US3452098A - Hydroxymethyl,beta-hydroxyalkylene phosphonium salts and the preparation thereof - Google Patents
Hydroxymethyl,beta-hydroxyalkylene phosphonium salts and the preparation thereof Download PDFInfo
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- US3452098A US3452098A US543081A US3452098DA US3452098A US 3452098 A US3452098 A US 3452098A US 543081 A US543081 A US 543081A US 3452098D A US3452098D A US 3452098DA US 3452098 A US3452098 A US 3452098A
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- United States
- Prior art keywords
- phosphonium
- reaction
- hydroxymethyl
- present
- acid
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Links
- 150000004714 phosphonium salts Chemical class 0.000 title description 9
- 238000002360 preparation method Methods 0.000 title description 4
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 title 1
- 239000000463 material Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 32
- -1 hydroxyalkyl phosphonium compounds Chemical class 0.000 description 32
- 239000004753 textile Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical group C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 230000037303 wrinkles Effects 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- RRPCXWQXVDBGBM-UHFFFAOYSA-M tris(2-hydroxyethyl)-(hydroxymethyl)phosphanium;chloride Chemical compound [Cl-].OCC[P+](CO)(CCO)CCO RRPCXWQXVDBGBM-UHFFFAOYSA-M 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- BDTXEXYHHSMQHB-UHFFFAOYSA-M tetrakis(2-hydroxyethyl)phosphanium;chloride Chemical compound [Cl-].OCC[P+](CCO)(CCO)CCO BDTXEXYHHSMQHB-UHFFFAOYSA-M 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- RDBMUARQWLPMNW-UHFFFAOYSA-N phosphanylmethanol Chemical class OCP RDBMUARQWLPMNW-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JMXMXKRNIYCNRV-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol Chemical compound OCP(CO)CO JMXMXKRNIYCNRV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical class O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229960002816 potassium chloride Drugs 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- MMTPNKFEGPOIRH-UHFFFAOYSA-M tetrakis(4-hydroxybutyl)phosphanium;bromide Chemical compound [Br-].OCCCC[P+](CCCCO)(CCCCO)CCCCO MMTPNKFEGPOIRH-UHFFFAOYSA-M 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
-
- 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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
Definitions
- the hydroxymethyl phosphonium salts are used for treating cellulosic textile materials to render them crease and flame resistant.
- This invention relates to novel hydroxyalkyl phosphonium compounds and more particularly it relates to novel hydroxyalkyl phosphonium halide compounds, their method of preparation and their use for treating cellulosic textile materials to render them crease and flame resistant.
- a further object of the present invention is to provide a novel method for preparing hydroxyalkyl phosphonium compounds, which method does not utilize reactants which are diflicult to handle.
- Another object of the present invention is to provide a method for treating cellulosic textile materials so as to impart flame and crease resistance to these materials.
- the present invention includes a hydroxyalkyl phosphonium halide having the formula OH 4-n P+z- R-CH-CH: a,
- n is a number from 2 to 3 and Z is the anion of a salt forming acid
- R is a lower alkyl group containing 1 to 3 carbon atoms and R is selected from the group consisting of hydrogen and lower alkyl groups containing 1 to 3 carbon atoms.
- the hydroxyalkyl phosphonium salts of the present invention are those compounds containing at least two Z-hydroxyalkyl groups, and desirably three Z-hydroxyalkyl groups.
- Exemplary of specific compounds falling within this class are di(2-hydroxyethyl)di(hydroxymethyl) phosphonium chloride; tris(2-hydroxyethyl)hydroxymethyl phosphonium chloride: tris(2-hydroxybutyl)hydroxymethyl phosphonium chloride; tris (2-hydroxypr0pyl)hydr0xymethyl phosphonium chloride; di (2 hydroxyethyl) di(hydroxyethyl)phosphonium chloride; tris(2 hydroxyethyl)hydroxybutyl phosphonium chloride and the like.
- the acid anion may be that of any suitable acid which will form a salt with the compound, such as chloride, bromide, iodide, fluoride, acetate, sulfate, and the like.
- suitable acid such as chloride, bromide, iodide, fluoride, acetate, sulfate, and the like.
- the preferred anion is the chloride and specific reference hereinafter will be made to this material,
- the hydroxyalkyl phosphonium salts of the present invention are prepared by reacting a neutralized tetrakis (hydroxyalkyl)phosphonium halide with an alkylene oxide.
- the tetrakis(hydroxyalkyl)phosphonium halide used in this reaction has the formula wherein R is selected from the group consisting of hydrogen and lower alkyl groups having from 1 to 3 carbon atoms and wherein X is halogen.
- the phosphonium halide is tetrakis(hydroxymethyl)phosphonium chloride although other phosphonium halides such as tetrakis(hydroxyethyl)phosphonium chloride; tetrakis (hydroxybutyl)phosphonium bromide; tetrakis(hydroxypropyl)phosph0nium chloride; and the like, may also be used.
- the preferred tetrakis(hydroxymethyl)phosphonium chloride is commercially available, typically as an aqueous solution, Moreover, it can be safely and conveniently handled, in air, either as a crystalline solid, having a melting point of about centigrade, or as an aqueous or non-aqueous solution. For these reasons, this is the preferred phosphonium halide compound for use in the present invention.
- the alkylene oxide used in forming the novel phosphonium compounds of the present invention has the formula:
- R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 2 carbon atoms.
- R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 2 carbon atoms.
- alkylene oxides which may be used, the preferred one has been found to be ethylene oxide although, in many instances, satisfactory results have been obtained when using propylene and butylene oxide as well.
- the preferred tetrakis(hydroxymethyl)phosphonium chloride is reacted With an excess of the preferred ethylene oxide in the presence of a base, whereby neutralization of the phosphonium chloride material is effected, in situ, in the reaction.
- the ethylene oxide should be present in an amount of at least 2 moles of ethylene oxide per mole of the tetrakis (hydroxymethyl)phosphonium chloride and is preferably present in an amount of at least 3 or more moles of ethylene oxide per mole of the phosphonium chloride.
- the base may first be reacted with the phosphonium chloride and thereafter the resulting neutralized material is reacted with the ethylene oxide.
- various acids may be used for this purpose to form the salts, including hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, acetic acid, and the like.
- the preferred acid has been found to be hydrochloric acid and for this reason, specific reference hereinafter will be made to this material. Accordingly, when using hydrochloric acid, thep referred product by the method of the present invention will be tri(2- hydroxyethyl)hydroxymethyl phosphonium chloride.
- the bases which may be employed in the reaction of the present invention are the various alkali metal hydroxides, oxides, carbonates, bicarbonates, as well as tertiary amines, quaternary ammonium hydroxide, and, in general, any strong base which is capable of forming hydroxide ions in aqueous solution.
- the base functions as a reactant, rather than as a catalyst and is consumed in the reaction in an amount which is proportional to the quantity of the phosphonium halide material which is employed. Accordingly, in many instances, it is preferred to employ the base in an amount which is about equivalent, on a molar basis, to the amount of the tetrakis(hydroxy methyl) phosphonium chloride which is used.
- the reaction of the present invention may conveniently be accomplished in either aqueous or non-aqueous media.
- exemplary of the mediums which may be used are water; non-aqueous liquids such as methyl alcohol, ethyl, alcohol, propyl alcohol, dimethyl formamide, acctonitrile; and mixtures of water and a non-aqueous liquid. In most instances, however, it is preferred to employ an aqueous medium.
- the reaction time Will vary from less than a minute to more than an hour, depending upon the temperatures, proportion of reactions and the like.
- the reaction temperatures will be maintained at not substantially in excess of about 50 centigrade, so as to avoid too vigorous a reaction with the consequent possibility of volatilizing the reaction constituents and undesired side reactions.
- the reaction is carried out by first neutralizing the terakis(hydroxymethyl)phosphonium chloride with the base, and thereafter, adding to the neutralized phosphonium chloride the ethylene oxide, in the amounts which have been indicated hereinabove.
- the reaction temperature may normally be maintained below the desired 50 centigrade, and by continuous addition of mineral acid, the pH may be kept within the preferred range of 8-9. Inasmuch as the reaction is exothermic, in some instances, it may be desirable to provide external cooling for the reaction.
- the hydroxylal-kyl phosphonium salts formed by the present reaction are separated from volatile components by a vacuum stripping and from the salt byproduct by extraction with alcohol or similar solvent. Distillation of the extracting solvent then affords the phosphonium salt as the product. Additionally, it has been found that in some instances, it may be desirable to carry out the reaction under pressure.
- the hydroxyalkyl phosphonium salts of the present invention may be used in the treatment of cellulosic textile materials so as to impart crease or wrinkle resistance as well as flame resistance to the treated materials.
- the present phosponium salts may be applied to the textile materials in any suitable formulation, as for example, an emulsion, a dispersion or a solution. These may be applied by dipping, spraying, rolling, or by the use of a textile pad bath, or other suitable techniques.
- the excess may be removed by squeezing, centrifuging, pressing, or other operations and, if desired, the materials may then be dried in any convenient manner, such as in a forced air oven, under infrared lamps, or by evaporation in air at room temperature.
- the treated cloth is then cured, that is, reacted with the modifying agent, by holding it for a period of time at an elevated temperature in the presence of a basic catalyst.
- the addition of excessive amounts may result in a decrease in the tensile strength of the treated material, the tensile strength being an inverse function of the amount of modifying agent employed.
- the loss in tensile strength is quite small.
- the amount of modifying agent used will be such as to result in a low loss of tensile strength while still providing high wrinkle and crease resistance as well as flame resistance.
- add-on refers to the modifying agent which has reacted with the textile material, that is, the modifying agent which remains as an integral chemical part of the textile material, after curing and washing to remove unreacted excess.
- the amount of add-on is given in percent by weight based on the original dry weight of the textile material. It has been found that good wrinkle resistance is imparted to the textile materials when add-ons within the range of about 3 to are used, while good flame resistance is provided with add-ons within the range of about 5 to 20%. Accordingly, in most instances, to obtain the desired wrinkle and flame resistant properties, add-ons within the range of about 5 to 10% are preferred.
- the treating solutions are formulated so as to contain the phosphonium salt of the present invention in an amount within the range of about 1 to about 40% by weight of the solution and preferably in an amount within the range of about 10 to about 20% by weight of the solution.
- the treating solutions may also contain a basic catalyst which is employed to assist the reaction between the phosphonium salts of the present invention and the textile material.
- these catalysts are preferably present in amounts which will provide a pH in the treating solution which is greater than about 7 and preferably a pH within the range of about 8 to 11.
- the basic catalyst may be applied in a separate step either before or after the application of the phosphonium salt of the present invention.
- Basic catalysts which may be employed include, for example, alkali metal or other suitable hydroxides, carbonates, bicarbonates, acetates, phosphates, metasilicates, and the like.
- Particularly suitable catalyst materials have been found to be sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate. Where these materials are added to the textile treating solution, they are preferably present in amounts within the range of about 0.5 to about 20% by weight of the composition.
- the textile material After the textile material has been treated with the present solution and the excess solution has been removed therefrom, it is cured at a temperature within the range of about 20 centigrade to about 250 centigrade, for a period of time sufiicient to permit the reaction between the phosphonium compound and the textile material to take place.
- the curing time may vary from several hours, at room temperature, to less than 1 minute when elevated temperatures are used. In many instances, excellent curing results have been obtained when using curing temperatures within the range of about 150 to 185 degrees centigrade for a period of from about 3 to 10 minutes.
- the treatment with the hydroxyalkyl phosphonium salts of the present invention may be supplemented by treatment with other materials for modifying or softening the hand of the material, water repellent agents, dyestuffs or the like, as are known to those in the art. These materials may be added simultaneously, in the same formulation as the hydroxyalkyl phosphonium salts, or they may be applied to the fabric either before or after the application of these salts, in a separate operation.
- the clear filtrate was then concentrated to substantially constant weight at a temperature of 45 centigrade and a pressure of 16 millimeters of mercury.
- Example 2 The procedure of Example 1 was repeated with the exception that 1.25 moles of tetrakis(hydroxymethyl) phosphonium chloride and 1.01 moles of potassium hydroxide were used. Additionally, the pH of the reaction was maintained within the range of about 9 to 10 and a total of about 1.13 moles of hydrochloric acid was used to maintain this pH and effect the neutralization of the reaction product to a pH of 7. A total of 4.12 moles of ethylene oxide were passed into the reaction mixture and it was found that in forming the reaction product, 2.71 moles of ethylene oxide were reacted. The product formed was determined to be a mixture of di(2-hydroxyethyl)di (hydroxymethyl)phosphonium chloride and tris(2 hydroxyethyl)hydroxymethyl phosphonium chloride.
- This treating solution also contained 3% by weight of sodium carbonate, as the curing catalyst. Bleached, desized, mercerized, 80 x 80 (threads per inch) cotton cloth, weighing 3.1 ounces per square yard was padded through the treating solution to eifect a wet pickup of about 80%. The thus-treated cloth was then cured by heating for 10 minutes at about 155 Centigrade to provide a final resin add-on on the cloth of 9.7%, after washing in hot soapy water, rinsing and pressing dry and fiat.
- the wrinkle recovery angles of the cloth were then determined using the Monsanto method, and the wrinkle recovery angles in the fill direction were found to be 108, dry, and 134, wet, as compared to 67, dry, and 83, wet, for an untreated control.
- Samples of the treated cloth were then subjected to the flammability test, American Association of Chemists and Colorist Test AATCC 33-1957, and it was found that 24 seconds were required for the flame to travel 5 inches up a strip held at a 45 angle, as compared to a time of only 9 seconds for an untreated control. Additionally, it was found that on the treated sample there was no flame propagation in a downward or horizontal direction although such propagation was obtained on the untreated control sample.
- Example 4 The procedure of Example 3 was repeated with the exception that the treating solution used was an aqueous solution containing 14% of the tris(2-hydroxyethyl)hydroxymethyl phosphonium chloride as prepared in Example 1 and 6% by weight of sodium bicarbonate as a curing catalyst. After curing as in Example 3, a resin add-on of 9.0% was obtained and the wrinkle recovery angles in the fill direction were found to be 107, dry, and 122, wet, as compared to 68", dry, and 60, wet, for an untreated control.
- phosphonium salt having the wherein n is a number from 2 to 3, Z is the anion of a salt-forming acid, R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 2 carbon atoms, and R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 3 carbon atoms.
- a method of preparing hydroxyalkyl phosphonium salts have the formula R Cll i: (Biliis-u wherein n is a number from 2 to 3, Z is the anion of a salt-forming :acid, R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 3 carbon atoms, and R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 2 carbon atoms, which comprises neutralizing a component (A) having the formula R1-CH I PX wherein R is as previously defined and X is halogen, with a base so as to provide a pH within the range of about 5 to 10, reacting the neutralized component (A) with an alkylene oxide having the formula wherein R is :as previously defined, maintaining the pH of the reaction mixture within the range of about 5 to 10, and adding an acid to the resulting product in an amount sufiicient to form a substantially neutral salt.
- Atteating Oificor change "R is a lower alkyl group containing 1 to 3 carbon atoms" to R is selected from the group consisting of hydrogen and lower alkyl snusn JUN 2 .1970
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Description
United States Patent 3,452,098 HYDROXYMETHYL, BETA-HYDROXYALKYLENE PHOSPHONIUM SALTS AND THE PREPARA- TION THEREOF William J. Vnllo, Tonawanda, N.Y., assignor to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York No Drawing. Filed Apr. 18, 1966, Ser. No. 543,081 Int. Cl. C071 9/02, 9/54; C09d /18 US. Cl. 260606.5 5 Claims ABSTRACT OF THE DISCLOSURE Hydroxymethyl phosphonium salts having the forwherein n is a number from 2 to 3, Z is the anion of a salt-forming acid, R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 2 carbon atoms, and R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 3 carbon atoms, and methods for producing same. The hydroxymethyl phosphonium salts are used for treating cellulosic textile materials to render them crease and flame resistant.
This invention relates to novel hydroxyalkyl phosphonium compounds and more particularly it relates to novel hydroxyalkyl phosphonium halide compounds, their method of preparation and their use for treating cellulosic textile materials to render them crease and flame resistant.
In the past, it has been known to form ethers by alkylating phosphonium halide materials, such as tetrakis (hydroxyorgano)phosphonium halide, which reactions have been carried out under acidic conditions, generally using equal molar amounts of the phosphonium halide component with the alkylene oxide in the reaction. Although the resulting ether compounds have been reported as having some effectiveness as flame-retarding agents for treating cellulosic material, effectiveness has not been found to be sufficiently great, particularly in view of their cost, to warrant the widespread adoption of such materials for flame retarding purposes. Additionally, attempts to utilize such ethers for imparting crease or wrinkle resistance to cellulosic textiles has not been successful.
It has further been proposed in the past to react a tris (hydroxyrnethyl)phosphine with an alkylene oxide, using equal molar amounts of the alkylene oxide and the phosphine, generally under acidic conditions. Here again, although the products obtained have some utility in the treatment of cellulosic textiles to render them flame retardant, the materials have not been found to be effective in imparting crease resistance to the fabric and like the ether products described hereinabove, have not been widely used. Additionally, the tris(hydroxymethyl)phosphine is normally a difiicult material to handle, being readily oxidized in the air and, thus, normally requiring handling in an inert atmosphere. Accordingly, because of these difficulties, these reaction products have not been used, even for imparting flame retardancy, to any great extent.
It is, therefore, an object of the present invention to provide novel hydroxyalkyl phosphonium compounds,
ice
useful in treating cellulosic textile material to impart crease and flame resistance thereto.
A further object of the present invention is to provide a novel method for preparing hydroxyalkyl phosphonium compounds, which method does not utilize reactants which are diflicult to handle.
Another object of the present invention is to provide a method for treating cellulosic textile materials so as to impart flame and crease resistance to these materials.
These and other objects will become apparent to those skilled in the art from the description of the invention which follows:
Pursuant to the above objects, the present invention includes a hydroxyalkyl phosphonium halide having the formula OH 4-n P+z- R-CH-CH: a,
wherein n is a number from 2 to 3 and Z is the anion of a salt forming acid, and R is a lower alkyl group containing 1 to 3 carbon atoms and R is selected from the group consisting of hydrogen and lower alkyl groups containing 1 to 3 carbon atoms.
More specifically, the hydroxyalkyl phosphonium salts of the present invention are those compounds containing at least two Z-hydroxyalkyl groups, and desirably three Z-hydroxyalkyl groups. Exemplary of specific compounds falling within this class are di(2-hydroxyethyl)di(hydroxymethyl) phosphonium chloride; tris(2-hydroxyethyl)hydroxymethyl phosphonium chloride: tris(2-hydroxybutyl)hydroxymethyl phosphonium chloride; tris (2-hydroxypr0pyl)hydr0xymethyl phosphonium chloride; di (2 hydroxyethyl) di(hydroxyethyl)phosphonium chloride; tris(2 hydroxyethyl)hydroxybutyl phosphonium chloride and the like. It is to be appreciated, that in these compounds, the acid anion may be that of any suitable acid which will form a salt with the compound, such as chloride, bromide, iodide, fluoride, acetate, sulfate, and the like. Of these, the preferred anion is the chloride and specific reference hereinafter will be made to this material,
The hydroxyalkyl phosphonium salts of the present invention are prepared by reacting a neutralized tetrakis (hydroxyalkyl)phosphonium halide with an alkylene oxide. The tetrakis(hydroxyalkyl)phosphonium halide used in this reaction has the formula wherein R is selected from the group consisting of hydrogen and lower alkyl groups having from 1 to 3 carbon atoms and wherein X is halogen. Preferably, the phosphonium halide is tetrakis(hydroxymethyl)phosphonium chloride although other phosphonium halides such as tetrakis(hydroxyethyl)phosphonium chloride; tetrakis (hydroxybutyl)phosphonium bromide; tetrakis(hydroxypropyl)phosph0nium chloride; and the like, may also be used. The preferred tetrakis(hydroxymethyl)phosphonium chloride is commercially available, typically as an aqueous solution, Moreover, it can be safely and conveniently handled, in air, either as a crystalline solid, having a melting point of about centigrade, or as an aqueous or non-aqueous solution. For these reasons, this is the preferred phosphonium halide compound for use in the present invention.
The alkylene oxide used in forming the novel phosphonium compounds of the present invention has the formula:
wherein R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 2 carbon atoms. Of the various alkylene oxides which may be used, the preferred one has been found to be ethylene oxide although, in many instances, satisfactory results have been obtained when using propylene and butylene oxide as well.
In carrying out the process of the present invention, the preferred tetrakis(hydroxymethyl)phosphonium chloride is reacted With an excess of the preferred ethylene oxide in the presence of a base, whereby neutralization of the phosphonium chloride material is effected, in situ, in the reaction. In carrying out the reaction, the ethylene oxide should be present in an amount of at least 2 moles of ethylene oxide per mole of the tetrakis (hydroxymethyl)phosphonium chloride and is preferably present in an amount of at least 3 or more moles of ethylene oxide per mole of the phosphonium chloride. Preferably, the base may first be reacted with the phosphonium chloride and thereafter the resulting neutralized material is reacted with the ethylene oxide.
While it is not intended to limit the present invention to a particular theory of reaction, the following equation is presented to illustrate the preparation of the compounds of the present invention, in terms of the stoichiometry for a typical specific embodiment thereof:
(HOCI-IzhPCl KOH HgC Cll (HOCHz)+P(CHgC1-I;OH)3 3HCHO KCL 21120 It is to be noted, that in order to form the hydroxyalkylphosphonium salt of the present invention, this reaction must be carried out at a pH of at least about 5 and preferably at a pH within the range of about 8 or 9. Accordingly, sufficient base will be provided in the reaction to obtain this pH. Additionally, it is to be noted that at a pH above about 10, oxidation of trivalent phosphorus takes place, which reaction is detrimental to the formation of compounds of the present invention. Accordingly, in order to prevent the pH of the reaction mixture from exceeding a value of about 10, an acid is added to the reaction media to control the pH. This acid will react with the phosphonium hydroxide product ('1) formed, forming the salt (II) of the acid and the phosphonium hydroxide compound, which salt is then recovered as the product of the present process.
As has been indicated hereinabove, various acids may be used for this purpose to form the salts, including hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, acetic acid, and the like. In many instances, the preferred acid has been found to be hydrochloric acid and for this reason, specific reference hereinafter will be made to this material. Accordingly, when using hydrochloric acid, thep referred product by the method of the present invention will be tri(2- hydroxyethyl)hydroxymethyl phosphonium chloride.
Among the bases which may be employed in the reaction of the present invention are the various alkali metal hydroxides, oxides, carbonates, bicarbonates, as well as tertiary amines, quaternary ammonium hydroxide, and, in general, any strong base which is capable of forming hydroxide ions in aqueous solution. It will be apparent from the equation presented hereinabove, that in the reaction, the base functions as a reactant, rather than as a catalyst and is consumed in the reaction in an amount which is proportional to the quantity of the phosphonium halide material which is employed. Accordingly, in many instances, it is preferred to employ the base in an amount which is about equivalent, on a molar basis, to the amount of the tetrakis(hydroxy methyl) phosphonium chloride which is used.
The reaction of the present invention may conveniently be accomplished in either aqueous or non-aqueous media. Exemplary of the mediums which may be used are water; non-aqueous liquids such as methyl alcohol, ethyl, alcohol, propyl alcohol, dimethyl formamide, acctonitrile; and mixtures of water and a non-aqueous liquid. In most instances, however, it is preferred to employ an aqueous medium. Normally, the reaction time Will vary from less than a minute to more than an hour, depending upon the temperatures, proportion of reactions and the like. Typically, the reaction temperatures will be maintained at not substantially in excess of about 50 centigrade, so as to avoid too vigorous a reaction with the consequent possibility of volatilizing the reaction constituents and undesired side reactions.
Preferably, the reaction is carried out by first neutralizing the terakis(hydroxymethyl)phosphonium chloride with the base, and thereafter, adding to the neutralized phosphonium chloride the ethylene oxide, in the amounts which have been indicated hereinabove. By controlling the rate of addition of the ethylene oxide to the neutralized phosphonium chloride, the reaction temperature may normally be maintained below the desired 50 centigrade, and by continuous addition of mineral acid, the pH may be kept within the preferred range of 8-9. Inasmuch as the reaction is exothermic, in some instances, it may be desirable to provide external cooling for the reaction. The hydroxylal-kyl phosphonium salts formed by the present reaction are separated from volatile components by a vacuum stripping and from the salt byproduct by extraction with alcohol or similar solvent. Distillation of the extracting solvent then affords the phosphonium salt as the product. Additionally, it has been found that in some instances, it may be desirable to carry out the reaction under pressure.
The hydroxyalkyl phosphonium salts of the present invention may be used in the treatment of cellulosic textile materials so as to impart crease or wrinkle resistance as well as flame resistance to the treated materials. The present phosponium salts may be applied to the textile materials in any suitable formulation, as for example, an emulsion, a dispersion or a solution. These may be applied by dipping, spraying, rolling, or by the use of a textile pad bath, or other suitable techniques. Following the application of the textile treating solution, the excess may be removed by squeezing, centrifuging, pressing, or other operations and, if desired, the materials may then be dried in any convenient manner, such as in a forced air oven, under infrared lamps, or by evaporation in air at room temperature. The treated cloth is then cured, that is, reacted with the modifying agent, by holding it for a period of time at an elevated temperature in the presence of a basic catalyst. As is the case with most textile modifying agents, the addition of excessive amounts may result in a decrease in the tensile strength of the treated material, the tensile strength being an inverse function of the amount of modifying agent employed. With low percentages of the modifying agents of the present invention, the loss in tensile strength is quite small. For practical purposes, the amount of modifying agent used will be such as to result in a low loss of tensile strength while still providing high wrinkle and crease resistance as well as flame resistance.
Based on the foregoing, it has been found that on addon of the modifying agent of from about 1 to 20% by weight will be satisfactory for most purposes. It is to be appreciated that the term add-on" as used herein refers to the modifying agent which has reacted with the textile material, that is, the modifying agent which remains as an integral chemical part of the textile material, after curing and washing to remove unreacted excess. The amount of add-on is given in percent by weight based on the original dry weight of the textile material. It has been found that good wrinkle resistance is imparted to the textile materials when add-ons within the range of about 3 to are used, while good flame resistance is provided with add-ons within the range of about 5 to 20%. Accordingly, in most instances, to obtain the desired wrinkle and flame resistant properties, add-ons within the range of about 5 to 10% are preferred.
In formulating textile treating composition utilizing the phosphonium salts of the present invention, it is preferable to formulate these materials as aqueous solutions. If desired, however, an emulsion dispersion or solution is a suitable non-aqueous solvent, such as an alcohol, or the like, may be used. Typically, the treating solutions are formulated so as to contain the phosphonium salt of the present invention in an amount within the range of about 1 to about 40% by weight of the solution and preferably in an amount within the range of about 10 to about 20% by weight of the solution.
Additionally, the treating solutions may also contain a basic catalyst which is employed to assist the reaction between the phosphonium salts of the present invention and the textile material. When incorporated in the treating solution, these catalysts are preferably present in amounts which will provide a pH in the treating solution which is greater than about 7 and preferably a pH within the range of about 8 to 11. Alternatively, the basic catalyst may be applied in a separate step either before or after the application of the phosphonium salt of the present invention.
Basic catalysts which may be employed include, for example, alkali metal or other suitable hydroxides, carbonates, bicarbonates, acetates, phosphates, metasilicates, and the like. Particularly suitable catalyst materials have been found to be sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate. Where these materials are added to the textile treating solution, they are preferably present in amounts within the range of about 0.5 to about 20% by weight of the composition.
After the textile material has been treated with the present solution and the excess solution has been removed therefrom, it is cured at a temperature within the range of about 20 centigrade to about 250 centigrade, for a period of time sufiicient to permit the reaction between the phosphonium compound and the textile material to take place. The curing time may vary from several hours, at room temperature, to less than 1 minute when elevated temperatures are used. In many instances, excellent curing results have been obtained when using curing temperatures within the range of about 150 to 185 degrees centigrade for a period of from about 3 to 10 minutes.
If desired, the treatment with the hydroxyalkyl phosphonium salts of the present invention may be supplemented by treatment with other materials for modifying or softening the hand of the material, water repellent agents, dyestuffs or the like, as are known to those in the art. These materials may be added simultaneously, in the same formulation as the hydroxyalkyl phosphonium salts, or they may be applied to the fabric either before or after the application of these salts, in a separate operation.
In order that those skilled in the art may better understand the present invention and the manner in which it may be practiced, the following specific examples are given. In these examples, unless otherwise indicated, temperatures are in degrees centigrade and parts and percents are by weight. It is to be appreciated, however, that these examples are merely exemplary of the present invention and are not to be taken as a limitation thereof.
6 EXAMPLE 1 To a reaction vessel, provided with a magnetic stirrer and cooled :by an ice bath, was added 238 grams (1.0 moles) of an aqueous solution of tetrakis(hydroxymethyl)phosphonium chloride in grams of boiled water. The reaction vessel was flushed with nitrogen and there was then added a solution of 5 3 grams (0.81 mole) of 86% potassium hydroxide pellets in grams of boiled water, while the reaction mixture was stirred. Thereafter, ethylene oxide, partially diluted with nitrogen, was bubbled through the reaction mixture while the temperature was maintained within the range of 23 to 42 degrees centigrade. Additionally, a solution of 97 grams 1.0 mole) of concentrated hydrochloric acid in 97 grams of boiled water was added portion-wise to the reaction mixture to maintain the pH within the range of 89 during the reaction. After the passage of 210 grams (4.77 moles) of ethylene oxide through the reaction mixture, the flow of ethylene oxide was stopped and a stream of nitrogen was blown through the reaction vessel for 50 minutes to remove unreacted ethylene oxide. Thereafter an additional quantity of hydrochloric acid solution was added to the reaction mixture to bring the solution to a final pH of about 7.0. The reaction solution was then concentrated in vacuum to a salty slurry to which was added 500 milliliters of denatured anhydrous alcohol. The mixture was agitated and filtered to remove potas sium chloride. The clear filtrate was then concentrated to substantially constant weight at a temperature of 45 centigrade and a pressure of 16 millimeters of mercury. 254 grams of a pale yellow mobile liquid product having an iodine equivalent weight of 144 and a phosphorus content of 11.44%, of which 85.2% was non-volatile at 72 centigrade and a pressure of 0.2 millimeter, was obtained. From this material, an anhydrous product was isolated as a viscous, amber oil by concentrating to constant weight at a temperature of 60 to 70 centigrade and a pressure of 0.2 millimeter of mercury. It was determined that 3.44 moles of ethylene oxide per mole of tetrakis(hydroxymethyl) phosphonium chloride was reacted in forming this product and that approximately 3 moles of formaldehyde, per mole of the phosphonium chloride had been released. This anhydrous product, determined to be tris(2-hydroxyethyl)hydroxymethyl phosphonium chloride had an iodine equivalent weight of 124, an acid equivalent weight of 242, and contained 13.33% phosphorus, as compared to the theoretical phosphorus content of 13.32%. Additionally, the ratio of combined formaldehyde to phosphorus was 1 and the tetraphenylboron derivative analyzed correctly for all elements.
EXAMPLE 2 The procedure of Example 1 was repeated with the exception that 1.25 moles of tetrakis(hydroxymethyl) phosphonium chloride and 1.01 moles of potassium hydroxide were used. Additionally, the pH of the reaction was maintained within the range of about 9 to 10 and a total of about 1.13 moles of hydrochloric acid was used to maintain this pH and effect the neutralization of the reaction product to a pH of 7. A total of 4.12 moles of ethylene oxide were passed into the reaction mixture and it was found that in forming the reaction product, 2.71 moles of ethylene oxide were reacted. The product formed was determined to be a mixture of di(2-hydroxyethyl)di (hydroxymethyl)phosphonium chloride and tris(2 hydroxyethyl)hydroxymethyl phosphonium chloride.
When the procedure of the above examples is repeated using tetrakis(hydroxyethyl)phosphonium bromide, the product obtained is tris(2 hydroxyethyl)hydroxyethyl phosphonium chloride and when the procedure is repeated using propylene oxide, the product obtained is di(2- hydroxypropyl) di (hydroxymethyl) phosphonium chloride. Additionally, when the procedure of the above example is repeated but using sulfuric acid and acetic acid, in place of the hydrochloric acid, similar products are ob- EXAMPLE 3 A textile pad bath was formulated containing 25% by weight of the tris(2-hydroxyethyl)hydroxymethyl phOS- phonium chloride as prepared in Example 1, in water. This treating solution also contained 3% by weight of sodium carbonate, as the curing catalyst. Bleached, desized, mercerized, 80 x 80 (threads per inch) cotton cloth, weighing 3.1 ounces per square yard was padded through the treating solution to eifect a wet pickup of about 80%. The thus-treated cloth was then cured by heating for 10 minutes at about 155 Centigrade to provide a final resin add-on on the cloth of 9.7%, after washing in hot soapy water, rinsing and pressing dry and fiat. The wrinkle recovery angles of the cloth were then determined using the Monsanto method, and the wrinkle recovery angles in the fill direction were found to be 108, dry, and 134, wet, as compared to 67, dry, and 83, wet, for an untreated control. Samples of the treated cloth were then subjected to the flammability test, American Association of Chemists and Colorist Test AATCC 33-1957, and it was found that 24 seconds were required for the flame to travel 5 inches up a strip held at a 45 angle, as compared to a time of only 9 seconds for an untreated control. Additionally, it was found that on the treated sample there was no flame propagation in a downward or horizontal direction although such propagation was obtained on the untreated control sample.
EXAMPLE 4 The procedure of Example 3 was repeated with the exception that the treating solution used was an aqueous solution containing 14% of the tris(2-hydroxyethyl)hydroxymethyl phosphonium chloride as prepared in Example 1 and 6% by weight of sodium bicarbonate as a curing catalyst. After curing as in Example 3, a resin add-on of 9.0% was obtained and the wrinkle recovery angles in the fill direction were found to be 107, dry, and 122, wet, as compared to 68", dry, and 60, wet, for an untreated control.
While there have been described various embodiments of the invention the methods and compositions described are not intended to be understood as limiting the scope of the invention, as it is realized that changes therewithin are possible and it is further intended that each element recited in any of the following claims is to be understood as referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent manner, it being intended to cover the in vention broadly in whatever form its principle may be utilized.
What is claimed is:
1. A hydroxyalkyl formula:
phosphonium salt having the wherein n is a number from 2 to 3, Z is the anion of a salt-forming acid, R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 2 carbon atoms, and R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 3 carbon atoms.
2. The composition as claimed in claim 1 wherein R is hydrogen, R is hydrogen, Z is chlorine and n is 3.
3. A method of preparing hydroxyalkyl phosphonium salts have the formula R Cll i: (Biliis-u wherein n is a number from 2 to 3, Z is the anion of a salt-forming :acid, R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 3 carbon atoms, and R is selected from the group consisting of hydrogen and lower alkyl groups containing from 1 to 2 carbon atoms, which comprises neutralizing a component (A) having the formula R1-CH I PX wherein R is as previously defined and X is halogen, with a base so as to provide a pH within the range of about 5 to 10, reacting the neutralized component (A) with an alkylene oxide having the formula wherein R is :as previously defined, maintaining the pH of the reaction mixture within the range of about 5 to 10, and adding an acid to the resulting product in an amount sufiicient to form a substantially neutral salt.
4. The method as claimed in claim 3 wherein the component (A) is tetrakis(hydroxymethyl)phosphonium chloride, the component (B) is ethylene oxide, the base with which the component (A) is neutralized is potassium hydroxide and the acid which is added to the reaction product to form a neutral salt is hydrochloric acid.
5. The method as claimed in claim 4 wherein the pH of the reaction is maintained within the range of about 8 to 9.
References Cited UNITED STATES PATENTS 3,257,460 6/ 1966 Gordon 260-6065 FOREIGN PATENTS 1,042,583 11/1958 Germany.
OTHER REFERENCES Shepherd: Chem. Abstracts (1958), vol. 52, pp. 13322-23.
TOBIAS E. LEVOW, Primary Examiner.
W. F. W. BELLAMY, Assistant Examiner.
U.S. C1. X.R. 117-136; 2528.1
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,52 ,098
Inventor(s) Dated June 24, 1969 William J. Vul 10 It is certified that error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:
Column 2 lines 25-26:
Column 3, line 35: Column 3 line 47: Column 3, line 68: Column 4, line 1: Column 4, line 7:
Column I, line 15: Column L, line 20:
Attest:
Atteating Oificor change "R is a lower alkyl group containing 1 to 3 carbon atoms" to R is selected from the group consisting of hydrogen and lower alkyl snusn JUN 2 .1970
ill! I. soaurmm. JR. Winner of Patents
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US773638A Expired - Lifetime US3552909A (en) | 1966-04-18 | 1968-11-05 | Treatment of cellulosic materials with hydroxyalkyl phosphonium salts |
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Cited By (3)
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US3619113A (en) * | 1969-09-26 | 1971-11-09 | American Cyanamid Co | Flame-retardant finish for cellulosic textile materials |
US4189449A (en) * | 1977-07-20 | 1980-02-19 | Hoechst Aktiengesellschaft | Production of quaternary phosphonium hydroxides |
US4761493A (en) * | 1986-03-12 | 1988-08-02 | Hokko Chemical Industry Co., Ltd. | Preparation process of quaternary phosphonium hydroxide |
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Publication number | Priority date | Publication date | Assignee | Title |
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DE3112945A1 (en) * | 1981-03-31 | 1982-10-07 | Hoechst Ag, 6000 Frankfurt | CELLULOSEETHER AND CELLULOSE MIXER WITH AT LEAST ONE PHOSPHORUS SUBSTITUENT AND A METHOD FOR THE PRODUCTION THEREOF |
WO2003021031A1 (en) * | 2001-09-01 | 2003-03-13 | Rhodia Consumer Specialties Limited | Phosphorus compounds |
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DE1042583B (en) * | 1957-05-25 | 1958-11-06 | Hoechst Ag | Process for the production of quaternary organic phosphorus compounds |
US3257460A (en) * | 1962-01-24 | 1966-06-21 | Hooker Chemical Corp | Preparation of tertiary phosphines |
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- 1966-04-18 US US543081A patent/US3452098A/en not_active Expired - Lifetime
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- 1968-11-05 US US773638A patent/US3552909A/en not_active Expired - Lifetime
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DE1042583B (en) * | 1957-05-25 | 1958-11-06 | Hoechst Ag | Process for the production of quaternary organic phosphorus compounds |
US3257460A (en) * | 1962-01-24 | 1966-06-21 | Hooker Chemical Corp | Preparation of tertiary phosphines |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US3619113A (en) * | 1969-09-26 | 1971-11-09 | American Cyanamid Co | Flame-retardant finish for cellulosic textile materials |
US4189449A (en) * | 1977-07-20 | 1980-02-19 | Hoechst Aktiengesellschaft | Production of quaternary phosphonium hydroxides |
US4761493A (en) * | 1986-03-12 | 1988-08-02 | Hokko Chemical Industry Co., Ltd. | Preparation process of quaternary phosphonium hydroxide |
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US3552909A (en) | 1971-01-05 |
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