US3505087A - Flame-retardant rayon containing halogenated phosphonitrilate polymer - Google Patents
Flame-retardant rayon containing halogenated phosphonitrilate polymer Download PDFInfo
- 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
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
- D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular 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
- C08G79/02—Macromolecular 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
- C08G79/025—Polyphosphazenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/22—Cellulose xanthate
- C08L1/24—Viscose
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.
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- 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
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)
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)
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 |
-
1969
- 1969-04-25 US US819483A patent/US3505087A/en not_active Expired - Lifetime
-
1970
- 1970-03-24 BR BR217704/70A patent/BR7017704D0/en unknown
- 1970-04-24 ZA ZA702767A patent/ZA702767B/en unknown
Patent Citations (2)
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)
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 |
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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 |