US3846373A - Flame-retardant acrylic synthetic fibers having improved properties - Google Patents

Flame-retardant acrylic synthetic fibers having improved properties Download PDF

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Publication number
US3846373A
US3846373A US00285664A US28566472A US3846373A US 3846373 A US3846373 A US 3846373A US 00285664 A US00285664 A US 00285664A US 28566472 A US28566472 A US 28566472A US 3846373 A US3846373 A US 3846373A
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phosphate
tris
acrylic synthetic
halogenated
fluid mixture
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US00285664A
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English (en)
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T Ichimaru
K Takeya
H Suzuki
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Japan Exlan Co Ltd
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Japan Exlan Co Ltd
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    • 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
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4

Definitions

  • the present invention relates to flame-retardant acrylic synthetic fibers with improved chemical and physical properties, and also to a method for producing such acrylic synthetic fibers.
  • the pres ent invention relates to a method for improving the various properties of the fibers such as touch, luster, antifibrillation property, heat-settability, resilience, etc.
  • acrylic synthetic fibers can be rendered flame retardant by introducing a halogenated aliphatic phosphate into the fibers.
  • a proper amount of a halogenated aliphatic phosphate is introduced into the fibers, the resultant fibers certainly show not only desirable flame retardant property but also good touch, good luster and other good properties.
  • the halogenated aliphatic phosphate to be introduced into the fibers is increased to such an amount as to make the fibers more flame-retardant, the flame retardant property is further improved, but other fiber qualities and properties will deteriorate with the increase of the amount of the flame retardant additive.
  • the various disadvantages resulting from the halogenated aliphatic phosphate introduced into the fibers such as the fibrillation caused in the steps of forming the fibers containing the halogenated aliphatic phosphate, lack in resilience of the products in use, change of touch with the passage of time, etc. were inevitable when a large amount of the halogenated aliphatic phosphate was introduced.
  • a solid flame retardant additive such as antimony oxide which is entirely incompatible with the halogenated aliphatic phosphate.
  • a flame retardant additive such as antimony oxide, which'has no interaction with acrylonitrile polymer in the fibers, has a disadvantage of being more liable to cause the problem of fibrillation than in the case of adding the halogenated aliphatic phosphate only.
  • the viscosity of the flame retardant additive to be introduced into the fibers remarkably influences the properties of the products, and further found that when a fluid mixture prepared as to have a viscosity of more than 6,000 centipoises by dissolving a particular organic compound containing halogen and/or phosphorus into the halogenated aliphatic phosphate is introduced into acrylic synthetic fibers, the fiber properties are remarkably improved, and the flame retardant property is synergistically improved.
  • the main object of the present invention is to improve the properties of flame retardant acrylic synthetic fibers.
  • An object of the present invention is to obtain acrylic synthetic fibers which are improved not only in the properties including touch, luster, anti-fibrillation, heat-settability, resilience, etc., but also effectively prevented from the fluctuation in dyeability, and moreover rendered highly flame retardant.
  • Another object of the present invention is to improve the various properties of acrylic synthetic fibers and to augment the flame retardant property to a further extent as well as to prevent the fluctuation of dyeability by incorporating a fluid mixture having a viscosity of at wherein each of R R and R stands for a halogenated aliphatic hydrocarbon radical having no more than 8 carbon atoms
  • the above-mentioned objects of the present invention can be attained by incorporating into the fibers a fluid mixture "having a viscosity of at least 6,000 centipoises at 25C-obtained by dissolving in the halogenated aliphatic phosphate a solid organic compound containing halogen and/or phosphorus which is soluble in the halogenated aliphatic phosphate.
  • the thus-obtained flame retardant acrylic synthetic fibers are excellent not only in the flame retardant property but also in other properties including touch, luster, anti-fibrillation, heat-settability, resilience,-etc. Therefore, for example, artificial hair products having I excellent toucn and luster like human hair and excelcausing fibrillated, branched or worn out hair upon combing or brushing, and of tending to lose the curls and waves by washing, i.e., free from the changes in the excellent human hair-like touch and luster with the passage of time during wearing.
  • the acrylic synthetic fibers according to the present invention shows a much higher flame retardant property than that of the conventional acrylic synthetic fibers containing only a halogenated aliphatic phosphate when the amount of the flame retardant additive incorporated into the fibers is the same.
  • the acrylic synthetic fibers obtained according to the present invention do not show any fluctuations in dyeability as contrasted to the conventional acrylic synthetic fibers containing only a halogenated aliphatic phosphate.
  • the flame retardant acrylic synthetic fibers obtained according to the present invention when used for preparing artificial hair, can give more excellent human hair-like luster, by using a compound having a refractive index at 25C ranging from 1.44 to 1.60 as the above-mentioned halogenated aliphatic phosphate. 1
  • halogenated aliphatic phosphate to be used in this invention and represented by the above indicated general formula include liquid compounds such as tris( ,B-chloroethyl)phosphate, tris(B-bromoethyDphosphate, tris( 3-chloropropyl)phosphate, tris( 3- bromopropyl) phosphate, tris(2- chloroprOpyDphosphate, tris( 2- bromopropyl)phosphate, tris(2,3- dichloropropyl)phosphate, tris(2,3-
  • each of R and R is alkyl, cycloalkyl, aralkyl or aryl group which is unsubstituted or substituted with halogen atom(s) and which has 2 to 20 carbon atoms, such as bis(benzyl)ether of tetrabromobisphenol-A, bis(chlorobromopropyl)ether of tetrabromobisphenol- A, etc.; precondensates of tetrabromobisphenol-A with polyhalogenated compounds or diepoxides, etc.; halogenated diphenyl ethers such as chlorinated'diphenyl ether, brominated diphenyl ether, etc.; halogenated phenols or its halogenated alkyl (preferably not more than 10 carbon atoms) ethers, etc. Besides these, any other solid organic compounds containing halogen and/or phosphorus and soluble in the halogenated aliphatic phosphate can be used.
  • Such a halogenated aliphatic phosphate and an organic compound containing halogen and/or phosphorus may be mixed in various combinations and dissolved to form a homogeneous fluid mixture having a viscosity of at least 6,000 centipoises.
  • Any mixing ratio (by weight) of such a halogenated aliphatic phosphate and such organic compounds containing halogen and- /or phosphorus can be used, if this ratio gives a fluid mixture satisfying the foregoing viscosity.
  • fluid mixture as used herein is meant a homogeneous composition which is fluid at room temperature'or upon the operation of introducing the mixture into the fibers. Also, it is an essential requirement that the viscosity of the fluid mixture should be at least 6,000 centipoises at 25C. When a fluid mixture of less than that viscosity is used, it is difficult to fully attain the objects of the present invention.
  • the upper limit of the viscosity of the fluid mixture according to the present invention may vary depending on the particular combination of the halogenated aliphatic phosphate and the organic compound containing halogen and/or phosphorus to be used or on the degree of the desired modifying effect of the fiber. Even a composition which is solid at room temperature but is fluid upon introducing it into the fibers can be used. However a viscosity of less than 300,000 centipoises is generally desirable for operation.
  • the upper limit of the amount of the fluid mixture to be introduced into the fibers is desirable to be not to be more than 40 percent in consideration of the other fiber properties.
  • the most advantageous procedure to introduce such a fluid mixture of halogenated aliphatic phosphate and organic compounds containing halogen and/or phosphorus into the acrylic synthetic fibers are to incorporate a fluid mixture having a viscosity within the abovementioned specified range into the spinning solution for producing the fibers. Then the spinning solution containing said fluid mixture is formed into filaments by a generally well known wet spinning or dry spinning method. The spun filaments may further be treated in a known manner. Thus, the filaments may be waterwashed, stretched, dried and heat-treated.
  • Another procedure for causing the above-mentioned fluid mixture to be contained in the fibers is to treat the gel filaments (obtained by dryor wet-spinning an acrylic polymer solution through spinneret orifices under general spinning conditions) in a treating bath containing a fluid mixture of a viscosity within the abovementioned specified range, and then to carry out the usual post treatment steps.
  • the gel filaments obtained by dryor wet-spinning an acrylic polymer solution through spinneret orifices under general spinning conditions
  • a treating bath containing a fluid mixture of a viscosity within the abovementioned specified range
  • Such compounds include, for example, vinyl esters of saturated aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, etc.; vinyl halides and vinylidene halides such as vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinylidene fluoride; allyl type alcohols such as allyl alcohol, methallyl alcohol, ethallyl alcohol, etc.; allyl, methallyl and other unsaturated alcohol ester of monobasic acids such as allyl or methallyl acetate, laurate, cyanide, etc.; acrylic acid, alkacrylic acids (such as methacrylic acid, ethacrylic acid, etc.), and esters and amides of such acids (such as methyl, ethyl, propyl, butyl acrylates and methacrylates; acrylamide, methacrylamide, N-methyl, -ethyl, -prop
  • Alkyl esters of a,B-unsaturated polycarboxylic acids such as dimethyl, -ethyl, -propyl, -butyl esters of maleic acid, fumaric acid, citraconic acid also copolymerize with acrylonitrile to form copolymers.
  • the. molecular weight (average molecular weight) of the acrylonitrile homopolymer or copolymer for producing polyacrylonitrile shaped products is within the range of from 25,000 or 30,000 to 200,000 or 300,000, or higher, and the particularly advantageous range is from 50,000 to 100,000.
  • These molecular weights are calculated from the viscosity of the polymer in dimethylformamide calculated by the Staudingers equation (refer to the specification of U.S. Pat. No. 2,404,713 dated June 23, 1946.).
  • the acrylic polymer to. be used in this invention is an acrylonitrile homopolymer or copolymer containing 30 percent or less of at least one of the above mentioned monoethylenically unsaturated monomer and at least percent acrylonitrile, but polymers containing a less amount of acrylonitrile may also be used for the practice of the present invention.
  • the representative solvents which are useful to dissolve the acrylonitrile polymer to prepare thespinning solution include organic solvents such as dimethylformamide, dimethylacetamide, ethylene carbonate, and dimethyl sulfoxide, and inorganic solvents such as concentrated aqueous solution of inorganic salts, for example sodium thiocyanate, zinc chloride, etc.
  • the spinning methods used for obtaining the fibers of the present invention may be the generally known wet or dry spinning processes described in Japanese Patent Publication Nos. 3645/50, 4821/53, 9516/57, 878/63 and 2589/61, and U.S. Pat. Nos. 2,404,725 to 2,404,728.
  • EXAMPLE 1 A fluid mixture having a viscosity of 230,000'centipoises at 25C consisting of 70 parts tris(l-bromo-3- chloroisopropyl)phosphate having a viscosity of about 3,000 centipoises at 25C and 30 parts chlorinated paraffin containing 70 percent chlorine was prepared. The fluid mixture was then added to a spinning solution composed of 11 parts of a copolymer consisting of 88 percent acrylonitrile and 12 percent vinyl acetate and 89 parts of a 44 percent aqueous solution of sodium thiocyanate, the amount of the fluid mixture being 40 percent on the basis of the weight of the polymer.
  • the thus-obtained acrylic synthetic fibers were evaluated for flammability to show extremely high self-extinguishability. Further, no fibrillation was observed upon dyeing, cutting and sewing the fibers to prepare artificial hair products.
  • EXAMPLE 2 in table 1 are shown several properties of various spinning solution thoroughly byahigh shear mixer.
  • the acrylic synthetic fiber obtain d by the th d as thus-obtained spinning solution was then extruded into shown in Example 1 in which va i a o nts f th a 12 percent aqueous solution of sodium thiocyanate at conventional flame retardant additive tris( l-bromo-3- 2C through a spinneret having 50 orifices of each 0.2 chloroisopropyl) phosphate singly as well as a h g mm in diameter.
  • the formed filaments were stretched neous fluid mixture having a viscosity of 24,400 centi- 10 times the Oflglha] length in hot Water, Washed With poises at 25C consisting of 70 percent said phosphate ater and then Steam-relaxed at l 15C to Obtain and 30 percent bis(2,3-dibr0m pr py1)eth f t t acrylic synthetic fibers of three denier per filament. bromobisphenol A were introduced i t th fib After combing the thus-obtained fibers 500 times, con- As apparent from the results in Table 1, it is observed Siderable brillation WaS observed.
  • the acrylic 15 On the other h a fluid m xture having a v1sc0s1ty synthetic fibers containing the conventional haloge- Of 6,800 Cent1po1ses at 25C cons1st1ng of i0 parts of nated aliphatic phosphate can be remarkably im d the above-mentioned flame retardant additive and 30 in the fiber properties including the flame retardant P i f P R y ether was P p This property and dyeability. flu1d m1xture was used instead of the above-mentioned In the above tabl the flammability w d t i d flame retardant additive, and acrylic synthetic fibers of by filling 4 g.
  • the spinning solution was extruded through a spinneret (50 holes, each 0.09 mm in diameter) into a 12 percent aqueous solution of sodium thiocyanate at 2C to form filaments.
  • the filaments were stretched times the length, washed with water and steam-relaxed at 120C to obtain acrylic fibers (referred to as A) having 3 denier per monofilament.
  • a flame-retardant monocomponent acrylic synthetic fiber comprising an acrylonitrile polymer selected from the group consisting of homopolymers of acrylonitrile and copolymers containing at least 70 percent acrylonitrile and up to 30 percent of at least one monoethylenically unsaturated monomer copolymerized therewith, and having incorporated in such fibers 3-40 percent by weight of a fluid mixture having a viscosity of at least 6,000 centipoises at 25C obtained by dissolving (1) an organic compound selected from the group consisting of halogenated paraffins, halogenated aralkyl phosphates, halogenated aryl phosphates, halogenated diphenyl ethers, halogenated phenols, halogenated alkyl ethers of the halogenated phenols, tetrabromobisphenol-A and etherified derivatives of tetrabromobisphenol-A represented by the formula Br CH, Br J
  • halogenated aliphatic phosphate is selected from the group consisting of tris(B-chloroethyl)phosphate, tris(B-bromoethyl)phosphate, tris(3- chloropropyl )phosphate, tris( 3- bromopropyl)phosphate, tris(2,3-dichloropropyl) phosphate, tris(2,3-dibromopropyl)phosphate, tris( 1- bromo-3-chloroisopropyl)phosphate, tris(2,3- dichlorobutyl) phosphate, tris(2,3- dibromobutyl)phosphate, bis(2,3-dichloropropyl)2,3- dibromopropyl phosphate and bis(2,3-dibromopropyl)2,3-dichloropropyl phosphate.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US00285664A 1971-09-04 1972-09-01 Flame-retardant acrylic synthetic fibers having improved properties Expired - Lifetime US3846373A (en)

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JP46068218A JPS5130607B2 (enrdf_load_stackoverflow) 1971-09-04 1971-09-04

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JP (1) JPS5130607B2 (enrdf_load_stackoverflow)
CA (1) CA951446A (enrdf_load_stackoverflow)
ES (1) ES406332A1 (enrdf_load_stackoverflow)
GB (1) GB1374907A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4083826A (en) * 1976-05-05 1978-04-11 Velsicol Chemical Corporation Polymeric compositions containing a flame retardant amount of a bis(2,3-dibromopropyl)-chloroalkyl phosphate
US5134182A (en) * 1989-08-29 1992-07-28 Thomas & Betts Corporation Hydrocarbon resistant sealant composition
US5301842A (en) * 1991-03-06 1994-04-12 Frank Ritter Multicomponent cartridge for plastic materials

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5315634A (en) * 1976-07-28 1978-02-13 Murata Manufacturing Co Ignition device for pilot burner
JPS5549685U (enrdf_load_stackoverflow) * 1978-09-30 1980-04-01
JPS6266513U (enrdf_load_stackoverflow) * 1985-10-18 1987-04-24
JPS63145416A (ja) * 1986-11-29 1988-06-17 Asahi Chem Ind Co Ltd パラ配向型アラミド繊維

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149089A (en) * 1959-08-27 1964-09-15 Du Pont Preparation of acrylonitrile fibers
US3645964A (en) * 1969-07-16 1972-02-29 Michigan Chem Corp Fire retardant acrylonitrile polymer compositions
US3658634A (en) * 1970-08-20 1972-04-25 Toray Industries Fire-retardant sheath and core type conjugate fiber

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149089A (en) * 1959-08-27 1964-09-15 Du Pont Preparation of acrylonitrile fibers
US3645964A (en) * 1969-07-16 1972-02-29 Michigan Chem Corp Fire retardant acrylonitrile polymer compositions
US3658634A (en) * 1970-08-20 1972-04-25 Toray Industries Fire-retardant sheath and core type conjugate fiber

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4083826A (en) * 1976-05-05 1978-04-11 Velsicol Chemical Corporation Polymeric compositions containing a flame retardant amount of a bis(2,3-dibromopropyl)-chloroalkyl phosphate
US5134182A (en) * 1989-08-29 1992-07-28 Thomas & Betts Corporation Hydrocarbon resistant sealant composition
US5301842A (en) * 1991-03-06 1994-04-12 Frank Ritter Multicomponent cartridge for plastic materials

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GB1374907A (en) 1974-11-20
JPS4844526A (enrdf_load_stackoverflow) 1973-06-26
JPS5130607B2 (enrdf_load_stackoverflow) 1976-09-02
ES406332A1 (es) 1976-01-16
CA951446A (en) 1974-07-16

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