US2261295A - Artificial textile materials - Google Patents

Artificial textile materials Download PDF

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US2261295A
US2261295A US16533337A US2261295A US 2261295 A US2261295 A US 2261295A US 16533337 A US16533337 A US 16533337A US 2261295 A US2261295 A US 2261295A
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acid
solution
cellulose
per cent
fibers
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Schlack Paul
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Walther H Duisberg
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives

Description

Patented Nov; 1941 -9 cl ims. 1 (C1. 18- -54) My present invention relatestoa process, of producing fibers and films.

L It isran object of the invention to provide a process bywhich fibers and films ,from organophilic polymerides may be dyed or printed in fast tints with acid =wool dyestuffs, directly dye-,

ing cotton dyestuffs, vat dyestutfsand insoluble dispersion dyestufis. I Further objects will be apparent from the detailed specification'ifoll'owinghereafter. V: I I 7 It has been proposed inmycopending applicationSer. No. 41,500 filed September 20, 1935, to make artificial .textile materials such as threads, sheets, films, bristles, horse-hair and the like from cellulose derivatives and artificial resins, soluble inorganic solvents by adding to the mass, synthetic resinous substances which contain reactive halogen,. oxidoorsulfoeester groups and, to treat the material during or after the shaping operation or the further working up with an aminating agent or its equivalent. 1 Films havealso been produced which contain strongly degraded chloracetyl cellulose in addition to acetyl cellulose and these have been subsequently causedto react with pyridine. 3

The present invention consists in making..valuable products of similar properties by using as dimethylsulfide, trim'ethylphosphine, ethylene thiourea, N.N,-dimethylethylene thiourea, N-cyclohexyl- Nfi-dimethyl -tl,iiourea, hexamethylene triamine, 'dimethylguanidine. V r These agents, insofar as 7, they are suificiently volatile, may, be applied in the. gaseous phase, in which"'c'ase the presence of moisture is fre quently advantageous Reaction can alsofbe favored by the presence of vapors of solvents which cause.,swelling for example vapor of methanol, of methylene chloride, of acetone, of benzene or of alcohol. Slightlyvolatile or nonvolatilematerials may be applied in liquid form or in the form of a solution in an inert solvent, which ,if' desiredmay exert a limited swelling action. Slightly volatile 'or non-volatile mate rials can also be used, when 'suiiiciently-sparingly' Y soluble in water, in the form of emulsionsor additional components soluble (organophilic) sulfonic acid esters of carbohydrateaparticularly cellulose and its derivatives, such ashydroxyethyl cellulose or mono-ethyl cellulose, further starch; the fibers and films obtained in the usual manner, for example vby dry, spinning or wet spinning,by casting on bands or the like, may be treated with aminating agents or their equivalents during the manufacture or at a laterperiod. In this manner there are obtained products having an enhanced afiinity for many dispersions nd applied or'printed on thestruct evq to, a preliminar product thereof, parw rly to a web.

In order to avoid as far as possible a yellowing owing tothe aminationtreatment it is desirable to keepthe temperature of the reactionas low asiis practicable and toavold unnecessary excess ofthe treating agent. The presence'of aldehydes orfof pronounced reducing, agents; may some times be favorable in this sense.

A yellowing which may have alreadyoccurred may beremoved or diminished by a bleaching agent, in particularacid bleaching agents, for instance potassium permanganate in presence of sulfuric'acid, acid dispersions or arylsulio'chloramides or a bleaching by exposure tolight.

dyestufi components and for agents for treating textiles, particularly those having acid groups. The increased affinity for dyestuffs is also by no means limited to acid wool dyestuffs but extends also to directly dyeing cotton dyestufis, also to V ;The reactivity of the structure may,-as will appearfpresently, be considerably increased-by i theadditioh of, further "components tothe film or fiber-fo'rming colloids before the" casting; or spinning which havea higher swelling capacity than that of "the main material or obtain an 7 increased degree jof swelling by a, moderate vat dyestuffs and particularly insoluble dispersion dyestuffs. These latter are particularly easily and quickly adsorbed, which is important in printing. In many cases they fastness of the dyeings, for instance towards acid gases, is considerably improved. Aminating agents, by means of which this increase of afilnity'may be attained, are for examplei Ammonia, methylamine, dimethylamine, .trimethylamine, cyclohexylamine, .piperidine, morpholine, N-methylmorpholine, ethylene-diamine, tetramethyl-diamine, piperazine, NJfl-dimethylpiperazine, ethylene-imine, C-methylethylene imine, N-

vmethylethylene imine, N-butylethylene imine, dimethylaniline, pyridine, picoline, pyridine-p carboxylic acid methyl ester, quinoline, isoquinoline, dimethylthiazole, i-methyl-imidazole,

easily decomposed vinyl formate hydrolysis" by which hydroxy ;groi1ps are*lib5 erated- Such materials are, for example poly-' meric vinyl esters such as'vinyl" formate, vinyl acetate," vinyl methoxy acetate. I Especially the 7 or'amixed poly merizate' having this j component produces; a

strong increase in swelling. "Hydrolysis of "this kind mayoccur before the amination proper. Generally, however, it is preferable to conduct hydrolysis and amination in a single operation.

Quite particularly active and valuable are additionsof substances'to' the fiber-forming colloids which contain acid orlatent acid groups which,

for example, become freed by hydrolysis o'rfoxidation. Hydrolytic decompositions may in this case also voccur simultaneously withthe amination;' anyoxidizing, however, must precede the animation. Suitable additional polymeric sub--' stances with acid or latent acid groups are, for

' 'MU'N-ITED: *sTArEs example, the polymerizates and mixed polymerizates which contain unsaturated acids, ior instance acrylic acid or maleic acid, as components, especially the anhydric mixed polymerizates from maleic anhydride and vinylderivatives, for example the mixed polymerizate from, vinyl alkyl ether with maleic anhydride, which products are easily obtainable in the manner described in German Specification No. 540,101. with acid groups described in my copending application Ser. No. 57,524 filed January 4, 1936 (British Patent No. 459,711), are available for the purposes of the invention.

The products which contain both acid and basic groups are particu-T larly valuable rrom the point of view or dyeing. They may be dyed with selected members irom practically all dyestufls classes and exhibit a remarkably good stability to boiling. The ai'iinity for dyestuffs and in many cases also to the reactivity in the amination may be further enhanced ii in addition to. the sulfonic acid ester '0! a polymeric carbohydrate a synthetic resinous substance, of high molecular weight is added which at the same timecontains groups capable of amination. Such substances are, for example,

' halogen derivatives like polyvinyl chloracetate,

mixed polymerizates containing vinyl-a-halogen acyl radicals, polyglycide chloracetate, 'y-ChIOIO- p-hydroxypropyl ethers of resinous polyhydroxy compounds, arylsulfonic acid esters or polyglycide of hydroxy-allrylated phenol formaldehyde condensation products of. the Novolak" type. Novolak is a soluble, non-hardened condensation product from phenol and formaldehyde produced by reacting the components in an acid medium. "Novolak is a registered trade-mark.

As a basis for the textile materials having the additions prescribed by this invention there come into consideration in the first place cellulose derivatives such ascellulose esters and ethers, polyvinyl formals, mixed polymerizates from acrylic acid nitrile and vinyl alkyl ethers, or from acrylic acid amide and vinyl alkyl ethers, also polyvinyl chloride soluble in acetone. V

The heterogeneous composition or fibers and nlms from dissimilar components results in a particularly good receptivity "of the aminated' tlber for dyestuffs of comparatively high molecular weight similar to that which is exhibited by products such as polyvinylchloracetate. Moreover, the embedded additional component acts as a protective against the washing out oi the aminated substance in an acid treating bath. The aminated product, however, may also be hired by after-treatment with an aldehydeor an anionic compound yielding sparingly soluble and/or hydrophobe salts.

The following examples illustrate the invention.

(1) An acetate artificial silk consisting of 90 parts of acetyl cellulose having 54.2 per centot bound acetic acid and parts of toluene suitocellulose, having about 2 toluene sulfo-radicals for each glucose unit, are heated in a chamber 50 times the volume of the silk with twice the cal:- culated proportion of pyridine for 16 hours at 80 C. In order that the evaporation of thepyridine may be uniform the liquid is absorbed in a porous body.

Instead of pyridine there may be used with like result trimethylamine, ethylene imine', N-methylethylene imine, N-butyl, ethylene imine. The aminated silk may be dyed with acid dyestufls such as Alizarine Cyanine Green 5G (Schultz Also other materials.

in aminated condition or vinyl carboxylic acid ester Farbstofitabellen, 7th ed., vol. II, page 68), Add Anthracene Red 5131.) (Schultz Farbstofltabellen, 7th ed., vol. II. page 187) Acid Anthracene Brown RE (Schultz Farbstofltabellen, 7th ed., vol. II, page 187), in the last chromlng; the dyeings are intense and. fast.

(2) A spinning solution consisting o! 17.5 per cent of acetyl cellulose having 54.2 per cent of combined acetic acid, 1.5 per cent of toluene sulfo-cellulose having 2 toluene sull'o-radlcals for each glucose unit, 1 per cent or the mixed polymerizate from 1 mol vinyl methyl ether and 1 mol maleic anhydride and 80 per cent of acetone isspun by the dry spinning process. The silk obtained after amlnatlon with N-butylethylene 1813131106 is dyed intensely by acid dyestufls at 70- (3) A spinning solution consisting or 18 per cent ot acetyl cellulose, 5 percent of polyvinyl chloraceta-te and 5 per cent of toluene suite-cellulose with 2 acyl radicals for each glucose unit p is spun by the dry spinning process. The silk has approximately the normal physical properties of an acetate silk from the same acetate without the addition of a substance capable of being aminated. By treatment with pyridine vapor in the manner described in Example 1 there is obtained a textile material which can be dyed fast intense tints with dyestuils having acid groups or with dyestufl derivatives such as Indigosol Green (Schultz Farbstoi'itabellen, 7th ed., vol. 11, page 133) by the nitrite method.

(4) A mixture or 80 parts of ethyl cellulose having 41 per cent of ethoxyl and 20 parts of toluene sulfo-cellulose having about 2 toluene sulfa-groups for each glucose unit is dissolved in a mixture of methylene chloride and alcohol (85:15) and cast to form films. After amination with pyridine or dimethyl thiazole the films may be dyed intensely by means of acid dyestufls.

(5) There is spun by the dry spinning process a solution of 17.5 parts of acetyl cellulose having 54.2 per cent or combined acetic acid, 1.5 per cent of toluene sulfo-cellulose having 2 acyl radiicals for each glucose unit and 1 per cent or the mixed polymerizate from 1 mol vinyl chloride and 1 mol maleic anhydride hydrolized to yield th polymeric acid, in80 parts of acetone (strictly speaking 79.15 it the water introduced together with the mixed polymer is calculated). By treatment with vapor of pyridine 'the silk lacquires basic properties. The mixed polymerizate is worked into the spinning solution in the form 4 of an aqueous solution of 60 per cent strength.

1 acetic acid,

(6) A solution or 17.5 parts of acetyl cellulose, 5 parts of polyvinyl acetate and 5 parts of ethane-sulio-cellulose in a mixture of methylene chloride and methanol (:15) is spun as artiilcial silk. By treatment from 12 hours withtwice the'calculated proportion 01 N-methylmorp'holine in toluene at 60 C. the silk is aminated and may now be dyed with acid wool dyestufls and with many substantive dyestun s.

(7) A solution containing 17.4 per cent or acetyl cellulose having 54.2 per cent or combined 0.8 per cent oi toluene sulfa-cellulose, 0.8 per cent of polyvinyl chloracetate and 0.8 per cent 0! the mixed polymerizate from 1 mol vinyl methyl ether and 1 mol maleic anhydrid is spun. The silk thus obtained may be dyed in presence of 7 per cent oi cyclohexyl dimethyl thiourea at 70-80 C. with 3 percent of Alizarine Extra (Schultz Farbstofltastrong tints are Cyanine Green G bellen, 7th ed., vol. 1, page 532); produced.

named case with aiter acid is spun by the wet spinning process.

(8) A solution of acetyl cellulose containing 7.5 per cent of toluene sulfo-cellulose and 2.5

per cent of the mixed polymerizate from vinyl formate and maleic anhydride is spun and the fiber is treated directly after it has left the spinning cell with a solution of 15 per cent strength of isoquinoline in dilute acetone. After evaporation of the acetone the fiber is heated at 70 C. in a closed chamber for some time; it is then cut to staple and further worked up in the usual manner.

(9) A spinning solution containing 18 per cent of'acetyl cellulose having 54.2 per cent of combined acetic acid and 4 per cent of an acetyltoluene-sulfonyl-cellulose containing about 2 acetyl radicals and about 0.7 toluene sulfonyl radicals for each glucose unit, the solvent being a mixture of methylene chloride and ethanol (85:15), is spun by the dry spinning process to form artificial silk. The silk is then aminated by means of trimethylamine; it may then be dyed deep tints with acid dyestuffs, for instance Orange II (Schultz Farbstofitabellen, 7th ed., vol. I, page 86), or Alizarine Direct Blue A (Schultz Farbstofftabellen, 7th ed., vol. II, page 9).

(10) A solution of hydroxyethyl cellulose acetate in acetone which contains 10 per cent of toluene suIfo-starch is worked up into a film from a mixture of methylene chloride and alcohol.

(80:20). The film is aminated by treatment with a solution of pyridine in toluene, whereupon it exhibits good affinity for acid dyestufis.

(11) 18 parts of acetyl cellulose having 52.5 per cent of combined acetic acid and 2 parts of the ether ester from dimethyl cellulose and diethylaminosulfochloride, in a mixture of methylene chloride and alcohol (80:20) is cast into the form of a film. The ether ester is obtained by heating the ether with the acid chloride in an indifierent solvent in presence of an agent which binds hydrogen halide.

(12) A 16 per cent solution of 92 parts cellulose acetate having 59.2 per cent of bound acetic I acid and 8 parts phenylsulfonyl starch in acetic The silk obtained is treated with a 4 per cent solution of benzylamine in aqueous pyridine of 25 per cent strength at 75 C. for one hour. The silk is aminated and slightly saponified and can now be dyed with many acid dyestuffs. By addition of swelling agents to the dye bath the number of dyestuffs available is increased.

What I claim is:

1. A process which comprises preparing a solution of cellulose acetate, adding thereto '10 parts of the weight of the cellulose acetate of toluene-sulfo cellulose, spinning artificial silk therefrom by the dry spinning process, heating the resulting silk at about 80 C. for about half a day to a day in an atmosphere containing pyridine vapor.

3. A process which comprises preparing a solution of about 18 per cent of acetyl cellulose, 5'

per cent of polymerized vinyl chloracetate and 5 per cent of toluene-sulfo cellulose, spinning fibers from said solution, and treating said fibers at 80 C. for a considerable time with dimethylthiazole.

4. A process which comprises preparing a solution of a polymeric organophilic colloid selected from the group consisting of cellulose derivatives and fiber-forming synthetic resins, adding to the said solution a soluble ester of a polymeric carbohydrate with a sulfonic acid, forming fibers or foils from said solution, and reacting said fibers and foils with a compound selected from the group consisting of amines and amine derivatives. 7

5. A process whichcomprises preparing a solution of a polymeric organophilic colloid selected from the group consisting of cellulosederivatives and fiber-forming synthetic resins, adding to the said solution a soluble ester of a polymeric carbohydrate with a sulfonic acid, forming fibers or foils from said solution, and reacting said fibers and foils with a compound selected from the group consisting of amines and amine derivatives in gaseous condition.

2. A process which comprises preparing a solu- 6. A process which comprises preparing a solution of a polymeric organophilic colloid selected from the group consisting of cellulose derivatives and fiber-forming synthetic resins, addme to the said solution a soluble ester of a polymeric carbohydrate 'with' a sulfonic acid, adding further to the said solution a synthetic resinous substance containing in its molecule an alkylating group, forming fibers and films from said solution, and treating said fibers and films with a compound selected from the group consisting of amines and amine derivatives.

7. A process which comprises preparing a solution of a film-forming polymeric organophilic colloid selected from the group consisting of cellulose derivatives and fiber-forming synthetic resins, adding to the said solution a soluble ester of a polymeric carbohydrate with a suifonic acid, adding further to the said solution a polymeric substance having a higher swelling capacity in Water than said first named film-forming compound, forming fibers or films from said solution, and treating said fibers or'films with a compound selected from the group consisting of amines and amine derivatives.

8. A process which comprises preparing a solution of an organic cellulose derivative, adding to said solution a soluble ester of a polymeric carbohydrate with an organic sulfonic acid, forming fibers or foils from said solution, and treating said fibers or foils with a compound selected from the group consisting of amines and amine derivatives.

9. Artificial fibers and films made of an organophil colloid which has incorporated and fixed within the body of the fibers and films a substance consisting of the reaction product of a soluble ester of a polymeric carbohydrate se-- lected from the class consisting of cellulose and starch with a sulfonic acid, and a compound selected from the group consisting of amines and amine derivatives.

PAUL SCHLACK.

US2261295A 1936-09-30 1937-09-23 Artificial textile materials Expired - Lifetime US2261295A (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2955014A (en) * 1955-03-04 1960-10-04 Segal Leon Process of treating native cellulose with a liquid alkylenepolyamine and a textile resin
US2966390A (en) * 1955-08-08 1960-12-27 Bemberg Ag Process for the production of etched textile material containing synthetic cellulosefibers
US2972606A (en) * 1956-05-31 1961-02-21 Wyandotte Chemicals Corp Catalytic aminoethylation of cellulose, cellulose derivatives or polyvinyl alcohol
US3513055A (en) * 1964-11-12 1970-05-19 Fmc Corp Method of preparing heat-sealable composite sheets
US20130174758A1 (en) * 2010-09-17 2013-07-11 Knauf Insulation Gmbh Organic acid carbohydrate binders and materials made therewith
US9040652B2 (en) 2005-07-26 2015-05-26 Knauf Insulation, Llc Binders and materials made therewith
US9039827B2 (en) 2007-08-03 2015-05-26 Knauf Insulation, Llc Binders
US9309436B2 (en) 2007-04-13 2016-04-12 Knauf Insulation, Inc. Composite maillard-resole binders
US9416248B2 (en) 2009-08-07 2016-08-16 Knauf Insulation, Inc. Molasses binder
US9447281B2 (en) 2007-01-25 2016-09-20 Knauf Insulation Sprl Composite wood board
US9492943B2 (en) 2012-08-17 2016-11-15 Knauf Insulation Sprl Wood board and process for its production
US9493603B2 (en) 2010-05-07 2016-11-15 Knauf Insulation Sprl Carbohydrate binders and materials made therewith
US9505883B2 (en) 2010-05-07 2016-11-29 Knauf Insulation Sprl Carbohydrate polyamine binders and materials made therewith
US9828287B2 (en) 2007-01-25 2017-11-28 Knauf Insulation, Inc. Binders and materials made therewith

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2955014A (en) * 1955-03-04 1960-10-04 Segal Leon Process of treating native cellulose with a liquid alkylenepolyamine and a textile resin
US2966390A (en) * 1955-08-08 1960-12-27 Bemberg Ag Process for the production of etched textile material containing synthetic cellulosefibers
US2972606A (en) * 1956-05-31 1961-02-21 Wyandotte Chemicals Corp Catalytic aminoethylation of cellulose, cellulose derivatives or polyvinyl alcohol
US3513055A (en) * 1964-11-12 1970-05-19 Fmc Corp Method of preparing heat-sealable composite sheets
US9464207B2 (en) 2005-07-26 2016-10-11 Knauf Insulation, Inc. Binders and materials made therewith
US9434854B2 (en) 2005-07-26 2016-09-06 Knauf Insulation, Inc. Binders and materials made therewith
US9926464B2 (en) 2005-07-26 2018-03-27 Knauf Insulation, Inc. Binders and materials made therewith
US9260627B2 (en) 2005-07-26 2016-02-16 Knauf Insulation, Inc. Binders and materials made therewith
US9745489B2 (en) 2005-07-26 2017-08-29 Knauf Insulation, Inc. Binders and materials made therewith
US9040652B2 (en) 2005-07-26 2015-05-26 Knauf Insulation, Llc Binders and materials made therewith
US9828287B2 (en) 2007-01-25 2017-11-28 Knauf Insulation, Inc. Binders and materials made therewith
US10000639B2 (en) 2007-01-25 2018-06-19 Knauf Insulation Sprl Composite wood board
US9447281B2 (en) 2007-01-25 2016-09-20 Knauf Insulation Sprl Composite wood board
US9309436B2 (en) 2007-04-13 2016-04-12 Knauf Insulation, Inc. Composite maillard-resole binders
US9469747B2 (en) 2007-08-03 2016-10-18 Knauf Insulation Sprl Mineral wool insulation
US9039827B2 (en) 2007-08-03 2015-05-26 Knauf Insulation, Llc Binders
US10053558B2 (en) 2009-08-07 2018-08-21 Knauf Insulation, Inc. Molasses binder
US9416248B2 (en) 2009-08-07 2016-08-16 Knauf Insulation, Inc. Molasses binder
US9505883B2 (en) 2010-05-07 2016-11-29 Knauf Insulation Sprl Carbohydrate polyamine binders and materials made therewith
US9493603B2 (en) 2010-05-07 2016-11-15 Knauf Insulation Sprl Carbohydrate binders and materials made therewith
US20130174758A1 (en) * 2010-09-17 2013-07-11 Knauf Insulation Gmbh Organic acid carbohydrate binders and materials made therewith
US9492943B2 (en) 2012-08-17 2016-11-15 Knauf Insulation Sprl Wood board and process for its production

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