US3505087A - Flame-retardant rayon containing halogenated phosphonitrilate polymer - Google Patents

Flame-retardant rayon containing halogenated phosphonitrilate polymer Download PDF

Info

Publication number
US3505087A
US3505087A US819483A US3505087DA US3505087A US 3505087 A US3505087 A US 3505087A US 819483 A US819483 A US 819483A US 3505087D A US3505087D A US 3505087DA US 3505087 A US3505087 A US 3505087A
Authority
US
United States
Prior art keywords
flame
viscose
retardant
yarn
halogenated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US819483A
Inventor
Leonard E A Godfrey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FMC Corp
Original Assignee
FMC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by FMC Corp filed Critical FMC Corp
Application granted granted Critical
Publication of US3505087A publication Critical patent/US3505087A/en
Assigned to KELLOGG CREDIT CORPORATION A DE CORP. reassignment KELLOGG CREDIT CORPORATION A DE CORP. AGREEMENT WHEREBY SAID HELLER AND RAYONIER RELEASES ALL MORTGAGES AND SECURITY INTERESTS HELD BY AVTEX ON APRIL 28, 1978, AND JAN. 11, 1979, RESPECTIVELY AND ASSIGNS ITS ENTIRE INTEREST IN SAID MORT-AGAGE AGREEMENT TO ASSIGNEE (SEE RECORD FOR DETAILS) Assignors: AVTEX FIBERS INC., A NY CORP., ITT RAYONIER INCORPORATED, A DE CORP., WALTER E. HELLER & COMPANY, INC. A NY CORP.
Assigned to BALBOA INSURANCE COMPANY C/O THE PAUL REVERE EQUITY MANAGEMENT COMPANY, JOHN HANCOCK MUTUAL LIFE INSURANCE COMPANY, NEW ENGLAND MUTUAL LIFE INSURANCE COMPANY, WESTERN AND SOUTHERN LIFE INSURANCE COMPANY THE C/O NEW ENGLAND MUTUAL LIFE INSURANCE COMPANY, PROVIDENT ALLIANCE LIFE INSURANCE COMPANY C/O THE PAUL REVERE EQUITY MANAGEMENT COMPANY, PAUL REVERE LIFE INSURANCE COMPANY THE C/O THE PAUL REVERE EQUITY MANAGEMENT COMPANY reassignment BALBOA INSURANCE COMPANY C/O THE PAUL REVERE EQUITY MANAGEMENT COMPANY AS SECURITY FOR INDEBTEDNESS RECITED ASSIGNOR GRANTS , BARGAINS, MORTGAGES, PLEDGES, SELLS AND CREATES A SECURITY INTEREST WITH A LIEN UNDER SAID PATENTS, SUBJECT TO CONDITIONS RECITED. (SEE DOCUMENT FOR DETAILS). Assignors: AVTEX FIBERS INC. A NY CORP.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08Composition of the spinning solution or the bath
    • D01F2/10Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/025Polyphosphazenes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/5399Phosphorus bound to nitrogen
    • 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
    • C08L1/22Cellulose xanthate
    • C08L1/24Viscose

Definitions

  • R and R are the same or different alkyl, alkenyl, arylalkyl or aryl radicals wherein the alkyl and alkenyl radicals have from one to six carbon atoms and the aryl groups have 6 to 10 carbon atoms and, at least one of the OR or OR' groups of the polymer has one or more halogen atoms attached to the carbon atoms of R or R, and n is an integer of at least 3.
  • R and R include halogen substituted and unsubstituted ethyl, propyl, isopropyl, butyl, isobutyl, arnyl, isoamyl, hexyl, allyl, crotyl, phenyl, naphthyl and cresyl radicals.
  • R is methyl R must be a radical of a greater number of carbon atoms since the methyl radical is not readily halogenated and also tends to make the polymer more Water-soluble.
  • R and R are both halogenated ethyl or propyl radicals since compounds where R and R are the same are more easily prepared, and phosphonitrilate polymers having fewer carbon atoms tend to be more water-soluble, whereas the presence of more carbon atoms provides products having a lower percentage of phosphorus thereby reducing their effectiveness.
  • mixed esters wherein R and R are different radicals depending on the combination of substituent groups and halogens, may provide superior results.
  • the halogen atoms included herein are chlorine, bromine and fluorine. Iodine is excluded since derivatives thereof are unstable.
  • the liquid phosphonitrilate polymer is a cyclic trimer, tetramer or higher cyclic polymer, or a linear polymer and is preferably employed as a mixture of these isomers for economic reasons. It has been found, however, that the pure polymeric isomer is effective for the purposes of this invention.
  • the amount of phosphonitrilate flame-retardant dis persed in the regenerated cellulose filament varies from about 5 to about 30% and preferably from 10 to 25%, based on the weight of the filament.
  • the method of this invention comprises incorporating the above described liquid phosphonitrilate in a viscose solution and spinning the viscose in the shape of one or more filaments into a coagulating and regenerating medium.
  • the formed filaments are aftertreated using techniques well-known in the rayon field to provide continuous filaments, fibers and yarn, as well as staple fibers. These may then be used to prepare any known textile article in which the flame-retardant property is desirable.
  • the flame-retardant phosphonitrilate of this invention is a liquid of pumpable consistency which is preferably used as a crude reaction product, prepared, for example, in a known manner by the conversion of the corresponding polymeric phosphonitrilic chlorides to the specified esters, and then halogenated. Refined products such as the trimer are also quite useful. Halogenation, for example, may be carried out as shown by Hamalainen et al., Textile Research Journal, February 1956, pp. 14l 144, and U8. Patent 2,825,718. The esters or mixed esters may also be chlorinated or fluorinated similarly.
  • halogenated esters are also former, for example, by reacting the liquid polymers of phosphonitrilic chloride with a compound which will form a halogenated ester of the phosphonitrilic chloride, for example, ethylene chlorohydrin and ethylene bromohydrin, or halogenated alkyl alcohols, for example, as shown in US. 2,681,295.
  • a compound which will form a halogenated ester of the phosphonitrilic chloride for example, ethylene chlorohydrin and ethylene bromohydrin, or halogenated alkyl alcohols, for example, as shown in US. 2,681,295.
  • the product formed by these reactions is an oily liquid and may be incorporated in viscose as such or in suitable solutions or aqueous emulsions.
  • a controlled amount of the flame-retardant halogenated phosphonitrilate is injected into the viscose just prior to its extrusion through the filament forming spinnerets.
  • the viscose is then spun into an acid bath and processed in a conventional manner.
  • EXAMPLE 1 295.5 grams (3.67 moles) of ethylene chlorohydrin was added dropwise over a 75 minute period to a stirred solution of 133.4 grams (2.3 mole equiv.) of the cyclic trimer of phosphonitrilic chloride in 1000 ml. of pyridine. Initially the reaction mixture was at 20 C., but the temperature rose rapidly reaching 38 C. after about 70 grams of ethylene chlorohydrin had been added. External cooling reduced the temperature to about C. where it was held for the remainder of the addition. The reaction mixture was then stirred at room temperature for 24 hours.
  • a compound prepared in this manner was injected into the viscose line supplying the spinnerets for manufacturing rayon in a metered amount based on the weight of the cellulose in the viscose.
  • This viscose was spun into a conventional aqueous acid spin bath comprising 9.0% sulfuric acid, 2.0% zinc sulfate and sodium sulfate at 55 C.
  • the resulting yarn was processed by passing it through a series of baths including water wash, desulfurization, bleaching, bleach acid, anti-chlorine, and soft finish baths. The yarn was dried and collected.
  • a yarn flammability test was conducted with yarn produced as described above. The test consisted of first preparing a yarn bundle by wrapping the yarn around the closed fingers of an extended hand to produce a bundle of 6000 denier and then removing it from the hand. The yarn bundle is twisted five times and then doubled on itself to produce an integrated yarn bundle, one and one-half inches long and of 12,000 denier size. The free ends of the yarn bundle are clamped in forceps, and the bundle, held in horizontal position, is passed through the tip of the flame of a Fisher burner in an oscillating motion at a rate of one pass per second. The burner flame is adjusted to a two inch height and a blue flame. The number of passes to induce flaming of the sample is determined.
  • a control yarn bundle (yarn con- .tains no flame-retardant inflames in 1 or 2 passes and flame-retardant yarns are classified for inflammability as follows:
  • EXAMPLE II A similar procedure for preparing the chlorinated ester of the cyclic trimer of phosphonitrilic chloride as shown in Example I was carried out except that a mixture of phosphonitrilic chloride polymers obtained as the crude product from the preparation of the liquid phosphonitrilic chloride polymer was employed in place of the pure cyclic trimer. The mixture contained mostly trimer and tetramers with some higher cyclic and linear polymers of phosphonitrilic chloride. The yield was 85.4% and analysis of the product showed 23.3% carbon, 4.05% hydrogen, 34.9% chlorine, 16.0% phosphorus and 7.4% nitrogen.
  • the product of the above reaction was similarly injected into viscose and the viscose spun and processed as described in Example I.
  • the yarn containing about 15% by weight of the injected product, was subjected to the flame test and showed very good flame retarding with no after-glow. After exposure to ultraviolet light in a Fadeometer for 50 hours, the loss of yarn strength was not greater than conventional rayon.
  • EXAMPLE III The 2,3-dichloropropyl hexaester of the cyclic trimer of phosphonitrilic chloride was prepared by chlorination of the hexaallyl ester of phosphonitrilic chloride. This was injected into viscose and the viscose spun and processed. The yarn, containing 25% by weight of the chlorinated phosphonitrilate was flame-retardant.
  • water-insoluble, liquid halogenated polyphosphonitrilic esters e.g. chlorinated, brominated and fluorinated allyl esters of polyphosphonitrilic chloride; adducts of bromoform and allyl ester of polyphosphonitrilic chloride; 2,3-dibromopropyl ester of polyphosphonitrilic chloride; 1,3-dichloropropyl ester of polyphosphonitrilic chloride; chlorophenyl ester of polyphosphonitrilic chloride; bromonaphthyl ester of polyphosphonitrilic chloride; halogenated or partially halogenated mixed esters, e.g.
  • bromopropyl, ethyl ester of polyphosphonitrilic chloride; fluoropropyl, methyl ester of polyphosphonitrilic chloride; chlorophenyl, methyl ester of polyphosphonitrilic chloride; etc. can be injected into viscose to prepare rayon as shown in the foregoing examples.
  • OR and OR groups attached to each phosphorus atom in the polymeric chain be halogenated. That is, for example, the hexaester of the cyclic trimer of phosphonitrilic chloride has six substituent groups. In accordance with this invention, from one to six of these groups can be halogenated.
  • halogenated esters will be more permanently retained in the yarn than others, some require addition in greater amounts to the viscose to obtain the desired flame-retardancy but the greatest advantage of the flameretardant of this invention is that it can be injected into viscose and spun into a yarn which retains its normal softness and hand. This is because the halogenated ester is a viscous liquid held within the regenerated cellulose matrix. Phosphonitrilic esters which are solids tend to produce harsh yarn and are difiicult to spin in viscose.
  • Regenerated cellulose filaments and filamentary articles said filaments having dispersed therein a flame-retardant amount of a substantially water-insoluble, liquid phosphonitrilate polymer having the following general formula:
  • R and R are the same or different alkyl, alkenyl, arylalkyl or aryl radicals wherein the alkyl and alkenyl redicals have from 1 to 6 carbon atoms and the aryl radicals have from 6 to 10 carbon atoms and, at least one of the -OR or -OR groups of the polymer ha one or more halogen atoms attached to the carbon atoms of R or R, and n is an integer of at least 3.
  • the regenerated cellulose filaments of claim 1 containing from about 5 to about 30% based on the Weight of the cellulose, of the liquid phosphonitrilate polymer.
  • a method of preparing a flame-retardant regenerated cellulose filament which comprises mixing viscose and a fllame-retardant amount of a substantially water-inlNi wherein R and R are the same or diflerent alkyl, alkenyl, arylalkyl or aryl radicals wherein the alkyl and alkenyl radicals have from 1 to 6 carbon atoms and the aryl radicals have from 6 to 10 carbon atoms and at least one of the -OR or OR' groups of the polymer has one or more halogen atoms attached to the carbon atoms of R or R, and n is an integer of at least 3; shaping the mixture into a filament, and coagulating and regenerating said filament.
  • R and R are the same and each contain at least 2 carbon atoms.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Description

United States Patent Ofifice 3,505,087 Patented Apr. 7, 1970 US. Cl. 106-15 9 Claims ABSTRACT OF THE DISCLOSURE Flame-retardant regenerated cellulose filaments and filamentary articles containing dispersed therein a flameretardant amount of a substantially water-insoluble, liquid, halogenated phosphonitrilate polymer, and a method of preparing the filamentary articles are disclosed herein.
This in a continuation-in-part application of eopending patent application Ser. No. 566,757, filed July 21, 1966, now Patent No. 3,455,713.
It is desirable for many textile purposes to provide cellulose fibers and yarns having greatly decreased flammability. The production of rayon which demonstrates acceptable flame-retardant properties for all textile requirements, using inexpensive and commercially suitable chemical flame-retardants, has not been satisfactorily accomplished to date.
The application of various organic and inorganic flameretardants to the surface of cellulose fibers and fabrics has not produced the desired result for a number of reasons. In many instances, the chemical flame-retardant is effectively removed when the fabric is washed with water or dry cleaned with solvents. Other flame-retardant chemicals which may be applied to the fabric surface and retained after washing are generally too costly. In other cases, the chemicals used may provide some lasting reduction in flammability but destroy fiber and fabric characteristics, such as tenacity, softness, whiteness, and dyeability, which are desirable and necessary for textile applications.
In the manufacture of rayon by the viscose method, it has been proposed to add various flame-retardant chemicals to the viscose prior to spinning. This approach presents many additional problems because of the particular chemistry of the viscose process. Accordingly, the flameretardant must be stable and inert with respect to the highly alkaline viscose and also with respect to the acid regenerating bath into which the viscose is extruded. It must not be extracted during spinning and processing. Furthermore, the added material must not interfere with the spinning process, i.e., cause clogging of the spinnerets. The rayon produced from the flame-retardant containing viscose must not be degraded in any of its properties and must have a substantially reduced flammability.
It is not an object of this invention to provide a flameretardant rayon fiber without appreciable degradation of any fiber properties.
It is a further object of this invention to provide a process for preparing a flame-retardant rayon fiber which retains substantially all of the properties of ordinary rayon.
These and other objects are achieved in accordance with this invention which comprises a regenerated cellulose filament having dispersed therein a substantially water-insoluble, liquid phosphonitrilate polymer having the following general formula:
wherein R and R are the same or different alkyl, alkenyl, arylalkyl or aryl radicals wherein the alkyl and alkenyl radicals have from one to six carbon atoms and the aryl groups have 6 to 10 carbon atoms and, at least one of the OR or OR' groups of the polymer has one or more halogen atoms attached to the carbon atoms of R or R, and n is an integer of at least 3. For example, R and R include halogen substituted and unsubstituted ethyl, propyl, isopropyl, butyl, isobutyl, arnyl, isoamyl, hexyl, allyl, crotyl, phenyl, naphthyl and cresyl radicals. Where R is methyl R must be a radical of a greater number of carbon atoms since the methyl radical is not readily halogenated and also tends to make the polymer more Water-soluble. In the preferred embodiment of this invention, R and R are both halogenated ethyl or propyl radicals since compounds where R and R are the same are more easily prepared, and phosphonitrilate polymers having fewer carbon atoms tend to be more water-soluble, whereas the presence of more carbon atoms provides products having a lower percentage of phosphorus thereby reducing their effectiveness. However, mixed esters wherein R and R are different radicals depending on the combination of substituent groups and halogens, may provide superior results. Furthermore, the halogen atoms included herein are chlorine, bromine and fluorine. Iodine is excluded since derivatives thereof are unstable.
The liquid phosphonitrilate polymer is a cyclic trimer, tetramer or higher cyclic polymer, or a linear polymer and is preferably employed as a mixture of these isomers for economic reasons. It has been found, however, that the pure polymeric isomer is effective for the purposes of this invention.
The amount of phosphonitrilate flame-retardant dis persed in the regenerated cellulose filament varies from about 5 to about 30% and preferably from 10 to 25%, based on the weight of the filament.
The method of this invention comprises incorporating the above described liquid phosphonitrilate in a viscose solution and spinning the viscose in the shape of one or more filaments into a coagulating and regenerating medium. The formed filaments are aftertreated using techniques well-known in the rayon field to provide continuous filaments, fibers and yarn, as well as staple fibers. These may then be used to prepare any known textile article in which the flame-retardant property is desirable.
The flame-retardant phosphonitrilate of this invention is a liquid of pumpable consistency which is preferably used as a crude reaction product, prepared, for example, in a known manner by the conversion of the corresponding polymeric phosphonitrilic chlorides to the specified esters, and then halogenated. Refined products such as the trimer are also quite useful. Halogenation, for example, may be carried out as shown by Hamalainen et al., Textile Research Journal, February 1956, pp. 14l 144, and U8. Patent 2,825,718. The esters or mixed esters may also be chlorinated or fluorinated similarly.
The halogenated esters are also former, for example, by reacting the liquid polymers of phosphonitrilic chloride with a compound which will form a halogenated ester of the phosphonitrilic chloride, for example, ethylene chlorohydrin and ethylene bromohydrin, or halogenated alkyl alcohols, for example, as shown in US. 2,681,295.
The product formed by these reactions is an oily liquid and may be incorporated in viscose as such or in suitable solutions or aqueous emulsions. Preferably a controlled amount of the flame-retardant halogenated phosphonitrilate is injected into the viscose just prior to its extrusion through the filament forming spinnerets. The viscose is then spun into an acid bath and processed in a conventional manner.
The following examples are set forth to demonstrate this invention.
EXAMPLE 1 295.5 grams (3.67 moles) of ethylene chlorohydrin was added dropwise over a 75 minute period to a stirred solution of 133.4 grams (2.3 mole equiv.) of the cyclic trimer of phosphonitrilic chloride in 1000 ml. of pyridine. Initially the reaction mixture was at 20 C., but the temperature rose rapidly reaching 38 C. after about 70 grams of ethylene chlorohydrin had been added. External cooling reduced the temperature to about C. where it was held for the remainder of the addition. The reaction mixture was then stirred at room temperature for 24 hours.
After the 24 hours of stirring, some excess of pyridine was distilled off under vacuum (150 minutes, 40-41 C.) and the residue poured onto ice water (1000 ml.). The product was extracted with chloroform (300 ml.) and the chloroform solution separated, washed twice with dilute hydrochloric acid (100 ml. per wash) and then twice with water (300 ml. per wash). The aqueous layers were extracted successively with chloroform (300 ml.) and the chloroform solutions combined, dried and filtered.
Evaporation of the chloroform on a rotary evaporator left an oily residue which was stirred under vacuum for 5.5 hours (40 C., 0.02 mm.). The final product was a straw colored oil (225.5 grams, 95%) with a faint mistiness which was not removed by filtering.
A nuclear magnetic resonance spectrum of this material showed a triplet 3.75 p.p.m. and a complicated, poorly resolved pattern at 1:1 ratio. This result was consistent with the formula for 2,2,4,4,6,6-hexa(2-chloroethoxy) cyclotriphosphazatriene or 2-chloroethyl hexaester of trimeric phosphonitrilic chloride, and there were no significant impurities. Analysis of the compound showed 22.8% carbon, 3.95% hydrogen, 34.7% chlorine, 7.54% nitrogen and 16.9% phosphorus. Theoretical requirements for the compound are 23.6% carbon, 3.95% hydrogen, 34.8% chlorine, 6.9% nitrogen and 15.2% phosphorus.
A compound prepared in this manner was injected into the viscose line supplying the spinnerets for manufacturing rayon in a metered amount based on the weight of the cellulose in the viscose. This viscose was spun into a conventional aqueous acid spin bath comprising 9.0% sulfuric acid, 2.0% zinc sulfate and sodium sulfate at 55 C. The resulting yarn was processed by passing it through a series of baths including water wash, desulfurization, bleaching, bleach acid, anti-chlorine, and soft finish baths. The yarn was dried and collected.
A yarn flammability test was conducted with yarn produced as described above. The test consisted of first preparing a yarn bundle by wrapping the yarn around the closed fingers of an extended hand to produce a bundle of 6000 denier and then removing it from the hand. The yarn bundle is twisted five times and then doubled on itself to produce an integrated yarn bundle, one and one-half inches long and of 12,000 denier size. The free ends of the yarn bundle are clamped in forceps, and the bundle, held in horizontal position, is passed through the tip of the flame of a Fisher burner in an oscillating motion at a rate of one pass per second. The burner flame is adjusted to a two inch height and a blue flame. The number of passes to induce flaming of the sample is determined. A control yarn bundle (yarn con- .tains no flame-retardant inflames in 1 or 2 passes and flame-retardant yarns are classified for inflammability as follows:
1-2 passes-poor 3-4 passes-fair 56 passes-good 7-9 passes-very good to excellent 10 or more passes-excellent Rayon yarn containing about 15 wt. percent of the 2-chloroethyl hexaester of trimeric phosphonitrilic chloride was rated excellent in the above test procedure with no evidence of after-glow. After-glow represents combustion without a visible flame.
Retention of the amount of flame-retardant in the yarn after the above. described complete processing of the spun yarn based on phosphorus analysis showed 91.0%. The yarns esthetic properties were substantially the same as ordinary rayon.
EXAMPLE II A similar procedure for preparing the chlorinated ester of the cyclic trimer of phosphonitrilic chloride as shown in Example I was carried out except that a mixture of phosphonitrilic chloride polymers obtained as the crude product from the preparation of the liquid phosphonitrilic chloride polymer was employed in place of the pure cyclic trimer. The mixture contained mostly trimer and tetramers with some higher cyclic and linear polymers of phosphonitrilic chloride. The yield was 85.4% and analysis of the product showed 23.3% carbon, 4.05% hydrogen, 34.9% chlorine, 16.0% phosphorus and 7.4% nitrogen.
The product of the above reaction was similarly injected into viscose and the viscose spun and processed as described in Example I. The yarn, containing about 15% by weight of the injected product, was subjected to the flame test and showed very good flame retarding with no after-glow. After exposure to ultraviolet light in a Fadeometer for 50 hours, the loss of yarn strength was not greater than conventional rayon.
EXAMPLE III The 2,3-dichloropropyl hexaester of the cyclic trimer of phosphonitrilic chloride was prepared by chlorination of the hexaallyl ester of phosphonitrilic chloride. This was injected into viscose and the viscose spun and processed. The yarn, containing 25% by weight of the chlorinated phosphonitrilate was flame-retardant.
Other water-insoluble, liquid halogenated polyphosphonitrilic esters, e.g. chlorinated, brominated and fluorinated allyl esters of polyphosphonitrilic chloride; adducts of bromoform and allyl ester of polyphosphonitrilic chloride; 2,3-dibromopropyl ester of polyphosphonitrilic chloride; 1,3-dichloropropyl ester of polyphosphonitrilic chloride; chlorophenyl ester of polyphosphonitrilic chloride; bromonaphthyl ester of polyphosphonitrilic chloride; halogenated or partially halogenated mixed esters, e.g. bromopropyl, ethyl ester of polyphosphonitrilic chloride; fluoropropyl, methyl ester of polyphosphonitrilic chloride; chlorophenyl, methyl ester of polyphosphonitrilic chloride; etc., can be injected into viscose to prepare rayon as shown in the foregoing examples.
As set forth in the statement of the invention, it is not necessary that the OR and OR groups attached to each phosphorus atom in the polymeric chain be halogenated. That is, for example, the hexaester of the cyclic trimer of phosphonitrilic chloride has six substituent groups. In accordance with this invention, from one to six of these groups can be halogenated.
Some of the halogenated esters will be more permanently retained in the yarn than others, some require addition in greater amounts to the viscose to obtain the desired flame-retardancy but the greatest advantage of the flameretardant of this invention is that it can be injected into viscose and spun into a yarn which retains its normal softness and hand. This is because the halogenated ester is a viscous liquid held within the regenerated cellulose matrix. Phosphonitrilic esters which are solids tend to produce harsh yarn and are difiicult to spin in viscose.
Those halogenated esters which are not permanently retained by fabric made of the rayon yarn after continued washing will be useful for rayon intended for use in disposable garments.
I claim:
1. Regenerated cellulose filaments and filamentary articles, said filaments having dispersed therein a flame-retardant amount of a substantially water-insoluble, liquid phosphonitrilate polymer having the following general formula:
wherein R and R are the same or different alkyl, alkenyl, arylalkyl or aryl radicals wherein the alkyl and alkenyl redicals have from 1 to 6 carbon atoms and the aryl radicals have from 6 to 10 carbon atoms and, at least one of the -OR or -OR groups of the polymer ha one or more halogen atoms attached to the carbon atoms of R or R, and n is an integer of at least 3.
2. The regenerated cellulose filaments of claim 1 containing from about 5 to about 30% based on the Weight of the cellulose, of the liquid phosphonitrilate polymer.
3. The regenerated cellulose filaments of claim 1 wherein R and R are both 2-chloroethyl radicals.
4. The regenerated cellulose filaments of claim 1 wherein R and R are both 2,3-dichloropropyl radicals.
5. The regenerated cellulose filaments of claim 1 wherein R and R are different radicals and one of said radicals is halogenated.
6. A method of preparing a flame-retardant regenerated cellulose filament which comprises mixing viscose and a fllame-retardant amount of a substantially water-inlNi wherein R and R are the same or diflerent alkyl, alkenyl, arylalkyl or aryl radicals wherein the alkyl and alkenyl radicals have from 1 to 6 carbon atoms and the aryl radicals have from 6 to 10 carbon atoms and at least one of the -OR or OR' groups of the polymer has one or more halogen atoms attached to the carbon atoms of R or R, and n is an integer of at least 3; shaping the mixture into a filament, and coagulating and regenerating said filament.
7. The method of claim 6 wherein the viscose is passed under pressure to a spinneret and extruded, and the liquid phosphonitrilate polymer is injected at a controlled rate into the viscose prior to extrusion. H
8. The method of claim 6 wherein about 5 to about 30% 0f the liquid phosphonitrilate is mixed with the viscose, based on the weight of the cellulose in the viscose.
9. The method of claim 6 wherein R and R are the same and each contain at least 2 carbon atoms.
References Cited UNITED STATES PATENTS 8/ 1966 Schappel et al. 7/1969 Godfrey.
US. Cl. X.R.
US819483A 1969-04-25 1969-04-25 Flame-retardant rayon containing halogenated phosphonitrilate polymer Expired - Lifetime US3505087A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US81948369A 1969-04-25 1969-04-25

Publications (1)

Publication Number Publication Date
US3505087A true US3505087A (en) 1970-04-07

Family

ID=25228291

Family Applications (1)

Application Number Title Priority Date Filing Date
US819483A Expired - Lifetime US3505087A (en) 1969-04-25 1969-04-25 Flame-retardant rayon containing halogenated phosphonitrilate polymer

Country Status (3)

Country Link
US (1) US3505087A (en)
BR (1) BR7017704D0 (en)
ZA (1) ZA702767B (en)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3732683A (en) * 1971-03-25 1973-05-15 Fmc Corp Regenerated cellulose filaments containing a flame-retardant phosphonitrilate polymer and an organic phosphate salt to reduce filament to metal friction
US3839244A (en) * 1970-05-01 1974-10-01 Akzona Inc Flame-resistant polymeric products from polyacyloxalamidrazones and viscose and their manufacture
FR2232568A1 (en) * 1973-06-11 1975-01-03 Horizons Research Inc
US3859249A (en) * 1972-12-07 1975-01-07 Akzona Inc Process for manufacture of flame retardant polyester
FR2234362A1 (en) * 1973-06-19 1975-01-17 Courtaulds Ltd
US3865604A (en) * 1972-04-06 1975-02-11 Sandoz Ltd Flame-retardant regenerated cellulose
US3865783A (en) * 1972-05-18 1975-02-11 Akzona Inc Flame-retardant polyester
US3869294A (en) * 1973-03-05 1975-03-04 Ethyl Corp Phosphonitrile polymer
US3891449A (en) * 1973-03-05 1975-06-24 Ethyl Corp Modified phosphazene fire retardants
US3891448A (en) * 1973-03-05 1975-06-24 Ethyl Corp Modified phosphazene flame retardant
JPS5092950A (en) * 1973-12-22 1975-07-24
US3919364A (en) * 1972-07-17 1975-11-11 Mo Och Domsjoe Ab Process for preparing phosphorus nitrilate polymers
DE2532521A1 (en) * 1974-07-30 1976-02-19 Sandoz Ag POLYMERIC MATERIALS AND THEIR PRODUCTION
JPS5136267A (en) * 1974-09-19 1976-03-27 Kuraray Co HORIESUTERUSEIKEIBUTSU NO NANNENKAHOHO
JPS5146346A (en) * 1974-10-18 1976-04-20 Kuraray Co Nannenseino ryokonahoriesuterusoseibutsu
US3990900A (en) * 1972-08-17 1976-11-09 Fmc Corporation Polymeric phosphazenes
US4029634A (en) * 1975-05-02 1977-06-14 E. I. Du Pont De Nemours And Company Flame retardant polymeric compositions containing halogen substituted hexakis-(substituted phenoxy)cyclotriphosphazene
US4042561A (en) * 1976-05-20 1977-08-16 Celanese Corporation Flame retardant compositions containing polyphosphazenes
US4111701A (en) * 1974-04-05 1978-09-05 Avtex Fibers Inc. Flame retardant regenerated cellulose filaments containing cross-linked polymeric phosphazenes
US4405738A (en) * 1982-03-05 1983-09-20 Akzona Incorporated Flame retardant additives and flame retardant polyester compositions
US4601843A (en) * 1985-04-02 1986-07-22 Borg-Warner Chemicals, Inc. Phosphazene based functional fluid compositions
US4908061A (en) * 1986-11-13 1990-03-13 Kansai Paint Co., Ltd. Antifouling coating
EP0336004A3 (en) * 1988-04-05 1990-10-31 Kohjin Co., Ltd. High functional regenerated cellulose composition
WO2012083318A1 (en) 2010-12-20 2012-06-28 Lenzing Ag Fireproof cellulosic man-made fibers
EP3476985A1 (en) 2017-10-27 2019-05-01 Lenzing Aktiengesellschaft Fireproof cellulosic man-made fibres

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3266918A (en) * 1962-12-19 1966-08-16 Fmc Corp Viscose solutions for making flame retardant rayon
US3455713A (en) * 1966-07-21 1969-07-15 Fmc Corp Flame-retardant regenerated cellulose

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3266918A (en) * 1962-12-19 1966-08-16 Fmc Corp Viscose solutions for making flame retardant rayon
US3455713A (en) * 1966-07-21 1969-07-15 Fmc Corp Flame-retardant regenerated cellulose

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839244A (en) * 1970-05-01 1974-10-01 Akzona Inc Flame-resistant polymeric products from polyacyloxalamidrazones and viscose and their manufacture
US3732683A (en) * 1971-03-25 1973-05-15 Fmc Corp Regenerated cellulose filaments containing a flame-retardant phosphonitrilate polymer and an organic phosphate salt to reduce filament to metal friction
US3865604A (en) * 1972-04-06 1975-02-11 Sandoz Ltd Flame-retardant regenerated cellulose
US3865783A (en) * 1972-05-18 1975-02-11 Akzona Inc Flame-retardant polyester
US3919364A (en) * 1972-07-17 1975-11-11 Mo Och Domsjoe Ab Process for preparing phosphorus nitrilate polymers
US3990900A (en) * 1972-08-17 1976-11-09 Fmc Corporation Polymeric phosphazenes
US3859249A (en) * 1972-12-07 1975-01-07 Akzona Inc Process for manufacture of flame retardant polyester
US3869294A (en) * 1973-03-05 1975-03-04 Ethyl Corp Phosphonitrile polymer
US3891449A (en) * 1973-03-05 1975-06-24 Ethyl Corp Modified phosphazene fire retardants
US3891448A (en) * 1973-03-05 1975-06-24 Ethyl Corp Modified phosphazene flame retardant
FR2232568A1 (en) * 1973-06-11 1975-01-03 Horizons Research Inc
FR2234362A1 (en) * 1973-06-19 1975-01-17 Courtaulds Ltd
JPS5092950A (en) * 1973-12-22 1975-07-24
US4111701A (en) * 1974-04-05 1978-09-05 Avtex Fibers Inc. Flame retardant regenerated cellulose filaments containing cross-linked polymeric phosphazenes
DE2532521A1 (en) * 1974-07-30 1976-02-19 Sandoz Ag POLYMERIC MATERIALS AND THEIR PRODUCTION
JPS5136267A (en) * 1974-09-19 1976-03-27 Kuraray Co HORIESUTERUSEIKEIBUTSU NO NANNENKAHOHO
JPS5146346A (en) * 1974-10-18 1976-04-20 Kuraray Co Nannenseino ryokonahoriesuterusoseibutsu
US4029634A (en) * 1975-05-02 1977-06-14 E. I. Du Pont De Nemours And Company Flame retardant polymeric compositions containing halogen substituted hexakis-(substituted phenoxy)cyclotriphosphazene
US4042561A (en) * 1976-05-20 1977-08-16 Celanese Corporation Flame retardant compositions containing polyphosphazenes
US4405738A (en) * 1982-03-05 1983-09-20 Akzona Incorporated Flame retardant additives and flame retardant polyester compositions
US4601843A (en) * 1985-04-02 1986-07-22 Borg-Warner Chemicals, Inc. Phosphazene based functional fluid compositions
US4908061A (en) * 1986-11-13 1990-03-13 Kansai Paint Co., Ltd. Antifouling coating
EP0336004A3 (en) * 1988-04-05 1990-10-31 Kohjin Co., Ltd. High functional regenerated cellulose composition
WO2012083318A1 (en) 2010-12-20 2012-06-28 Lenzing Ag Fireproof cellulosic man-made fibers
US9988743B2 (en) 2010-12-20 2018-06-05 Lenzing Ag Process of making flame retardant cellulosic man-made fibers
US10577723B2 (en) 2010-12-20 2020-03-03 Lenzing Ag Flame retardant cellulosic man-made fibers
EP3476985A1 (en) 2017-10-27 2019-05-01 Lenzing Aktiengesellschaft Fireproof cellulosic man-made fibres
WO2019081617A1 (en) 2017-10-27 2019-05-02 Lenzing Aktiengesellschaft FLAME-RESISTANT CELLULOSIC MAN-MADE FIBERS
US12116701B2 (en) 2017-10-27 2024-10-15 Lenzing Aktiengesellschaft Flame retardant cellulosic man-made fibers

Also Published As

Publication number Publication date
ZA702767B (en) 1971-01-27
BR7017704D0 (en) 1973-01-18

Similar Documents

Publication Publication Date Title
US3505087A (en) Flame-retardant rayon containing halogenated phosphonitrilate polymer
US3455713A (en) Flame-retardant regenerated cellulose
US2205042A (en) Softening of textile materials and compositions therefor
US4063883A (en) Manufacture of flame-retardant regenerated cellulose fibres
DE2521926A1 (en) NEW POLYMERS CONTAINING PHOSPHORUS AND BROMOMON AND THEIR USE IN REFRACTORY BULK
US3974251A (en) Production of flameproof fibers of regenerated cellulose
US3645936A (en) Flame-retardant regenerated cellulose filaments
CH533718A (en) Bis (halogenmethyl)-5,5-dioxaphosphanes-1,32-as flame retardants
US3994996A (en) Polymeric phosphazenes and process for preparation
US3532526A (en) Flame - retardant rayon containing mercapto-phosphonitrilate polymer
US3845167A (en) Polymeric phosphazenes and process for making same
US3836608A (en) Process for self condensing phosphonitrilic chloroesters and product
US4040843A (en) Flame-retardant regenerated cellulose filaments containing oligomeric phosphonitrilic compounds
DE2809773A1 (en) FULLY AROMATIC POLYAMIDE FIBERS AND THE PROCESS FOR THEIR PRODUCTION
US4030933A (en) Phosphorus and halogen containing polymers of bis-hydroxyethyl terephthalate as flame retardant additives
US4076933A (en) Process for producing a regenerated shaped cellulosic fiber
US4191715A (en) Flame retarding compound
US3990900A (en) Polymeric phosphazenes
US4447568A (en) Flame-retardant polyacrylonitrile fiber
US3877952A (en) Flame-proofing agents, especially for use with cellulosic materials
US3556825A (en) Flame retardant rayon incorporating bis-diphenyl phosphate derivative of polyalkylene glycols
US3315329A (en) Process for the manufacture of chemical lace
US3019509A (en) Crimped regenerated cellulose fibers
JPH08158201A (en) Flame retardant fabric excellent in light fastness
US4111701A (en) Flame retardant regenerated cellulose filaments containing cross-linked polymeric phosphazenes

Legal Events

Date Code Title Description
AS Assignment

Owner name: WESTERN AND SOUTHERN LIFE INSURANCE COMPANY THE C/

Free format text: AS SECURITY FOR INDEBTEDNESS RECITED ASSIGNOR GRANTS , BARGAINS, MORTGAGES, PLEDGES, SELLS AND CREATES A SECURITY INTEREST WITH A LIEN UNDER SAID PATENTS, SUBJECT TO CONDITIONS RECITED.;ASSIGNOR:AVTEX FIBERS INC. A NY CORP.;REEL/FRAME:003959/0219

Effective date: 19810301

Owner name: PROVIDENT ALLIANCE LIFE INSURANCE COMPANY C/O THE

Free format text: AS SECURITY FOR INDEBTEDNESS RECITED ASSIGNOR GRANTS , BARGAINS, MORTGAGES, PLEDGES, SELLS AND CREATES A SECURITY INTEREST WITH A LIEN UNDER SAID PATENTS, SUBJECT TO CONDITIONS RECITED.;ASSIGNOR:AVTEX FIBERS INC. A NY CORP.;REEL/FRAME:003959/0219

Effective date: 19810301

Owner name: KELLOGG CREDIT CORPORATION A DE CORP.

Free format text: AGREEMENT WHEREBY SAID HELLER AND RAYONIER RELEASES ALL MORTGAGES AND SECURITY INTERESTS HELD BY AVTEX ON APRIL 28, 1978, AND JAN. 11, 1979, RESPECTIVELY AND ASSIGNS ITS ENTIRE INTEREST IN SAID MORT-AGAGE AGREEMENT TO ASSIGNEE;ASSIGNORS:WALTER E. HELLER & COMPANY, INC. A NY CORP.;ITT RAYONIER INCORPORATED, A DE CORP.;AVTEX FIBERS INC., A NY CORP.;REEL/FRAME:003959/0350

Effective date: 19800326

Owner name: PAUL REVERE LIFE INSURANCE COMPANY THE C/O THE PAU

Free format text: AS SECURITY FOR INDEBTEDNESS RECITED ASSIGNOR GRANTS , BARGAINS, MORTGAGES, PLEDGES, SELLS AND CREATES A SECURITY INTEREST WITH A LIEN UNDER SAID PATENTS, SUBJECT TO CONDITIONS RECITED.;ASSIGNOR:AVTEX FIBERS INC. A NY CORP.;REEL/FRAME:003959/0219

Effective date: 19810301

Owner name: JOHN HANCOCK MUTUAL LIFE INSURANCE COMPANY JOHN HA

Free format text: AS SECURITY FOR INDEBTEDNESS RECITED ASSIGNOR GRANTS , BARGAINS, MORTGAGES, PLEDGES, SELLS AND CREATES A SECURITY INTEREST WITH A LIEN UNDER SAID PATENTS, SUBJECT TO CONDITIONS RECITED.;ASSIGNOR:AVTEX FIBERS INC. A NY CORP.;REEL/FRAME:003959/0219

Effective date: 19810301

Owner name: NEW ENGLAND MUTUAL LIFE INSURANCE COMPANY 501 BOYL

Free format text: AS SECURITY FOR INDEBTEDNESS RECITED ASSIGNOR GRANTS , BARGAINS, MORTGAGES, PLEDGES, SELLS AND CREATES A SECURITY INTEREST WITH A LIEN UNDER SAID PATENTS, SUBJECT TO CONDITIONS RECITED.;ASSIGNOR:AVTEX FIBERS INC. A NY CORP.;REEL/FRAME:003959/0219

Effective date: 19810301

Owner name: BALBOA INSURANCE COMPANY C/O THE PAUL REVERE EQUIT

Free format text: AS SECURITY FOR INDEBTEDNESS RECITED ASSIGNOR GRANTS , BARGAINS, MORTGAGES, PLEDGES, SELLS AND CREATES A SECURITY INTEREST WITH A LIEN UNDER SAID PATENTS, SUBJECT TO CONDITIONS RECITED.;ASSIGNOR:AVTEX FIBERS INC. A NY CORP.;REEL/FRAME:003959/0219

Effective date: 19810301