US3900285A - Process for producing fireproof fibers - Google Patents

Process for producing fireproof fibers Download PDF

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Publication number
US3900285A
US3900285A US299401A US29940172A US3900285A US 3900285 A US3900285 A US 3900285A US 299401 A US299401 A US 299401A US 29940172 A US29940172 A US 29940172A US 3900285 A US3900285 A US 3900285A
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fiber
contacted
accordance
hydroxylamine
heated
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Michakaze Ono
Hajime Sahara
Masonori Akasaka
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Mitsubishi Chemical Corp
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Mitsubishi Rayon Co Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/63—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with hydroxylamine or hydrazine

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  • the invention relates to a process for the production of fireproof fibers from acrylic fibers. More particularly, it relates to a process for the production of fireproof fibers wherein an acrylic fiber is chemically modified by treating the fiber with hydroxylamine and the fiber so modified is then heated in an gaseous atmosphere.
  • Japanese Patent Publication Nos. 15254/66 and 15726/66 teach to impregnate acrylic fibers with an aqueous solution containing ammonium sulfamate and a nitrogen-containing phosphate followed by heating the impregnated fibers in air.
  • the acrylic fibers essentially as such, are heated in air in the presence of a certain chemical which is intended to act as a catalyst.
  • none of the proposed chemicals give fully satisfactory catalytic effects.
  • a process for the production of fireproof fibers which comprises treating an acrylic fiber with hydroxylamine at a pH of not higher than 7 to such an extent that the treated fiber has a solubility of not more than 50 percent in dimethylformamide at 90C and heating the treated fiber in a gaseous atmosphere.
  • Acrylic fiber referred to herein can be in the form of tows, filamentary yarns, slivers spun yarns, woven fabrics, knitted fabrics, non-woven fabrics, or a paper.
  • the treated fibers may be fabricated into fabrics before being heated.
  • the acrylic fiber is composed of a fiber-forming polymer containing at least 85 percent by weight of units from acrylonitrile and up to percent by weight of units from at least one unsaturated vinyl or allyl compound which is copolymerizable with acrylonitrile.
  • Examples of such comonomers are vinyl esters such as vinyl acetate; acrylates such as methyl acrylate and ethyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate and Z-diethylaminoethyl methacrylate; vinyl ethers such as methyl vinyl ether; acrylic acid and metal salts thereof; methacrylic acid and metal salts thereof; acryloyl or methacryloyl chloride; acrylamide and methacrylamide, itaconic acid and metal salts thereof; itaconamide; N-substituted derivatives of vinyl acid amides such as N-methyl acrylamide, N-methoxy acrylamide, N-methyl methacrylamide and N-methoxy methacrylamide; vinyl chloride; vinylidene chloride; vinyl pyridines; vinyl glycidyl compounds such as glycidyl acrylate and glycidyl methacrylate; vinylsulfonic
  • the hydroxylamine should preferably be in the form of acid addition salts such as sulfate, hydrochloride, nitrate, phosphate, acetate, formate, oxalate, succinate, fumarate, maleate, lactate, tartrate, benzoate and the like.
  • a pH of the reaction medium can be adjusted to a level of not higher than 7, preferably from 3.0 to 7.0, by addition of appropriate amounts of suitable known buffering agents ifdesired.
  • suitable buffering agents include, for example, sodium, potassium, ammonium-, zincor other soluble metal phthalate, secondary phosphate, tertiary phosphate, pyrophosphate, triphosphate, secondary citrate, tartrate, oxalate or acetate.
  • a preferred reaction medium is an aqueous solution of hydroxylamine sulfate or hydrochloride maintained at a pH of 3 to 7 by addition of at least one of the above-mentioned buffering agents.
  • the reaction can be carried out at a temperature of below 200C, preferably from about 80C to about 130C. Higher temperatures often lead to an unacceptable loss of desirable mechanical properties.
  • ticular reaction conditions involving a temperature and a concentration of the hydroxylamine reactant, it usu ally varies from 30 to 90 minutes for immersion, or from 5 to 30 minutes for padding.
  • acrylic fibers having different values of solubility in DMF were heated in a hot air circulating oven at a temperature of 270C until the products having a fire resistance of grade B, as hereinafter defined, were obtained.
  • the values of solubility (in and the times (in minutes) required for the heat-treatment were plotted in a curve, which is shown
  • the acrylic fiber may be immersed and heated in a bath containing a hydroxyamine reactant and maintained at a prescribed pH level.
  • the fiber may be padded with a liquid containing a hydroxylamine reactant and kept at a prescribed pH level, and then heated e.g. by steaming and then dry heating.
  • the reaction should be carried out to such an extent that the treated fiber has a solubility in dimethylformamide of not more than 50 percent, and preferably not more than 30 percent, as measured at 90C.
  • solubility is more than 50 percent, it is impossible to obtain fireproof fibers having excellent fire resistance in a short period of time.
  • the factors which influence the reaction are concentration of the hydroxylamine reactant, pH, temperature, reaction time, a ratio of goods to liquid and a mode of operation. Preferred reaction conditions will be further described with reference to the attached drawing, in which:
  • FIG. 1 is a graph showing a relation between a concentration (in g/l) of hydroxylamine sulfate in the liquid reaction medium and a solubility (in of the treated fiber in DMF:
  • FIG. 2 is a graph showing a relation between a solubility (in of the treated fiber in DMF and a time (in min) of the heat-treatment required for attaining a fire resistance of grade B as defined hereinafter.
  • Samples of Vonnel 17" an acrylic fiber produced by Misubishi Rayon Co., Ltd. and composed of a copolymer containing 93 percent by weight of units from acrylonitrile and 7 percent by weight of units of vinyl acetate
  • Vonnel 17 an acrylic fiber produced by Misubishi Rayon Co., Ltd. and composed of a copolymer containing 93 percent by weight of units from acrylonitrile and 7 percent by weight of units of vinyl acetate
  • the concentrations of hydroxylamine sulfate and the values of a solubility of the treated fiber in DMF as measured at 90C were plotted in a curve, which is shown in FIG. 1.
  • a pick-up of the hydroxylamine reactant on the fiber may be I to 10% by weight.
  • reaction time required for achievement of the intended degree of modification i.e. solubility in DMF of not more than 50 percent, preferably not more than 30 percent, as measured at 90C depends on parin FIG. 2.
  • FIG. 2 shows that the modified acrylic fibers having values of solubility in DMF of 50 and I0 percent require a heating period of about 120 and about 5 minutes, respectively, to achieve the identical fireproof grade of B. It is also noted from FIG. 2 that the solubility values of not more than 50 percent are essential in order to achieve the desired grade of fire resistance within a relatively short time of heating.
  • the acrylic fiber which has chemically been modified with hydroxylamine in a manner as described above and has a solubility in DMF of not more than 50 percent, preferably not more than 30 percent, as measured at C is then heated in a gaseous atmosphere to provide a fireproof product.
  • gaseous atmosphere in which the modified fiber is heated may advantageously be air, other oxidizing atmospheres such as an oxygen-enriched air, nitrogen monoxide, nitrogen dioxide and a halogencontaining gas may also be used.
  • gaseous atmosphere may contain nitrogen or argon as diluent.
  • Preferred temperatures at which the modified fiber may be heated are from about 245 to about 305C.
  • a fireproof product can readily obtained within a short period of usually I to I20 minutes, with a minimum loss of desirable mechanical properties.
  • Excessively high temperatures should be avoided because they lead to deterioration of mechanical properties of the products.
  • temperatures substantially lower than 245C are undesirable since the intended fire resistance cannot be attained within a reasonable period of time.
  • the modified acrylic fiber is heated under conditions such that the fiber undergoes little or no shrinkage although it is not essential to do so. It has been found that the products obtained by heating the modified fiber under no tension still have acceptable mechanical properties and are superior to those comparable products obtained from an unmodified acrylic fiber.
  • yarns and slivers 0 20 percent stretch is preferable; for woven fabrics, non-woven fabrics, and papers 0 l5 percent stretch in both longitudinal and transverse directions, and; for knitted fabrics 0 30 percent stretch in both longitudinal and transverse directions.
  • the products obtained by a process of the invention may be carbonized, for example, by heating them in an inert gaseous atmosphere at temperatures of about 300 to l,000C to produce carbon fibers which may further be graphitized, for example, by heating them in an inert gaseous atmosphere at temperatures of about l,000 to about 2,500C.
  • Solubility of a given acrylic fiber was determined as follows:
  • a sample of the fiber to be tested was dried at a temperature of 105C for 1 hour. At an angle of 45 the dried specimen was contacted with a flame of butane burning on a micro-burner for 60 seconds, a length of the flame being 45 mm. At the end of the period, the specimen was removed from the flame, and its behavior was observed and rated as follows:
  • Grade A No flame and no smoke Grade B: A slight smoke without flame Grade C: Some flame, but self extinguishing Grade D: Burned.
  • EXAMPLE 1 A tow of acrylic filaments, Vonn-el 17 (produced by Mitsubishi Rayon Co., Ltd. and composed of a copolymer containing 93 percent by weight of units from acrylonitrile and 7 percent by weight of units from vinyl acetate) having a filamentary denier of 1.5 and a total denier of 480,000 was treated in an Obermayer dyeing machine with an aqueous bath containing 8 g/l of hydroxylamine sulfate and 12.5 g/l of sodium secondary phosphate at a temperature of 100C for 60 minutes. A ratio of goods to liquid was 1 10. A pH of the bath was 5.6. At the end of the period the tow was removed from the bath, washed with water and dried. The tow so treated, which will be designated as treated tow A, had a solubility of 12% in dimethylformamide (DMF). The starting untreated tow was completely soluble in DMF.
  • DMF dimethylformamide
  • the product obtained from the treated tow A in accordance with the invention (Run No. l) is far superior in fire resistance and mechanical properties to those obtained from the treated tow B and the untreated tow (Run Nos. 2 and 3).
  • the table further shows that the products obtained from Run Nos. 4 and 5, wherein the treated tows A were heated at lower and higher temperatures outside the preferred range, are unstaisfactory with respect to fire resistance and mechanical properties, respectively.
  • the fabric was padded with an aqueous solution of pH 6.3 containing g/l of hydroxylamine sulfate and g/l of sodium tripolyphosphate, squeezed to a liquor content of 60 percent by weight, and steamed in a J-type normal pressure steamer at a temperature of 100C for 20 minutes. At the end of the period, the fabric ws removed from the steamer, washed with water and dried. These procedures were carried out continuously. The fabric so treated had a solubility of 6% in DMF, while the untreated fabric was completely soluble in DMF.
  • the treated and untreated fabrics were then continuously fed to a tender-type heater using high voltage at a rate of 1 m/min and heated in the heater at a temperature of 300C for 15 minutes under conditions such that the fabric underwent 2% weft (transverse) stretch based on the Corresponding property of the unheated fabric.
  • EXAMPLE 3 A cheese of acrylic filamentary yarn 150 den/60 til-- aments) of a copolymer containing 85% by weight of units from acrylonitrile, 10% by weight of units from methyl acrylate and 5% by weight of units from acrylamide was treated with an aqueous bath containing 6 g/l of hydroxylamine sulfate and 6 g/l of sodium acetate trihydrate at 100C for 60 minutes. A ratio of goods to liquid was 1 20, and a pH of the bath was 5.4. At the end of the period, the yarn was removed from the bath, washed with water and dried. The yarn so treated had a solubility of 18% in DMF, whereas the untreated yarn was completely soluble in DMF.
  • each of the treated and untreated yarns was knitted into plain knittings.
  • Samples of the knittings were heated in a hot air circulating oven at a temperature of 250C for 115 minutes under no tension as well as under conditions such that the knitting underwent 10% stretch in both warp and weft directions. Results are shown in Table 11] below.
  • the products obtained by a process in accordance with the invention exhibit an improved fire resistance and retain desirable mechanical properties, when compared with those obtained from untreated yarns.
  • EXAMPLE 4 A tow of bright acrylic filaments of a copolymer containing 99 percent by weight of units from acrylonitrile and 1 percent by weight of units from sodium vinylbenzene sulfonate having a filament denier of 1.5 and a total denier of 480,000 was treated in an Obermayer dyeing machine under super-atmospheric pressures with an aqueous bath containing 30 g/l of hydroxylamine sulfate at a temperature of 120C for 90 minutes. A ratio of goods to liquid was 1 7 and a pH of the bath was 3.5. At the end of the period, the tow was removed from the bath, washed with water and dried. The tow so treated had a solubility of 14.5 in DMF, while untreated tow was completely soluble in DMF.
  • a half of the treated tow was drawn 1.39 and cut to staple fibers of 64 mm in length, which had a steam shrinkage at 100C of about 30 percent. Another half of the tow was cut to fibers of the same length without drawing. Both the drawn and undrawn fibers were blended, made into a web, needle-punched and steamed at 125C for 15 minutes to produce a nonwoven fabric of treated fibers.
  • Each of the non-woven fabrics was heated in a hot air circulating oven to a temperature of 200C, and from 200C to 270C over a period of 40 minutes, and then maintained at 270C for further 40 minutes. Results are shown in Table IV below.
  • EXAMPLE 5 A tow of acrylic filaments of a copolymer containing 93 percent by weight of units from acrylonitrile, 5.5 percent by weight of units from vinyl acetate and 1.5 percent by weight of methylvinylpyridine having a filamentary denier of 1.5 and a total denier of 480,000 was treated in an Obermayer dyeing machine with an aque ous bath containing 15 g/l of hydroxylamine sulfate and 9 g/l of sodium tertiary phosphate at a temperature of C for 60 minutes. A ratio of goods to liquid was 1 z 7 and a pH of the bath was 5.5. At the end of the period, the tow was removed from the bath, washed with water and dried. The tow so treated had'a solubility of l 1.5% in DMF, while the untreated tow was completely soluble in DMF.
  • the bank of the yarn was treated with an aqueous bath containing g/l of hydroxylamine hydrochloride and 8 g/l of ammonium secondary phosphate at a temperature of 85C for 60 minutes.
  • a ratio of goods to liquid was 1 50 and a pH of the bath was 5.0.
  • the yarn so treated had a solubility of 20.5 percent in DMF, while the untreated yarn was completely soluble in DMF.
  • Each of the treated and untreated hank was placed in a hot air circulating oven at 100C and a temperature of the oven was raise to 280C at a rate of 3C/rnin during which the hanks were prevented from shrinking by circular frames around which they had been reeled.
  • the hanks were then formed into cones and tested for fire resistance and mechanical properties. Results are shown in Table VI below.
  • Table Vl Properties of products Table VI shows the same tendency as revealed in Table Example 7
  • a tow of Vonnel 17 as employed in Example I was cut to staple fibers 56 mm in length, spun into a twofolded yarn of a meter count of No. 56, which was then knitted into a flat fabric by means of a 14 G V bed knitting machine.
  • a sample of the knitted fabric was treated in a beaker with an aqueous bath containing 10 g/l hydroxylamine phosphate at 100C for 60 minutes.
  • a ratio of goodsto liquid was 1 40 and a pH of the bath was 5.3.
  • the fabric was then removed from the bath, washed with water and dried.
  • the treated fabric had a solubility of 9% in DMF.
  • the fabric was then heated in a hot air circulating oven at 280C for 60 minutes under conditions such that the fabric underwent no shrinkage in both warp and weft directions.
  • B. The procedures as in (A) above were repeated except that the bath was replaced by one containing 10 g/l of ammonium hydroxide. A pH of the bath was 9.2. The treated fabric was still completely soluble in DMF.
  • C. A sample of the untreated fabric was heated in a manner as described in (A) above.
  • a process for producing fireproof fibers which comprises contacting an acrylic fiber with hydroxylamine to effect chemical reaction at a pH of not higher than 7 at a temperature of below 200C for a time sufficient that the contacted fiber has a solubility of not more than 50% in dimethylformamide at 90C and heating the contacted fiber to oxidize the fiber at a temperature of 245C to 305C in a gaseous atmosphere.
  • the starting acrylic fiber is in the form of a tow, a filamentary yarn, a sliver, a spun yarn, a woven fabric, a knitted fabric, a non-woven fabric, or a paper.
  • a process in accordance with claim 4 wherein the acrylic fiber is contacted with hydroxylamine in one of the forms of sulfate and hydrochloride in an aqueous solution and wherein the heating of the contacted fiber is performed in air for a period of not more than 2 hours under conditions such that the fiber undergoes little or no shrinkage.
  • the contacted fiber is in the form of a tow, a filamentary yarn, a sliver or a spun yarn and wherein the contacted fiber is heated in air under conditions such that it undergoes 0 20 percent stretch.
  • the contacted fiber is in the form of woven fabric, a non-woven fabric, or a paper and wherein the contacted fiber is heated in air under such conditions that it undergoes 0 15 percent stretch in both longitudinal and transverse directions.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Inorganic Fibers (AREA)
  • Paper (AREA)
  • Fireproofing Substances (AREA)
  • Artificial Filaments (AREA)
US299401A 1971-10-21 1972-10-20 Process for producing fireproof fibers Expired - Lifetime US3900285A (en)

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JP (1) JPS5410677B2 (cs)
DE (1) DE2251320C3 (cs)
FR (1) FR2156805B1 (cs)
GB (1) GB1401649A (cs)
IT (1) IT969753B (cs)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070142515A1 (en) * 2004-02-20 2007-06-21 Toray Industries, Inc. A Corporation Of Japan Solution containing flame-resistant polymer and carbon molding
US20080299389A1 (en) * 2005-08-09 2008-12-04 Toray Industries, Inc. Flame Resistant Fiber, Carbon Fiber and Production Method Thereof
CN117739256A (zh) * 2024-01-10 2024-03-22 沈阳欧施盾新材料科技有限公司 一种耐腐性、抗老化的储气瓶及其制造方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5259799A (en) * 1975-11-12 1977-05-17 Mitsubishi Rayon Co Production of porous flame resistant fiber
JPS5263428A (en) * 1975-11-14 1977-05-25 Mitsubishi Rayon Co Ltd Production of porous carbon fiber
CN100348787C (zh) * 2005-11-30 2007-11-14 江苏华佳丝绸有限公司 茧丝脱胶后的增重工艺

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3592595A (en) * 1968-11-21 1971-07-13 Celanese Corp Stabilization and carbonization of acrylic fibrous material
US3668236A (en) * 1970-03-23 1972-06-06 Universal Oil Prod Co Reaction product of alkanolamine and two particular acids
US3729549A (en) * 1971-07-07 1973-04-24 Celanese Corp Process for the formation of stabilized and carbonized acrylic fibrous material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3592595A (en) * 1968-11-21 1971-07-13 Celanese Corp Stabilization and carbonization of acrylic fibrous material
US3668236A (en) * 1970-03-23 1972-06-06 Universal Oil Prod Co Reaction product of alkanolamine and two particular acids
US3729549A (en) * 1971-07-07 1973-04-24 Celanese Corp Process for the formation of stabilized and carbonized acrylic fibrous material

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070142515A1 (en) * 2004-02-20 2007-06-21 Toray Industries, Inc. A Corporation Of Japan Solution containing flame-resistant polymer and carbon molding
US7655716B2 (en) * 2004-02-20 2010-02-02 Toray Industries, Inc. Solution containing flame-resistant polymer and carbon molding
US20100086762A1 (en) * 2004-02-20 2010-04-08 Toray Industries, Inc. Solution containing flame-resistant polymer and carbon molding
CN1922214B (zh) * 2004-02-20 2011-04-13 东丽株式会社 含耐火聚合物的溶液及碳成形品
US8043693B2 (en) 2004-02-20 2011-10-25 Toray Industries, Inc. Solution containing flame-resistant polymer and carbon molding
US20080299389A1 (en) * 2005-08-09 2008-12-04 Toray Industries, Inc. Flame Resistant Fiber, Carbon Fiber and Production Method Thereof
EP1921183A4 (en) * 2005-08-09 2009-12-09 Toray Industries HEAVY FLAMMABLE FIBER, CARBON FIBER AND MANUFACTURING PROCESS FOR BOTH
US7976945B2 (en) 2005-08-09 2011-07-12 Toray Industires, Inc. Flame resistant fiber, carbon fiber and production method thereof
KR101291965B1 (ko) 2005-08-09 2013-08-09 도레이 카부시키가이샤 내염 섬유, 탄소 섬유 및 이들의 제조 방법
CN117739256A (zh) * 2024-01-10 2024-03-22 沈阳欧施盾新材料科技有限公司 一种耐腐性、抗老化的储气瓶及其制造方法和应用

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FR2156805A1 (cs) 1973-06-01
DE2251320C3 (de) 1975-09-25
JPS4845697A (cs) 1973-06-29
IT969753B (it) 1974-04-10
DE2251320A1 (de) 1973-08-16
JPS5410677B2 (cs) 1979-05-09
FR2156805B1 (cs) 1986-02-21
DE2251320B2 (de) 1975-02-13
GB1401649A (en) 1975-07-16

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