot and decomposition of the protein as well as to achieve a uniform and a stable mixture of this protein derivative, we submit this invention.

We stated that (1) a protein derivative produced by chemical bonding of a nitrile compound, which is known as functional group an epoxy radical, a halogen radical or carries an unsaturated ethyl radical to a protein is obtained »(2) a protein derivative which is obtained by further chemical treatment of the protein derivative (1) or (3) a protein derivative obtained by graft polymerization of (1) ■ with a conomer because it has an unsaturated ethylene group » is obtained is difficult to rot and decompose and the viscose to form more uniform and stable Products can be added

We have further found that fibers with excellent crimp and a woolly "handle ·· as well as high elasticity and kink resistance by mixing an aqueous solution of such a protein derivative or an emulsion of such Protein graft copolymer produced with viscose and spinning the mixture in the usual factory-made manner can be

009844/1636

U94641

The one mentioned in the present invention substituted with a nitrile group Protein derivative is structured as follows!

a protein derivative that duroh addition reaction a nitrile compound substituted with an epoxy group is obtained on a protein,

f £] a protein derivative that by addition reaction of a is obtained from an unsaturated ethylene group substituted hi / tril compound on a protein "

[3] sin graft polymer, the duroh graft polymerisation one substituted with an unsaturated ethylene group Iitrile compound obtained from a protein will}

Pas duroh further brazen implementation of a nitrile-substituted The derivative obtained from protein derivatives is constructed as follows 1

a protein derivative which, through implementation, united low- or high molecular weight aldehyde obtained with one of the nitrile-substituted protein derivatives listed above will.

That by graft polymerisation of an unsaturated EthylenrerblnAung obtained with a nitrile-substituted protein derivative Graft polymer is structured as follows!

• 01044/163

IjQ a graft polymer, which by graft polymerization

a vinyl or yinylidene monomer with one of the nitrile-substituted protein derivatives listed above is obtained.

Details about the to be used according to the invention Protein derivatives and inre common spinning uit Viacose should be explained below.

Spinning of a mixture of viscose with the derivative obtained by addition reaction of one with an epoxy group substituted nitrile compound and a protein is produced.

A nitrile compound substituted by an epoxy radical can an addition reaction bit to the active hydrogen of an amino radical, a carboxyl or alcoholic hydroxyl radical of a protein in (regenwart of a basic catalyst enter, with a protein derivative containing a nitrile radical, arises ι in the following manner

P _r -HH ₂ + OHg-GH- (OH ₂ ) _n -Cai ₁

P _r denotes the polypeptide of the protein, -NH ₂ the terminal amino radical of the protein and η is 0, 1 or 2.

For example, 2-0yanomethyl-ethylene oxide goes into a protein

BATH

Addition reaction with formation of a hydroxy-cyanopropylated Protein:

P _r -NH ₂ + QHp-JH-CH ₂

CN

Are one example, a 5 ^ sodium hydroxide solution of a protein 0.3 to 2.0 moles of 2-cyanomethyl-ethylene oxide per LoI amino acid residue in protein dEiu added and Äset react for 1 to 2 hours at 4O ⁰ C, then an addition to the smooth alcoholic hydroxyl radical, the amino and carboxyl radical and a hydroxy-cyanopropylated protein is obtained.

Compared to unchanged protein, this protein derivative possesses a higher resistance to rot and resilience to alkali and can be mixed evenly. Those obtained in the usual way by admixing Fibers have a woolly "handle" and are excellent Curl and kink resistance.

Contain the nitrile compounds suitable for use Epoxy radicals such as 2-oyanoethylene oxide, 2-cyanomethylethylene oxide etc., which can undergo an addition reaction with the active hydrogen of a protein

Since these nitrile compounds have an active epoxy group, the addition reaction with the protein proceeds quantitatively.

809844/1636

All catalysts are suitable based on compounds such as hydroxide, potassium hydroxide, primary, secondary and tertiary amines and salts of amines. They can be under suitable reaction Reaktionebedingungen in a Temperaturbereioh from 10 to 9O ⁰ C and for a reaction time of 10 minutes to 5 hours.

The proportion of protein derivative that can be added to the viscose is 5 to 50%, preferably 10 bi 30>, based on the weight of the fibers to be spun from the Gemisoh.

ο GO spinning a mixture of viscose with the derivative, the addition reaction of a nitrile-substituted, unsaturated ethylene compound with a protein is obtained.

Unsaturated ethylene compounds which are substituted with a radical which is strongly negative in relation to a protein can be activated in the presence of an alkaline catalyst and then go with the active hydrogen an addition reaction of the Michael reaction type on the protein, with an oyanoalkylated in the following manner Protein is formed ι

? _r -ra ₂ ♦ f - ο

fi b

P "HH _O + Ö« C »P _r -NH-C-CH

A ₂ CN I ₂ ' OT

009Θ44 / 1636

U94641

A ₁ and A ₂ and H or an OH radical, A, iet H ₁ «in CH-ladikal or an OHj-hadicle.

When using tetraoyanoethylene or vinylidenoyanide becomes a tetracyanoethylated protein in the following way

or a CI ₁ CJ -dioyanoethylated protein obtained

CN CN basic CN CN

CN

CN CN Asian C P-NH ₉ + C »C ^ _{p NH} _ _σ _ <j _H

^{Γ 2} IIII

CN CN ON CN

CN basic OV

P _r -HH ₂ + CH ₂ -O ^ ^ _m . ₀ E ₂ 0 ^

CN CN

If 0.3 to 3.0 moles of tetraoyanoethylene per mole of amino acid residue in the protein are added to a protein dissolved in a 5% aqueous sodium hydroxide solution and an addition reaction is effected for 3 hours ^{at 3O 0 O 2} , «Ο a tetraoyanoethylated protein is produced.

The protein thus produced and substituted with nitrile radicals is resistant to rot and decomposition and can be combined with viscose to form a stable Gemisoh When the mixture is spun, it will be in the usual way Fibers with woolly "feel" and excellent crimp and kink resistance are obtained.

• *

The unsaturated ethylene groups substituted with nitrile radicals

9099U / 1636

Compounds used in the present invention are reagents in which one of the nitrile group is one + B effect on the -OC bond of the active unsaturated radical, i.e. the ethylene, vinylidene or vinyl radical, starts.

Among these unsaturated ethylene compounds are nitrile compounds with ethylene radicals and vinylidene radicals such as tetracyanoethylene, tricyanoethylene ,, vinylidene anide, methacrylonitrile and OC- chloroacrylonitrile and nitrile compounds old a vinyl radical such as acrylonitrile. They can be used as one or as an Oemieoh of two or more of these substances

Suitable catalysts are strongly basic compounds such as basic inorganic salts, e.g. 3. Sodium hydroxide, potassium hydroxide, Potassium yanide and sodium cyanide, also quaternary Ammonium hydroxides such as trimethyl-benzyl-acimonium hydroxide, Dime thy1-phenyl-bcmzyl-ammonium hydroxide, etc.

Sa having the above-mentioned nitrile active unsaturated radicals, they react in the presence of a base catalyst easily with a protein, but the reaction is preferably carried out in a temperature range of 20 to 9O ⁰ C and at a Reaktionedauer from 20 minutes to 5 hours.

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The proportion of protein derivative that can be added to the Yiekoee is 5 to 50%, preferably 10 to 30%, based on the weight of the fibers to be spun from the mixture.

Spinning a mixture of viscose with a Graft polymer obtained by graft polymerization of a is obtained with an unsaturated ethylene radical substituted nitrile compound with a protein.

When a monomeric nitrile compound that is an unsaturated Contains ethylene group, so see B. a monomeric vinylidene or vinyl compound in the presence of a polymerization catalyst old a protein as a stem polymer graft polymerized is obtained, a graft polymer is obtained which has a ■ Vinyl or vinyl or vinyl polymer substituted with a nitrile radical al · Zweigpolpolymerβ contains · Pie conversion takes place duroh transmission reaction 4 # r chain

For example, when hydrogen peroxide "(catalyst) and vinylidenecyanide to a 0.5% aqueous sodium hydroxide solution of a protein are added and the reaction is duroh carried out at 65 ° O with stirring, then a graft polymerization takes place of the vinylidencyanJrds with the protein and ee will in about 3 hours the following protein vinylidene cyanide graft polymer received as Bonlslon.

9008U / 1636

U9A6A1

CN

P _r -HH - - '

~ CN

We have found that the solution of a protein derivative (graft polymer) produced by the above-described graft copolymerization was obtained only with difficulty to Päulnie and decomposition is to be brought about and under formation a permanent, spinnable Gemisohee can be mixed with viscose can.

As unsaturated ethylene compounds with nitrile radicals are substituted, nitro compounds and acrylonitrals are suitable with -CH-C ^ - radicals such as vinylidenecyanide, .ot-ethylacrylonitrile, o ^ -chloro-acrylonitrile, oC-ethyl-acrylonitrile, Methacrylonitrile etc.

Winn such a graft polymer as an emulsion with viscose mixed and the mixture is spun in the usual way, fibers with a woolly "handle" and a get high elasticity. The graft polymerization can be carried out with any desired mixing ratio of monomers Protein. But it is favorable when the amount of monuments which are polymerized with a protein should be about 0.3-2.0 times as large as the weight of the protein will.

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1494841

The proportion of graft polymer that is added to the viscose can be, is 5 to 5 <#, preferably 10 bie based on the weight of the su spinning from the mixture Fibers.

A water-soluble peroxide such as ammonium persulphate, potassium persulphate or hydrogen peroxide can be used as the catalyst. The catalyst should be used in an amount of 3 to 0.05% by weight, based on the lionomer. The most favorable polymerization temperature is 50 to 85 ° 0. It is also possible to use a redox catalyst by adding a reducing agent. Triethanolaain or sodium sulphide can be used as reducing agent in an amount of between 3 and 0.05 pounds. The appropriate temperature for dis graft Oopolyaerieatlon is 20 to 70 ⁰ O.

The fibers spun from this mixture are strong Not inferior to ordinary staple fibers »they have many fine crimps and are advantageous in the Slastism and under the "handle".

[4I spinning a mixture of viscose with a derivative, this is achieved by reacting high-molecular or low-molecular aldehydes with nitrile-substituted protein derivatives will receive.

0OMU / 1636

Wean a hdehyde compound instead of the nitrile-substituted one mentioned above Derivative, e.g. a cyanoalkylated protein, is converted into a derivative of this in the following manner

Preserve proteins »

H U0- (0H ₂ ) _n -HH-P _r -NH ₂ ♦ RCHO> KC- (OH ₂ ) _n -HH-P _r -HH-CR

OH

Let hydrogen, an alkylene radical with 1-4 carbon atoms, -GH-CH ₂ or a high molecular chain.

For example, if a hydroxy-cyanopropylated protein is used as a nitrile-substituted Protein derivative used and a vinyl alcohol-aorolein copolymer of a high molecular aldehyde is reacted with this protein derivative, it becomes the following Get protein derivative »

H ₂ MP _r -MH-CH-CH ₂ OH ₂ CH

♦ F-CH ₂ -OH-CH ₂ -CHrCH ₂ -CHl L OH OHO QHJ

OHl η

HO-

-Py-IH-CH-OH ₂ -CH ₂ -CH

As epeeielles example, the following may be cited} When 33 mol * allylidene diacetate and 67 UOI ^ i Vinylaoetat using azo-bie-isobutyronitrile as a catalyst are copolymerized with each other and \ $ öew. ^ Of a vinyl alcohol-acrolein Copolymeriaats obtained by alkaline hydrolysis of

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U94641

dtr oUfta copolymerization is obtained .iu an alkaline Lo "wag eiste hydroxy-oyanopropylierten proteins • ugegeben be and dae mixture at 30-5O ⁰ C 2 bie 3 hours ungeeetzt is, the desired protein derivative.

In this derivative, the aldehyde group and the amino group are des Proteins linked together and the aldehyde radical dee Aorolel molecule is free. Therefore, when the named derivatives are increased, a temperature similar to a polypeptide chain occurs and an active hydrogen atom in cellulose and the product is alkaline-soluble. You au · a «Qtaisoa the ··· protein derivatives with Tlako ·· geeponneaen Paeerm «own particularly good resistance to alkali. The protein derivative is easily miscible alt Tiekoee. I'm Gemieoh The protein derivatives old viscose can be spun excellently and have the paeern produced by this mixture a woolly "handle" and have an excellent crimp and great strength.

The nitrile-substituted protein derivatives that can be used in the reaction with the aldehyde are not limited to those listed above, but any of the compounds listed in Sections Q ^ and JjJ can be used.

AldetydrerbinduneeD, which at the ^

BATH

be used, a low molecular weight aldehyde such as adipaaldehyde, glyoxal, butyraldehyde, acetaldehyde, ormaldehyde. Acrolein, methacrolein etc. and high molecular * aldehyde compounds such as polyaorolein, polymethaoron, dialdehyde steVs, Dialdehyde compounds produced by opening the 1,2-ulykolve * bond are obtained from polyvinyl alcohols η and polyvinyl alcohols old called aldehydes, which are obtained by saponification of the copolymers from allylidene diaoetate and vinyl acetate can be obtained. Also a mixture of two or more thieves Aldehydes can be used. Haoh leave it to your liking The compounds can also be used as an addition product with sodium sulfite let the reaction be used.

SIs above angsftthrtva AldeÄyd connections react right ewithout11 with the straight protein to form a gel, and the reaction is sohwisrlf under control su bring you Srfindungegemäaeea, oil-substituted protein derivatives react but because of the steric effect of the sterile group slower and more uniform with these aldehydes »so that a stable and uniform solution is obtained.

As catalysts in the above reaction between an aldehyde and the protein derivative, alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium phosphate, etc. can be used. The reaction can take place in a temperature range from 10 to 70 ^° C. and with a reaction time of 30 minutes

909844/1636

up to 3 hours. The Seaktlon is however not limited to the ·· Conditions limited.

The proportion of aldehyde-sensitive item protein derivative that can be added to the viscose is about 5-50% (rorr zugβweie · 10-30 ^), be sheet on the weight of the fibers spinning from the gern is oh su. The mixture can be spun or shaped into fibers in the usual way. * ■

It is not necessary for the fibers obtained to undergo a Maoh treatment Subjugate with formalities, fenn the fibers Jedoom WMrasbehelten weroeB, to let sioh the Geaalt aa

Protelnderirmt (in the Faeera), the alkali is resistant to water is, nooh further increase.

Spinning a mixture of Viekoee old one » Graft polymer, since then graft polymerisation of a monomeric unsaturated ethylene compound with a Permitted protein derivative is inherited.

When an ethylene unsaturated monomeric compound such as e.B. a monomeric vinyl or vinylidene compound in the presence of a Polymerieationekatalyeators with a nitrile sub-titled Protein derivative is graft-copolymerized, so will -duroh transferring the chain a Pfropfpolyaerisat with a obtained polymeric vinyl or vinylidene branching.

0O98U / 1636

BAD OWGINAL

U946A1

If, for example, styrene is used with a U, Cl • -dicyanoethylated protein dissolved in an aqueous alkali solution tob polymerized hydrogen peroxide as a catalyst becomes, BQ becomes the following graft polymer as white flecked (white-polluted) stable building emulsion obtained.

We have found that the solution of the acidic vinyl or Vinylidea-Protein-Graft-PolyBerisate ■ · Resistant on the other hand, the public is open to the fact that ·· «it is Tislco ·· to invite ·“ η Qemisoh susasa given can · As aonoaere vinyl compounds see acrylonitrile, styrene, aoryl ester, Methyl ester and vinyl chloride · If a single graft polymer emulsion Kit viscose fexalsoht and in the Ubliohen Wise Terspvnnen becomes "so Tasergealeons" it becomes a "woolly" one "öriff · and hoter llaetliitftt received.

The nitrile-substituted protein diets that make up the invention can be used in the copolymerization are not particularly limited, and all of the above can be included Sections (1), (2), (3) and (4) listed connections

use.

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U9A641

Even with the addition of about 2 <# (parts by weight) or more (based on based on the weight of the cellulose component) of graft copolymer there is no noticeable reduction in the strength of a viscose detect (spun) fibers that were produced. When the emulsion of the graft copolymer is spun mixed with viscose is and the strength of the formed strands is noticeably reduced, this can be achieved by adding a small amount of a surfactant »to the dope be avoided. Also by adding a small amount of a water-soluble polymeric solvent the reduction in strength is limited to a minimum will.

If an -onanier vinyl compound is graft copolymerized with a protein alone, the protein becomes considerably more resistant to putrefaction. But if, for example, the protein has been dloyanoethylated beforehand, this effect is even more pronounced. The Cyanoäthyllerung _r * or Dloyaaoäthflieraag can be done by reacting acrylonitrile or vinylideneoyanide with an alkaline solution of the protein. With such a reaction, unused acrylonitrile or vinylideneoyanide remain. Therefore, the process in which the remaining, unreacted monomers (substituted with a nitrile group) with the addition of a polymerization catalyst with the dicyano-

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14946A1

ethylated protein is plug-polarized for 41 · indu · tril · lie Practice an advantage.

The graft polymerization can also be carried out with other monomers such as a.B. Styrene * Acrylic acid, Acrylfeter, Methaoryltstsr, Vinyl pyridine, acrylamide and vinyl pyrrolidone etc. that old nitrile-substituted monomers (see e.g. acrylonitrile), tetracyanoethylene, Vinylidene anide, etc.) are copolymerizable, carried out «earth. By Oopolymerieierung τοη vinylpyridine or acrylamide can reduce the dyeability of the oil for wool dyes increase. A special dyeability for basic dyes is obtained when aoryleic acid or your ifter are polymerized

The regenerated cellulose fibers obtained from the invention, the tin graft polymer of a nitrile substitute Proteins contained in an artificial shari are resistant to it Lasser, aSsr somewhat quellable old alkalis · By treatment old roraalim, however, you will be completely komaen with water alkali-resistant.

For the production of the nitrile-substituted protein rat-synthetic resin copolymers, that is to be mixed with a viscose, an aqueous polymerization is suitable. Bs In general, it is therefore advantageous if the polymerization is carried out in an alkaline Protein solution carried out, the emulsion produced old

a viscose is mixed and then spun. In the case of • 09844/1636

U94S41

Alkaline solution forms the polymerization catalyst bee time te subs tarit limited, abar ea baataht dar Tor tail, daae Poljaorlaationagrad and yield of graft oopolynerieate heoh are · Xb FmUa daaa PolyBerieationageeoh Speed and Pdlyaeriaationagrad niadrig aind, laaaan eioh dlaaa laohteile durah using ainaa ledox-Polymerieationesystena wia · ..! · alnaa Vaeeerstoffperoxyd-Anin-SysteBs odar ainaa Waeeeretoffperexyd-Iatrluaeulflt ~ 3ysteBe antfpraohand de «vanrandatan Monaaaran ttbarwindaa

▲ la Katalyaator aignat a ^ oh «in« aaaarlualianaa peroxide wia ▲ ■ »aniuaparaulfat, KaliuaparaHlfat © der Waaaeratoffparozyd In ainar Mtnga τοη 5 Ua 0,2jC based on da · Oa« iaht to » Menoaaria« n · Maate Poly »traturatian liaft in diaaan PaUa in Btraioh tob 20 bia 85 ⁰ Q. Ale Baduktlonwittftl tu dan Badezkatalyaator-Syattn own * eioh 5 bia 0,1 Ji Iatrlunaulfit _t aauraa lätriuaaulfit odar Vatriumthioaulfat · Dia gaaignaia. Polynarlaationataapendix lies in the aan »all bal 50 bia. 60 ° 0.

As already mentioned above, aa eioh aai allan ar t indungagemäea rerwendeten Protaindarlratan among other things so-called nltrilaubitituierte Protaindarirate, in which a nitrile bond, the Terechi * aene can carry a functional group »

• *

duroh an ohemieohe Umsatiung instead of the active Waaaar-. Substances of a polypeptide have been introduced into the protein

• 09044/1636

Ia general In ·· η · loh eoloh · ProtelnderlYate in the following White oharacterieierenι

(1) the influence of the Duroh is bound to 4m Proteinaolekül Nttrilgruppe du feu roteinderiTat ^p-β lni resistant UMD stable · Irrespective of the 1st Substitusnten Aas Ii * trilradlkal of dl · Polypeρtidetruktur bound · J · Höber the content of nitrile groups, üb the stronger the effect

I-

(2) You colloidalIgenso adhere to the aqueous reading of the Protein derivatives are different from those of the starting protein ^ luoh if the solution holds in any? et> Viscose Termisoht never gets old, al ο L changes the DureH-look the solution and the reliability is auege & eiohnet. B's lets ei oh so a spinning solution. put »without releasing or releasing

(3) In the case of preparation of the spinning solution ... will be 10 to 30 Parts of protein act In the «ice old viscose isrmlsefct, that 90 to 70 parts Oelluloeekoaponente In the TisksjM can be used · 9a «Otaitoli is turned from nozzles into a §» · bräuohliohes fällbad extrudlert (sur formation kräuse ^ tsr fibers).

(4) OIE so erseugten fastrgeaiaohe besitsen a "wag · # Knlokfestigkeit, a woolly" öriff · wei "ea Tiels V Ripples and are τοη high Blastlaität. Dieee ■ *

909144/1636

BATHROOM OKGINAL

Crimps in particular are very resistant · Xm following the characteristics are given in an example.

Incorrect ordinary Fibers staple fibers

Degree of curling (0)

original sample 28.0 21 »2

Crimp degree (£)

the one smoothed with soda

Sample 12.5 9.3

Krause Iuneegrad U)

the first with steam

treated sample 21.0 14 »β

EräuselungsrUokgswinn (jf) 85 69

In comparison with ordinary staple fibers, those according to the invention have the advantages fibers are significantly higher at the beginning of the curling and also have a higher ability to recover from crimps, when the fibers are first stretched by mechanical action and then treated with steam.

This is a Bigsneohaft tob great evil, tenn the fa-

sern are GewtthnUUh belB Terspinnen, tebea BBeT HbH j

series of mechanical influences and lYrBSb subjected «beror they are finished in the end products · If the loss of crimp in these treatments is great ··· the effect is lost. Za with regard to ils ·· ligensonaften it can be said that the inventions preserve their original high curling ability and in this they are superior to ordinary staple fibers 909844/1636

BAD OftiGINAL

The 10 / £ igt 8treo-elasticity of fiber mixtures produced by joint spinning τοη viscose with a derivative «ground» the further conversion of a high molecular aldehyde with a nitrile substituted protein derivative or with a duroh graft polymerisation of an OH ₂ -Ok substituted monomer graft polymer obtained * tends to have a value that can be compared with acrylic acid synthetic fibers.

Eeien as an example of proteins which can be used according to the invention luhailohoasein, grain protein oaaein, soybean protein,

Irdnuasoastln etc. listed. example 1

A mixture of 110 g (absolute weight 100 g) casein. 400 g water and 23 g Iatriuahydroxjrd was stirred for 5 to 10 minutes · Sann 28 g of 2-Cyanonethjl "-äthylenoxjrd su cugegeben the solution and dlt Additienertaktion erfolfte under ttühren at 45 ⁰ O in 3 hours. Manufactured in this way ·! The solution containing cyano-propylated protein was cooled to the cold temperature and mixed with 169 g of 20% aqueous sodium hydroxide solution and 3800 g of viscose. The mixture was decolorized and spun. Pas spinning bath containing 7 _# 5 ^ sulfuric acid. 28, <> / <sodium sulfate and 1,2 # zinc sulfate · The other

• - *

• 09044/1616

U94641

Spinning conditions and # reohiedeji do not differ from the liohen spinning process eur production of crinkled oars from Viscose applied

The fibers were then treated with Fonaalin, desulphurized and subjected to the usual post-treatment. In the formalin treatment, the fibers were treated for 2 hours at 6O ⁰ C with a solution of 5 $ formalin and 159 * sodium sulfate.

The fibers obtained showed the following fairness

Dealer 2.32 Trooke oven activity 2.44 g / d leak strength 1.57 g / d Trooksndtnung 16.0 * Hate stretching 17.7 * Degree of curl 14.1 l Number of ripples 16.1 / 25 am Kink resistance S36 times

The fibers possessed an exceptionally good curling ability a wavy "handle" and a high buckling resistance.

Example 2

100 g of casein were in 900 ml of a 0.5% sodium hydroxide solution solved. Then 40 g of tetracyanoethylene were added while charging added to the solution. After the action for 90 minutes

909844/1636

had expired at 5O ⁰ C, tetracyanoäthyiiertes casein in the form of a stable solution was obtained. The conversion was 25 #. 200 g of this solution were mixed with 2 kg of viscose and the mixture was spun into fibers in the manner described in Example 1. The physical properties of the fibers produced are given in the following table. The fibers exhibited excellent frizziness, a woolly "feel" and a high kink resistance.

rehearse

Physical
properties Brfi ndungsgemäsae
Fibers 894 times Ordinary
Staple fibers denier 2.86 2.85 Dry strength g / d 2.65 2.81 Wet strength g / d 1.86 1.75 Dry stretch £ 14.8 21.0 Wet expansion 17.3 23.7 Degree of curl £ 24.8 19.8 Number of crimps / 25 ma 18.5 11.2 Kink resistance 1265 eel

Example -3

100 g casein became 750 al one

aqueous sodium * -

909844/1636

bad okginal

U94641

Hydroxide solution was added and the mixture was stirred for 30 minutes. Then, 25 g of acrylonitrile were added to this and the Caseinlöeung Kondeneationereaktion tone occurred within 2 hours at 6O ⁰ C. Bs eo cyanoäthyliertt · Oaeein was obtained in the form of a solution. After cooling, this solution was mixed with viscose so that the ratio of cellulose to casein was 87:13. The mixture was then converted into fibers as described in Example 1. The physical properties of the fibers are shown in the following table

rehearse

Physical constraints

According to the invention
Fibers Ordinary
Staple fibers 2.66 2.82 1.82 1.78 15.9 21.5 17.3 23.7 1205 849 24.4 19.8 ■ * 19.8 11.0 i 60.8 49.0

Dry strength g / d
lassfeatigkeit g / d
Dry stretch £
Wet elongation Jf
Buckling resistance, times
Crimp degree ff
Number of crimps / 25 ■■
Ripple degree of relaxation

As can be seen from the table above, the column strengths were and crimpability improved and the fibers relaxed a woolly "handle.

909844/1636

Example 4

100 g of casein * were dissolved in 900 ml of 0.5% sodium hydroxide solution. Then 60 g vinylidenecyanide are mixed with this solution. With stirring, the mixture was kept at a temperature of 75 ⁰ G. Upon addition of 3 ml of 30> »IGEU Wasseratoffperoxyd polymerisation starts the Vinylidencyanids and the initial temperature rose to about 80 ⁰ C. after the bulk of the vinylidenecyanide had polymerized, the temperature dropped again to 75 ° C. After the reaction had been carried out for 3 hours at this temperature, a stable emulsion with slightly white spots had formed. The proportion of polymerized vinylidenecyanide was about 83ji. 100 g of this emulsion were mixed with 2 kg of a viscose and the Qemisoh was spun into fibers which, after post-treatment with the usual methods, were used to produce crimped staple fibers. The recovered fibers had excellent crimp and feel. The strength was 2.78 g / d and the elongation was 18 pounds. The recovery in elasticity during a 10b elongation was 56st. For comparison, common staple fibers have a strength of 2.83 g / d, an elongation of 11V * and a blasticity recovery of $ 48 with a 10 ^ elongation.

Example 5

100 grams of casein was dispersed in 671 grams of water and then became

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BAD OKQINAL

U94641

72 g of a 10% aqueous sodium hydroxide solution are added dropwise to this dispersion while stirring. Bas mixture was about 30 minutes weitergerUhrt · Sann, 25.0 g of acrylonitrile to the Lusung sugegebsni the addition reaction was carried out at 3stUndigem stirring the solution at 55 ⁰ O. Sann were 2 moles of acrolein (1), 2 moles of formaldehyde (2) and 1 mol of dialdehyde starch (3) eu the protein cugesttit and the addition took place within 2 hours at 50 ⁰ * Bas.

mixes that the ratio of cellulose eu casein 9 «1 and then spun fibers in the usual way The following results were obtained

Sample Mr.

Physical
properties

untreated

Added amount Aldehyde linkage 2

in moles *

Denier 2.90

Trooken strength g / d 2.51

Trooke elongation t 15.4

Kräussluagsgrad ft 15.5

Number of crimps ·!) / 22.0

25 am

Buckling strength * eel 1307 Solubility (0) in Seigern Alkali 12.1

Protel retention in ft 93.4

nothing

2.86 2.90 2.90 2 * 58 2.54 2.48 14. « 15 »9 17 ·· 16.8 18.8 13.0 22.8 22.6 14.2 834 648 535 12.0 11.0 18.5 96.0 96.8 83.0

• 09044/1616

As can be seen from the table above, strength, curling ability, alkali resistance and retention were all noticeably improved «

Example 6

167 β (absolute dry weight 190 g) casein were mixed with 1269 g of water and 30.9 g of 21 # strength liatric hydroxide solution and the mixture was stirred for one hour. Mused were 3315 g of 2-Cyanoäthylenoxyd added and the reaction was carried out for 2 hours at 45 ⁰ C to give € -hydroxy-oyanoäthyliertem casein. Then, separately, by dissolving in a 1 # strength borax solution, a 10 # Lge solution of a copolymer was prepared which had been obtained from 33 mol # acrolein and 67 mol # vinyl alcohol. Of this solution just described, 30 g were added directly to the casin derivative so that the mixing ratio was 50: 1. The mixture was brought to reaction by ^{stirring for 2} hours at 20 ° C.

The solution obtained was mixed with 16.875 kg · viscose with: a normal cellulose concentration of Bj . The ratio of cellulose to casein was 9t1. A precipitation bath of the same composition was used for spinning as is also used for the spinning of the ordinary casein-viscose mixture. Compared old den'with hydroxycyano-

909844/1636

U94641

Ethylene casein blended fibers were among the produced Fibers "handle, thread quality and tear resistance not impaired, the protein loss after spinning and the washing test was low and it was found to be increasing Trend towards elasticity in elongation and fatigue resistance. The following comparison is given as an example of these properties. You comparison fibers were spun with the sole admixture of 6-hydroxycyanoethylated product. The properties of the obtained Fibers and those made from a mixture of hydroxycyanoethylated casein and viscose are listed in the following table. The properties of common staple fibers are also given.

Physical
properties Determination
moderate fibers 100
86.3
70.4 Comparative
faeern ordinary
.staple fibers denier 5.10 5.06 5.08 Dry strength g / d 2.87 2.81 2.80 Trooke elongation JL 18.9 17.8 17.9 Degree of ripple fi 24.6 24.1 13.4 Number of crimps / 25 mm 22.4 20.5 14.2 5 pound elongation
degree of elasticity £ 52.1 46.7 42.5 Kink (flexibility)
strength, times 869 672 520 Protein retention coefficient: before _# washing - *
after washing for 4 hours
after 8 hours of washing 1DO
69.8
60.1 . -

909844/1636

BATH

U94641

Notes Waeohbedbedingungenent launder-o-meter procedure Bath composition 0.5 Gew.jl Mareeille soap and

0.2% by weight of He ₂ CO ₅

Temperature * 70 - 2 ⁰ C Protein retention

koeffisienti The nitrogen content was determined according to j

Waβ0heη determined, with a basis laid down was, daea the nitrogen content the Auagangefaser 100 iat.

Example 7

In each case, Tsraohiedene monomers were polymerized in an aqueous, alkaline solution of oyanoethylated oasein, which had been prepared in the manner described in Example 2. Polymerization and addition of the imule ions obtained at 75 ⁰ O within 4 hours are listed in the same table A.

Table A. Versttoh-Ir>

6-1 6 - 2 6 - 3

Oyanoethylated oil solutions ♦ Concentration.jt 11.90 11, ββ It, (6

Quantity, g 168 168 168

Water, al U 14 14

3 * H ₂ O ₂ , al 6 6 6

Monomeres, g St. 20 MHa 20 Wed 20

Polymerisationaumaats, 1 » 99 »5 97.8 79 t 9

Closing of the Sauls ion
near the polymerization (H)

Cyanoethylated Casein 9.68 9.65 10.17

Polymer 9 t 68 9.4f 9 60 • OltU / 1636

The physical properties of spinning together The patern obtained for the individual emulsions and viscose are listed in labe11 · B. Both "handle and Also curling ability were good. You had fibers good elasticity.

Tabel B. 6 - Experiment no 6-3 usually·
Staple fibers Physical
Properties 6 - 1 2,
2,
18th • 2 3.13
2.78
16.3 2.96
2.66
20.2 Fineness, denier
strength, g / d
Tendon, 1 » 3.
2,
15th 94
58
, 6 93
66
, 5

llaetiaitätarüokgewlnn in Ji at a 10bigen .Strain '

51.0 55.6

59.0

41.6

Notez In the table, styrene is used for the monomers St, ethyl methaorylate with uli and methyl aorylate with HAt-ahgekürst.

9098U / 1636

Claims (1)

U94641 - 33 AneprUohe 1. Process only production τοη Kunetfaeergeaieohen, da · duroh gekennaeiohnet, da ·· «la Qoaleoh tob viscose and some sub-titled protein rat T * rspön VIvA ₉ « oWl dl · ·· Per% «lnd« rlT * t · duroh w »it« r f dtr nitill «ub« tltul «rl« n i * rot «louad / odtr duroh Pfvopfpol | serleatloa alt tln «r «« Rd «a 2 · Procedure gur UorMelluae tob KunetfaMrg «alooh« n _t da · duroh goteaaatlohaott da ·· «la Qaaieoh tob Vl» ko ·· and • lara Frot «laderlTat Tcrepoonta becomes, since · duroh addition» · reaction au · «Inta Protola and an epozj-eubetltultrlon HitrllTormlBdung has been obtained 1% 3φ method iur production tob Kunetfaaergemleohen * daduroh geifnnaelohnet, da ·· a Ueaiioh tob Vltlco ·· and elaea ProteladerlTat Toreponnen, because «duroh addition ·· reaction to · «lnaa Protela and an old one ungoelttif» ten Athylenrwat autatitulerton llitrllTerblndung received been 1% 4 Process only manufacture tob JCunatfaMrgealeohen, since duroh gekonnMlohnot, there ·· an Oemlech tob Tlako ·· and 9098A4 / 1636 U94641 - 34 - • Inta i'rotelndorlvat is spun, since · duroh graft polymerisation from a protein and an olefin compound previously substituted by an unsaturated ethylene oxide receive «orden let · 5. Method sur Ueratell von Kunetfoeorgenleohen, characterized »daae a ttemlsoh τοη viscose and a protein derivative is spun, the duroh Uaeetsung of a low or high molecular weight aldehyde with a nitrile substituted protein derivative has been obtained. 6 · Request for creation of Kunotfaeergealeohen, daduroh gexennse that a Gemisoh of viscose and a protein derivative is spun that duroh copolymerization or graft polymerization of an ethylenic substrate unsaturated monomers with an intrilubstituiorten iroteindrat received 1st · BATH 909844/1636