US3709940A - Phosphorus compounds for flameproofing fabrics - Google Patents

Phosphorus compounds for flameproofing fabrics Download PDF

Info

Publication number
US3709940A
US3709940A US00120740A US3709940DA US3709940A US 3709940 A US3709940 A US 3709940A US 00120740 A US00120740 A US 00120740A US 3709940D A US3709940D A US 3709940DA US 3709940 A US3709940 A US 3709940A
Authority
US
United States
Prior art keywords
treated
phosphorus compounds
web
organic phosphorus
textiles
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
US00120740A
Other languages
English (en)
Inventor
W Flugel
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.)
Quehl & Co dt GmbH
Quehl & Co GmbH
Original Assignee
Quehl & Co GmbH
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
Priority claimed from DE19702010531 external-priority patent/DE2010531A1/de
Priority claimed from DE19702055289 external-priority patent/DE2055289A1/de
Application filed by Quehl & Co GmbH filed Critical Quehl & Co GmbH
Application granted granted Critical
Publication of US3709940A publication Critical patent/US3709940A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5304—Acyclic saturated phosphine oxides or thioxides

Definitions

  • Polymerisable compounds such as acrylamide can also be used, which are reactable with the methylol groups of the tetrahydroxymethylphosphoniurn salt or trishydroxymethylphosphine oxide.
  • the treated textiles can be subjected to the efiect of heat, especially in the region of about 40 to 170 C. By the additional treatments a water or solvent resistance can be obtained.
  • the object of the invention is the provision of a material for improving textiles, especially for making them flameproof, which in use gives the textiles not only a high flame resistance but also a particular permanency of the effect of the treatment, wherein the textile properties 3,709,940 Patented Jan. 9, 1973 P CC of the treated goods are retained and their technological properties are practically not adversely influenced.
  • the organic phosphorus compounds according to the invention have the general formula in which R is hydrogen or an alkyl residue of l-3 carbon atoms and X is halogen, particularly chlorine, or OH.
  • organic phosphorus compounds according to the invention are substantially wetted with respect to the fibrous materials; this can suitably take place by condensation at tempera tures in the range of 120-180 0., especially 140-160 C., and suitably also in the presence of a reaction accelerator such as o-phosphoric acid, ammonium salts or the like.
  • a reaction accelerator such as o-phosphoric acid, ammonium salts or the like.
  • the length of time for the heating depends on various factors, inter alia on the type of fibrous material to "be treated, the temperature used, and the construction of the condensation plant or apparatus used. Generally good results are achieved with condensation times in the region of 1-10 minutes. In some cases it can be necessary to extend this time somewhat.
  • the flameproofed textiles are treated after condensation with an oxidative agent or an oxidising rinsing treatment, in order to remove insufficiently fixed organic phosphorus compound and to make the treated goods wholly non-odorous.
  • the invention includes also a process for the manufacture of organic phosphorus compounds of the general formula in which R is hydrogen or alkyl of 1-3 carbon atoms and X is halogen, particularly chlorine, which is characterised in that 2 mol. tetrahydroxymethylphosphonium salt are recated with 1 mol N-methylolacrylamide at a pH 'value of 4-8, particularly 6-7, and at temperatures of -140" C., particularly -130 C., preferably under reduced pressure, e.g. in the range of 10-50 torr.
  • the resulting product can be extracted from the reaction mixture without isolation with a l-3 carbon atom alcohol at room temperature or slightly elevated temperature up to 50 C. in acid conditions (pH value of 1-5).
  • the invention further includes a process for the manufacture of organic phosphorus compounds of the general formula in which R is hydrogen or alkyl of 1-3 carbon atoms and X is OH, in which tetrahydroxymethylphosphoniumhalidc, particularly tetrahydroxymethylphosphoniumchloride (THPC) is reacted under such conditions that the entire amount of halide ions, particularly chloride ions, are removed from the reaction mixture and replaced by hydroxyl ions.
  • THPC tetrahydroxymethylphosphoniumhalidc
  • chloride ions particularly chloride ions
  • a useful embodiment of the process according to the invention is characterised in that 1 mol tetrahydroxymethylphosphonium salt, particularly 1 mol THPC, is neutralized in aqueous alcoholic solution with sodium carbonate at 20-40 C., the sodium halide, particularly NaCl, separated otf, the alcohol containing filtrate is reduced under vacuum and the viscous solution is reacted with stirring and intense cooling with half 21 mol of N-methylolacrylamide added in portions, the reaction being carried out under reduced pressure, particularly from 10-50 torr and then heated to about 100 C.
  • tetrahydroxymethylphosphoniurnchloride or bromide are particularly suitable.
  • EXAMPLE 1 240 grams of an 80% aqueous solution of THPC (1 mol) and 50.5 grams N-methylolacrylamide (0.5 mol) were stirred together and treated with about 10 grams Na C in portions of l-2 grams, until a pH value of 6-7 was obtained. This mixture was then dewatered under reduced pressure (20 torr) and slowly increasing temperature and brought to reaction. In this way the temperature of' the reaction mix is brought to 125 C. and is held at this temperature for about 2 hours. After removal of the by-products formed (essentially NaCl) a water soluble condensation product which at this temperature was viscous, of the following constitution resulted.
  • This reaction product was diluted with water to a concentration of about 80% in order to give the necessary handleability in practice.
  • the web After squeezing out to 80% liquid take-up, the web was dried and condensed at about 140 C. Finally it was subjected at about 60 C. to a weakly alkaline peroxide or percarbonate containing wash, rinsed out and dried.
  • the so treated web was flameproof according to DIN 53906 and according to the so-called match test (British Standard 2963, method A).
  • the flameproof efiect according to DIN 53906 still remained also after 30 machine washes at 60 C.
  • the textile properties of the fiameproofed material were exceptional, the feel of the goods being practically nonchanged compared to the non-treated goods.
  • the technological properties were good; the wash and wear proper'ties were substantially improved.
  • the fabric After squeezing out to liquid take-up the fabric was dried and condensed at about 160 C. Thereafter it was treated at about 60 C. with a weakly alkaline peroxile gr percarbonate containing after-wash, n'nshed and A web resulted with a take-up of treatment agent of about 25-30%.
  • the so-treated web was fiameprooi (according to DIN 53906 and match test).
  • the flameproof efi'ect still remained even after 13 machine washes at 90 C.
  • EXAMPLE 5 240 grams of an 80% aqueous solution of THPC (1 mol) were evaporated under vacuum to about and diluted with about 100 ml. methanol, and the methanolic solution was neutralized with stirring with about 50g. sodium carbonate at 2240 C. The NaCl arising was separated. The methanol containing filtrate was. reduced under vacuum at temperatures of 2050 C. and under reduced pressure (1050 torr). The viscous solution was then reacted with 50.5 g. (half mol) N-m'ethylol-acrylamide, the N-methylolacrylamide being introduced in portions (25 g.) with striring and intensive cooling at 20- 50 C. Thereafter vacuum was applied, and the temperature rose within 2 /2 hours to 100 C. A viscous end product resulted (about 182 grams) which was diluted with about 80 grams water to a 70% solution for better handleability.
  • the web After squeezing to about 80% liquid take-up, the web was dried and condensed at about 140 C. Then it was treated at about 30 C. with a weakly alkaline, peroxide or percarbonate containing afterwash, rinsed and dried.
  • the so-treated web was flameproof according to DIN 53906 and according to the so-called match test (British Standard 2963, method A).
  • the fiameproof effect according to DIN 53906 still remained after 30 machine washes at 60 C.
  • the textile properties of the flameproofed web were very good, and the feel of the goods compared to nontreated goods was practically unchanged.
  • the technological properties were good; wash and wear was substantially improved.
  • EXAMPLE 7 A web (160-g./m. of pure cotton was treated on the foulard with the following bath:
  • the web After squeezing out the 90% liquid take-up the web was dried and condensed at about 160 C. Thereafter it was treated at about 60 C. with a weakly alkaline, per- 6 oxide" or percarbonate'containingafterwash, rinsed and dried. A web loaded with 25-30% treatment agent resulted.
  • the so-treated web was flameproof (according to' DIN 53906 and the match test). The flameproof effect still remained after 30 machine washes at C.
  • the technological properties of the treated web were good; wash and wear properties were substantially improved.
  • the loss in tear strength was surprisingly small; it amounted to only 0-20%.
  • HOCHr-P-CHaOH in which R is selected from the class consisting of hydrogen and alkyl of 1 to 3 carbon atoms, and X is hydroxy, wherein 1 mole tetrahydroxymethyl phosphonium salt is neutralised in aqueous alcoholic solution at 20-40 C. with sodium carbonate, the sodium halide formed is removed,theelcohol-containingfiltrate is reduced under No references cited.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US00120740A 1970-03-05 1971-03-03 Phosphorus compounds for flameproofing fabrics Expired - Lifetime US3709940A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19702010531 DE2010531A1 (en) 1970-03-05 1970-03-05 Organo phosphorus textile flame proofers
DE19702055289 DE2055289A1 (en) 1970-11-10 1970-11-10 Organophosphonium salts prepn - used for fireproofing textiles

Publications (1)

Publication Number Publication Date
US3709940A true US3709940A (en) 1973-01-09

Family

ID=25758772

Family Applications (1)

Application Number Title Priority Date Filing Date
US00120740A Expired - Lifetime US3709940A (en) 1970-03-05 1971-03-03 Phosphorus compounds for flameproofing fabrics

Country Status (3)

Country Link
US (1) US3709940A (enExample)
FR (1) FR2084257A5 (enExample)
GB (1) GB1346937A (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3958932A (en) * 1974-08-28 1976-05-25 The United States Of America As Represented By The Secretary Of Agriculture Flame-resistant textiles through finishing treatments with vinyl monomer systems
US3980614A (en) * 1975-03-14 1976-09-14 Hoechst Aktiengesellschaft Flame retarding plastic materials
US3980615A (en) * 1974-10-07 1976-09-14 Hoechst Aktiengesellschaft Flame retarding plastic materials

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3958932A (en) * 1974-08-28 1976-05-25 The United States Of America As Represented By The Secretary Of Agriculture Flame-resistant textiles through finishing treatments with vinyl monomer systems
US3980615A (en) * 1974-10-07 1976-09-14 Hoechst Aktiengesellschaft Flame retarding plastic materials
US3980614A (en) * 1975-03-14 1976-09-14 Hoechst Aktiengesellschaft Flame retarding plastic materials

Also Published As

Publication number Publication date
FR2084257A5 (enExample) 1971-12-17
GB1346937A (en) 1974-02-13

Similar Documents

Publication Publication Date Title
US4975209A (en) Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids
US4820307A (en) Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids
US4936865A (en) Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids
US3969437A (en) Cyclic phosphorus esters
US3746572A (en) Process for flame retarding fabrics
Tesoro et al. Nitrogen-Phosphorus Synergism in Flame-Retard Ant Cellulose
US3698854A (en) Process for producing flame resistant organic textiles
CA1147077A (en) Flameproofing agents
JP4495457B2 (ja) セルロース繊維を防炎加工する方法
US5352242A (en) Formaldehyde-free easy care finishing of cellulose-containing textile material
US4136037A (en) Phosphoramide-hydroxymethyl phosphine condensation products for textile fire retardation
US2828228A (en) Textile fire retardant treatment
US4092108A (en) Compositions and process for imparting durable flame resistance to cellulosic textiles
US3528964A (en) Process for the chemical modification of cellulosic polymers and products produced thereby
Tesoro et al. Chemical modification of cotton with derivatives of divinyl sulfone
KR790001788B1 (ko) 직물의 방염 처리법
US3278561A (en) Hydrophobic diglycidylamines
US3888779A (en) Flame retardant composition containing tetrakis (hydroxymethyl) phosphonium oxalate
US3765837A (en) Flame retardant finish for polyester/cotton blends
US2906592A (en) Flame- and crease-resistant textiles from aziridine carboxyalkylcellulose
US3908051A (en) Method for processing cellulose containing materials to impart thereto flame resistance
US2294435A (en) Process for rendering textiles water-repellent
US3690941A (en) Process for providing cellulose fibre material with a flame-proof finish fast to washing
Drake Jr et al. Phosphonomethylation of cotton
US3503793A (en) Cellulosic fibrous materials