US3877952A - Flame-proofing agents, especially for use with cellulosic materials - Google Patents

Flame-proofing agents, especially for use with cellulosic materials Download PDF

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Publication number
US3877952A
US3877952A US341187A US34118773A US3877952A US 3877952 A US3877952 A US 3877952A US 341187 A US341187 A US 341187A US 34118773 A US34118773 A US 34118773A US 3877952 A US3877952 A US 3877952A
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US
United States
Prior art keywords
compound
amide
dibromopropyl
phosphoric acid
shaped article
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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
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US341187A
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English (en)
Inventor
Kurt Dahmen
Alois Kunschner
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Stockhausen GmbH and Co KG
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Chemische Fabrik Stockhausen GmbH
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Priority claimed from DE19722213274 external-priority patent/DE2213274C3/de
Application filed by Chemische Fabrik Stockhausen GmbH filed Critical Chemische Fabrik Stockhausen GmbH
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Publication of US3877952A publication Critical patent/US3877952A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B16/00—Regeneration of cellulose
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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

Definitions

  • the agents are of the formula wherein, R and R which may be the same or different, each represents an alkyl, alkoxyalkyl or haloalkyl radical,
  • R represents a monoor multi-halogenated alkyl radical, and R represents a monoor multi-halogenated alkyl radical, which may be the same as or different from that represented by R or an alkyl or alkenyl group.
  • Some flame-retarding agents e.g. l-aziridinyH- phosphinous oxide and tetrakis-(hydroymethyl)- phosphonium chloride. give reasonably permanent flame-proofing but are toxic and very difficult to handle. necessitating precautionary steps.
  • the acid catalysts frequently used with these agents may damage the cellulose (see M.W. Ranney. Flame Retardant Textiles. 1970. Noyes Data Corporation, Park Ridge. New Jersey. U.S.A., page 133 onwards and 17] onwards).
  • the flame-proofing agents proposed are either relatively inaccessible. such as alkoxy phospazcnes (German Offenlegungsschriften 1,906.38]. 1.904.427; French Pat. No. 2.()l2.440'. US. Pat. Nos. 3.455.713 and 3.532.526 and British Pat. No. l.l53.955 or else. if they are accessible. lead to discolouration of the regenerated articles. such as red phosphorus (German Offenlegungsschrift l.944.056) and haloalkyl phosphates. e.g. tris-(2.3-dibromopropyl)-phosphate (US Pat. No. 3.266.918 and Dutch Application 69.14207).
  • the present invention is based on our surprising discovery of a new class of compounds which can be incorporated into cellulose articles to give excellent flame-proofing whilst substantially avoiding the disadvantages of the hitherto proposed agents.
  • R and R which may be the same or different. each represents an alkyl. alkoxyalkyl or haloalkyl radical. preferably containing up to 6 carbon atoms.
  • R represents a monoor multihalosubstituted alkyl radical. preferably CH CHBrCH Br, and R represents a monoor multi-halosubstituted alkyl radical (which may be the same as or different from that represented by R.-;) or an alkyl or alkenyl radical.
  • Suitable alkyl radicals may be straight-chained or branched. Radicals having from 2 to 6 carbon atoms are preferred and amongst suitable radicals there may be mentioned ethyl. n-propyl. n-butyl. n-pentyl and nhexyl (straight-chained) and isopropyl, isobutyl and isopentyl (branched).
  • Suitable alkoxyalkyl radicals are, for example. methoxy alkyl. ethoxyalkyl. propoxyalkyl and butoxyalkyl radicals.
  • the halogen atom in the haloalkyl radicals may be fluorine. chlorine. bromine or iodine.
  • the compounds of the present invention may be prepared by methods known per se. for example by (a) condensing dialkyl halogen phosphates or alkyl dihalogen phosphates with diallyl amine, alkyl-allyl amine or N monoallyl amine in the presence of acidbinding bases such as tertiary amines. sodium carbonate or sodium hydroxide or (b) condensing dialkyl phosphite with diallyl amine. alkylallyl amine or monoallyl amine according to the Todt reaction (J. Org. Chem. l p 637 1950; J. Chem. Soc. 1945 p 660; J. Chem. Soc. 1947 p 674) to form dialkyl phosphoric acid ester-N- diallylamide or dialkyl-phosphoric acid ester-N-alkyl- N-allylamide. or alkyl phosphoric acid ester-N.N'-
  • alkyl halogen phosphates or dialkyl phosphites instead of alkyl halogen phosphates or dialkyl phosphites one can use the alkoxyalkyl or haloalkyl ana- 40 logues.
  • the present invention also provides a method of producing a flame-proofed article wherein at some stage before manufacture of the final article there is incorporated into the basic material at least one compound of the formula (I) and/or (ll).
  • the present invention further provides a flameproofed article madefrom a basic material in which there is incorporated at least one compound of the formula (I) and/or (ll).
  • the compounds of the formula (I) and (II) are effective flame-proofing agents which may advantageously be used in many types of basic material. e.g. polymers. but they are especially applicable to cellulosic materials and. in particular. regenerated cellulose which is used to form rayon. artificial wool fibres and films well other shaped articles.
  • the compound(s) of the formula (l) and/or (ll) are preferably incorporated in an amount of from I to 40 60 percent. especially from 10 to 30 percent. by weight of the cellulosic material. e.g. regenerated cellulose.
  • the cellulosic material e.g. regenerated cellulose.
  • the flame-proofing agents of the formula (I) or (II) can. if required. be brought into solution in a suitable solvent to produce a pumpable consistency and for this purpose surfactants or other dispersing agents may be used to assist introduction into the cellulose solution which can be effected by stirring it into the solution or by adding it into the solution just before it leaves the nozzle during regeneration.
  • surfactants or other dispersing agents may be used to assist introduction into the cellulose solution which can be effected by stirring it into the solution or by adding it into the solution just before it leaves the nozzle during regeneration.
  • Other substances. such as modifiers and pigmenting agents. commonly used in cellulose fibre production can. if desired. be simultaneously incorporated.
  • viscoses of the composition 6.75 percent cellulose. 5.8 percent soda lye. 2.2 percent sulphur were produced. The ripeness for spinning of these viscoses corresponded to gamma values of 45. After the incorporation of the amounts. quoted in the separate Examples. ofa flame-proofing agent according to the invention. if necessary diluted with an inert solvent and a surfactant. the viscoses were spun from spinning nozzles (numbering 1000. each 60 pm in diameter) into spinning baths which contained 60 g sulphuric acid. 133 g sodium sulphate and 90 g zinc sulphate per litre.
  • the spinning bath temperature was 42C and the immersion distance of the bundle of fibres in the spinning bath 80 cm.
  • the bundle of fibres was stretched by 80 percent in a stretching bath at 98C containing g sulphuric acid per litre and then washed and further processed in the usual manner. After drying. the fibres were processed into a yarn. the twisting of which was limited to a protective spin of 100 turns per metre.
  • the over-all titre of the yarn was 1650 den in the blank test and increased. depending on the type and quantity of the flame-proofing agents incorporated. up to 1850 den.
  • EXAMPLE 2 Into the viscose were introduced. in relation to its' cellulose content, 3.26 percent of the ethoxylated coconut oil amine. 3.9 percent perchlorethylene as liquefacient. and 30 percent phosphoric acid dimethoxyethyl ester-N-bis-(2,3-dibromopropyl)-amide.
  • EXAMPLE 3 Similar to Example 2. but using 20 percent of the above-mentioned flame-proofing agent of the present invention in the presence of 3.26 percent ethoxylated coconut oil amine. and 2.6 percent perchlorethylene.
  • EXAMPLE 4 Similar to Example 2. but using 3.26 percent ethoxylated coconut oil amine. L95 percent perchlorethylene and 15 percent of the above-mentioned flame-proofing agent.
  • EXAMPLE 5 To the viscose were added. in relation to its cellulose content. 3.26 percent ethoxylated coconut oil amine and 30 percent phosphoric acid di-n-propylester-N- bis(2.3-dibromopropyl)-amide.
  • EXAMPLE 7 Similar to Example 5. but using 3.26 percent of the ethoxylated aliphatic amine and percent of a mixed phosphoric acid ethyl ester-N.N diallylbis-(2.3-dibromopropyl)-amide.
  • EXAMPLE 8 Similar to Example 7. but using phosphoric acid ethylester-N.N '-allyl-tris-( 2.3-dibromopropyl )-amide as flame-proofing agent.
  • EXAMPLE 1 1 Similar to Example 5. but using phosphoric acid-di-nhexyl-ester-N-bis-(2.3-dibromopropyl)-amide as flame-proofing agent.
  • EXAMPLE 13 Similar to Example 5. but using phosphoric aciddichlorocthylester-N-bis-( 2.3-dibromopropyl )-amide as flame-proofing agent.
  • EXAMPLE 14 Similar to Example 5. but using phosphoric acidethyl-isopropylester-N-bis( 2.3-dibromopropyl )-amide as flame-proofing agent.
  • EXAMPLE 15 Similar to Example 5. but using phosphoric aciddiethylester( N-methyl-N-2.3-dibromopropyl )-amide as flame-proofing agent.
  • EXAMPLE 17 Similar to Example 5. but using phosphoric acid-diisopropylester-N-bis-( 2.3-dibromopropyl )-amide as flame-proofing agent.
  • EXAMPLE 18 (Comparison) The viscose was mixed with, in relation to its cellulose content, 3.26 percent of ethoxylated coconut oil amine and 30 percent of tris-(2.3-dibromopropyl)- phosphate, a known commercial agent.
  • One of the main advantages of the flame-proofing agents of the present invention is that good flameretarding properties can be obtained with smaller amounts of agent than has hitherto been the case. This means that, for yarns. the reduction in strength in relation to titre caused by the 'present of the agent can be kept significantly lower.
  • Example Fire-proofing agent Appearance Combustion behaviour Type quantity used of the foil of the foil after /1 removing the igniting flame 23 colourless. almost non flammable clear. transparent 24
  • H that represented by R;,, or an alkyl or alkenyl l. A compound of the formula group.
  • R represents a monoor multi-halogenated alkyl alkyl and alkenyl each contain up to 6 carbon radical. and atoms.
  • R represents a monoor multi-halogcnated alkyl and forming the material having said compound inradical. which may be the same as or different from corporated therein into a shaped article.
  • each of R R R and R contains up to 6 carbon atoms.
  • R represents CH- ,CHBrCH- ,Br.
  • a method of improving the flame-resistance of a shaped article which comprises incorporating into the basic material of the article a compound of the ii R3 1 1) P n or (II) material of the article is a cellulosic material.
  • a shaped article as claimed in claim 16 which is a fibre or a film.
  • a shaped article made from a basic material into which there has been incorporated to increase flame resistance a compound of the formula wherein.
  • R and R which may be the same or different. each represents an alkyl. alkoxyalkyl or haloalkyl radical.
  • R represents a monoor multi-halogenated alkyl radical.
  • R represents a monoor multi-halogenated alkyl radical, which may be the same as or different from that represented by R or an alkyl or alkenyl group.
  • alkyl, alkyl residue of the alkoxy group and the haloalkyl each contain up to 6 carbon atoms. and for R and R the haloalkyl. alkyl and alkenyl each contain up to 6 carbon atoms.
  • a shaped article as claimed in claim 18 which is in the form of a fibre or film.
  • each of R R R and R contains up to 6 carbon atoms.
  • each of R R R and R contains up to 6 carbon atoms.
  • each of R,, R R and R. contains 2-6 carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Fireproofing Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US341187A 1972-03-18 1973-03-14 Flame-proofing agents, especially for use with cellulosic materials Expired - Lifetime US3877952A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19722213274 DE2213274C3 (de) 1972-03-18 Nicht entflammbare Formkörper aus Regeneratcellulose und Verfahren zu ihrer Herstellung

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US3877952A true US3877952A (en) 1975-04-15

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JP (1) JPS496028A (enrdf_load_html_response)
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GB (1) GB1429531A (enrdf_load_html_response)
IN (1) IN138702B (enrdf_load_html_response)
IT (1) IT981449B (enrdf_load_html_response)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059532A (en) * 1974-12-09 1977-11-22 Ciba-Geigy Corporation Phosphorus-containing reaction products useful as flameproofing agents
US4124400A (en) * 1975-07-28 1978-11-07 Monsanto Company Flame retardant polymer compositions
US4167603A (en) * 1976-12-13 1979-09-11 Ethyl Corporation Flame resistant cotton/polyester blend substrates
US6107242A (en) * 1996-08-22 2000-08-22 Coir Peat Aust Pty Ltd Absorbent material including coir fibres and/or coir dust
KR20030023264A (ko) * 2001-09-13 2003-03-19 제일모직주식회사 난연성 고무강화 폴리스티렌 수지 조성물

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5847702B2 (ja) * 1974-07-01 1983-10-24 富士写真フイルム株式会社 カラ−シヤシンカンコウザイリヨウ
US6617379B2 (en) 2001-12-04 2003-09-09 Albemarle Corporation Flame retardant polymer compositions
CN116200950B (zh) * 2023-03-29 2023-10-31 无锡琳华新材料科技有限公司 一种阻燃汽车内饰材料及其生产工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3244586A (en) * 1962-04-30 1966-04-05 Dow Chemical Co Omicron-pyridyl phosphates and phosphorothioates
US3387980A (en) * 1965-04-07 1968-06-11 Raybestos Manhattan Inc Heat resistant inorganic bodies
US3584085A (en) * 1967-07-18 1971-06-08 Atlas Chem Ind Phosphoramidates
US3767736A (en) * 1970-10-13 1973-10-23 Du Pont Dialkyl n substituted phosphoramidate containing flame retardants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3244586A (en) * 1962-04-30 1966-04-05 Dow Chemical Co Omicron-pyridyl phosphates and phosphorothioates
US3387980A (en) * 1965-04-07 1968-06-11 Raybestos Manhattan Inc Heat resistant inorganic bodies
US3584085A (en) * 1967-07-18 1971-06-08 Atlas Chem Ind Phosphoramidates
US3767736A (en) * 1970-10-13 1973-10-23 Du Pont Dialkyl n substituted phosphoramidate containing flame retardants

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059532A (en) * 1974-12-09 1977-11-22 Ciba-Geigy Corporation Phosphorus-containing reaction products useful as flameproofing agents
US4124400A (en) * 1975-07-28 1978-11-07 Monsanto Company Flame retardant polymer compositions
US4134877A (en) * 1975-07-28 1979-01-16 Monsanto Company Flame retardant phosphoramidate compositions
US4167603A (en) * 1976-12-13 1979-09-11 Ethyl Corporation Flame resistant cotton/polyester blend substrates
US6107242A (en) * 1996-08-22 2000-08-22 Coir Peat Aust Pty Ltd Absorbent material including coir fibres and/or coir dust
KR20030023264A (ko) * 2001-09-13 2003-03-19 제일모직주식회사 난연성 고무강화 폴리스티렌 수지 조성물

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DE2213274A1 (de) 1973-09-27
IN138702B (enrdf_load_html_response) 1976-03-20
GB1429531A (en) 1976-03-24
ES412763A1 (es) 1976-05-16
ATA236073A (de) 1976-05-15
AT334317B (de) 1976-01-10
JPS496028A (enrdf_load_html_response) 1974-01-19
SE400301B (sv) 1978-03-20
DE2213274B2 (de) 1975-03-20
IT981449B (it) 1974-10-10

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