CA2113239A1 - Fluorinated carboxylic acid esters of phosphono-and phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, a method for their preparation, and their use - Google Patents
Fluorinated carboxylic acid esters of phosphono-and phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, a method for their preparation, and their useInfo
- Publication number
- CA2113239A1 CA2113239A1 CA002113239A CA2113239A CA2113239A1 CA 2113239 A1 CA2113239 A1 CA 2113239A1 CA 002113239 A CA002113239 A CA 002113239A CA 2113239 A CA2113239 A CA 2113239A CA 2113239 A1 CA2113239 A1 CA 2113239A1
- Authority
- CA
- Canada
- Prior art keywords
- radical
- phosphono
- carboxylic acid
- acid esters
- acids containing
- 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.)
- Abandoned
Links
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 28
- 125000003396 thiol group Chemical group [H]S* 0.000 title claims abstract description 26
- MEUIIHOXOWVKNP-UHFFFAOYSA-N phosphanylformic acid Chemical class OC(P)=O MEUIIHOXOWVKNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 150000001733 carboxylic acid esters Chemical class 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000004078 waterproofing Methods 0.000 claims abstract description 6
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical class [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000010985 leather Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000011111 cardboard Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims 1
- 239000000123 paper Substances 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000012209 synthetic fiber Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 9
- -1 MERCAPTO GROUPS Chemical group 0.000 abstract description 3
- 150000007513 acids Chemical class 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- DSRUAYIFDCHEEV-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluoro-n-(2-hydroxyethyl)-n-methylbutane-1-sulfonamide Chemical compound OCCN(C)S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DSRUAYIFDCHEEV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- SOFPIAMTOZWXKT-UHFFFAOYSA-N 2h-1,2,4-triazine-3-thione Chemical group SC1=NC=CN=N1 SOFPIAMTOZWXKT-UHFFFAOYSA-N 0.000 description 1
- 241000385654 Gymnothorax tile Species 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- DLEPCXYNAPUMDZ-UHFFFAOYSA-N butan-2-ylphosphonic acid Chemical compound CCC(C)P(O)(O)=O DLEPCXYNAPUMDZ-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical class O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003573 thiols Chemical class 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
- D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
- D06M13/29—Phosphonic or phosphonous acids or derivatives thereof containing halogen atoms
-
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
FLUORINATED CARBOXYLIC ACID ESTERS OF PHOSPHONO- AND
PHOSPHINOCARBOXYLIC ACIDS CONTAINING HYDROXYL AND/OR MERCAPTO
GROUPS, A METHOD FOR THEIR PREPARATION, AND THEIR USE
ABSTRACT
The present invention relates to fluorinated carboxylic acid esters of phosphono- and phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, their use as waterproofing and/or oil-repellency agents, and a method for their preparation.
PHOSPHINOCARBOXYLIC ACIDS CONTAINING HYDROXYL AND/OR MERCAPTO
GROUPS, A METHOD FOR THEIR PREPARATION, AND THEIR USE
ABSTRACT
The present invention relates to fluorinated carboxylic acid esters of phosphono- and phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, their use as waterproofing and/or oil-repellency agents, and a method for their preparation.
Description
S~ 2 ~ 9 FL~ORINA~ED CARBOXY~IC ACID ~8TER8 OF P~08P~ONO- AND
1 P~08P~INOCARBo~Y~IC ACID~ CO~AINING ~YDRO~YL ~ND/OR M~RCAPT3 i 5 G~OU~, A ~E~OD FOR T~EIR pR~p~RaTIo~5 ~ND T~EIR ~B
!
,~, The present invention relates to fluorinated carboxylic acid esters of phosphono- and phosphinocarboxylic acids ~ontaining hydroxyl andlor mercapto groups, their use as waterproofing i and/or oil- repellency agents, and a method for their ~`! preparation.
~; .
!~ Compounds containing perfluDroalkyl groups are widely used in ; 15 impregnation agents in industry due to their waterproofing and oil-repellency properties (see Ullmann, ~nzyklopadie der . technischen Chemie, Fourth Edition, 1976, Volume 11, page 644;
~ and ibid, Fi~th ~ditio~, 1988, Volume A11, pages 373-3743.
.IR~`3 Typical applications comprise their use as an impregnation agent for waterproofing and imparting oil-repellency to textiles (see Ullmann, Enzyklopadie der technischen Chemie, ! Fourth Edition~ 1983, Volume 23, page 87), leather (see Ullmann, Enzyklop~die der tschnischen Chemie, ~ourth Edition, -~
1978, Volume 16, page 168) and pap~r (see JoN~ MeuBdoer~er and H. Niederpr~m, Chemikerzeitung 104 (1980) 45-52).
~,~ Examples of proofing agents such as these comprise alcohols and acrylates containing perfluoro groups, or their polymer dispersions (see J.N. MeuBdoerf~er and H. Niederprum, Chemikerzeitung 104 (1980) 45-52; and Ullmann, Enzyklop~die der terhnischen Chemie, Fourth Edition, 1983, Volume Z3, page 87). Routes for their synthesis are described by J~No MeuBdoerf~er and H. ~iederprum in Chemikerzeitung 104 ~1980) ; ~5-52.
-:, Le A_zs 527 - FC
:',''`' :
.,!
... ~ :
~:'~ , .
~ - 2 - 21~323~
The perfluorinated compounds used as starting materials in the above-mentioned ~luorinated surfactants are produced industrially by three different routes:
-,. 5 a) electrochemical fluorination;
j b~ telomerization of perfluorolefines, particularly , tetrafluoroethylene; and 'l 10 c) oligomerization of tetrafluoroethylene.
, i , The above~mentioned methods of preparing per~luorinated i~ starting materials are very expensive on an industrial scale, vhich results in high manufacturing costs for the desired lS chemical compounds containing perfluoro ~roups.
. j ~, The object of the invention is to provide modi~ied organic compounds containing fluoro groups which have watsrproofing and/or oil-repellency properties, and which can be produced simply and inexpensively.
This object is achi~ved by means of the fluorinated carboxylic i acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to the invention.
The present invention relates to fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, of general formula (I):
p Z-C-O-(cH2)n~ (I)m~Ym-~F
H0 0 R~ -Le A 29 527 .' . ` ~
~ - 3 - 2~323~
., ;' where ~, Rl is a hydroxyl group, a methyl group, an ethyl group or a phenyl radical, ~, 5 RF is a linear or branched fluoroalkyl radical with 1 to 18 carbon atoms, or a fluoxinated, branched or linear monomeric ether or polyethler with 1 to 1~ carbon atoms, .,.j I!
10 RH is a linear or branched alkyl radical with 1 to 10 ~i, carbon atoms, `~-! R is a hydroxyl or mercapto group, X represents a linear or branched alkylene radical with 1 .~l to 20 carbon atoms, or a linear or branched alkylene ;~, radical with 1 to 20 carbon atoms and with one or more `~ substituent R groups, where ~ has the same meaning as -~
~, above, ~, Y represents a -:~. o O O
j C=0, ~S ~ , 0 ~S- or -0-C~ group, `1 2 5 / 11 11 :
: ~
,, .
l~ Z represents a linear or branched alkanetriyl radical (trivalent hydrocarbon radical) with 1 to 20 carbon : 30 atoms, or a linear or branched alkanetriyl radical with ~l 1 to 20 carbon atoms, interrupted by amino groups which may themselves contain C1 to C10 alkyl groups or aryl groups as substituents~ or a linear or branched alkanetriyl radical with 1 to 20 carbon atoms with one or more substituant groups of structure -COR2l or a linear or branched alkanetriyl radical with 1 to 20 carbon atoms with one or more substituent groups of Le A 29 527 ~`: 2~3'~9 structure -PO2HR1, where Rl has the same meaning as above, m may be 0 or 1, . 5 ~ n is an integer from 0 to 6, and j'l `~` R2 represents a hydroxyl radical, or a radical of structure ~;,1 ~(C~I2)n (N~m~Ym RF
q~ R~
i,y or a radical of structure 0-X-RI or a linear or branched alkoxy radical with 1 to 30 carbon atoms, where n, m, RHI RF~ R, X and Y have the same meaning as above, .. . . .
~l and their salts.
.
~g 20 The fluorina~d carboxylic acid est~rs of phosphono- or i¦ phosphinocarboxylic acids containing hydroxyl andlor mercapto 1 groups are pre~erably those in which RF is ~ linear cr 3J branched fluoroalkyl radical with 3 to ~0 carbon atoms~
Fluor~nated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, in which RH represent~ an alkyl radical wi~h one or ~ two carbon atoms, are pre~erred.
i. 30 Fluorinated carboxylic acid esters of phosphono- or ` phosphinocarboxylic acids containing hydroxyl and/or mercapto i~ groups, in which n is one or two, are particularly pre~erred.
Fluorinated carboxylic acid esters o~ phosphono or ~; 35 phosphinocarboxylic acids containing hydroxyl and/or mercapto ;j groups, in which m is equal to one, are particularly preferred.
Le A 29 527 I
.. . .
. . , _ - 5 - 2~3~ ff For example, particularly preferred fluorinated carboxylic ~ acid esters of phosphono- or phosphinocarboxylic acids !:', containing hydroxyl and/or mercapto groups have the following structure:
' f O CH2 ~C (O) -O-CH2--CH2-N(CH3) - 5G2- C4Fs \ P - C - C~O~ - o -CH2-CH2-N(CH3~ - 52-C4F9 ~ HO
'i'f I 2 :
''3 15 ~/ CH2~ C(O~ - O~f~H2 -CH2 OH
f'f i 20 ''if O CH C~O) ~f~CH2~ CH2~ N(f~3) ~ SO2- C4Fg ~, 25 / P - C- C(O) -O -CH2-CH2-~(CH3)-502-C4F9 ~3f E~O
`;:f~ I ~2 ,':3330 ,~j CH2--ff''()----CH2--CEi2--H
3';
;~ 35 O CH2 C(O) ~O ~CH2~ CH2~-N (f~H3) - S2- C4~s HO
P -C - C(O) ~ - ~17~37 ~ 40 /
;~ HO -:f C 'H2 f ' I
1 45 CH2- C(o) -O - CH2 CH(OH) - CH2-1 :`
I
`; e A 29 527 f ._ , ~ .
: "
:
:: 6 2~323~
- , The radicals listed below are particularly preferred:
j ,.
Examples of RF
CF3-(CF2)2-CF3-(cF2)3-CF3-(~Fz) 5 -CF3-(CF2) 6 -CF3-(CF2) 7 -f CF3-(CF2)ll-;~' H--(CF2)6--'i: H-(CF2~2-o-, 15 CF2-CF2-CF2-0-CF(CF3)-CF3-CF2-~CF2-0-CF(cF3j]2-CF3-CF2-[~F2-0-CFfcF3?~3-., 1 20 Examples of_Z:
.f ~ CH , C(CH3)-, /
' 25 Z-c:H2--cH-cH2 CH-CH-PO3~2 -CH2-C-CH2-CH2-COOH, Le A 29 527 ., ~ 7 _ 2~32~ ~
.~
i~
A, --cH2-c-cH2--cM2po3H2 l ! -CH2-C-CH(CooH)-CH2-CooH
.~. .
;'! 10 ` / ' -~ .
.; I
-CH2-CH2~C-cH2-cH2-Po3H2~ :
-CH2-C-CH2-CH2-cN ~ ~
: :-ll~ HO-C(CH3~-CH-CH2-!~ 25 ?~ -CH2-N-CH2 ~, CH2 The fluorinated carboxylic acid esters o phosphono- or phosphinocarbo~ylic acids containing hydroxyl and/or mercapto ~':` groups according to the invention may be prepared by multi-stage synthesis for example, employing esterification : reactions of the corresponding phosphono- or )~ phosphinocar~oxylic acids or their salts with alcohols ¦: containing ~luoro groups and polyhydric alcohols or hydro~yfunctional thiols: -'.
) ~
Le A 29 527 ''' , .. .
~ 8 21 ~3239 ; 1 8 U C-O
z I ,P--Z~--ol K~ H0-tCH2)n-( 1 )m~Ym-RF
:J
o _ . O C-O
l~ll I
. ~ . ~z ~ - o- t CH2 ) n ~ ~ I ) m~ Ym RF Ka~ ~ t HO ) aK
`,? O R~ a ~l 15 r 1l 7-,. I o C O
,E~Z~-O- (CH~ ~ t ~ )m~Ym~RFI K
~ 20 '' 11 C Cl X--R
Z 1l~0~ (C~2)n- ( I )m~Ym RF ~ (HO)aK
.l 0 RH
~l~ 25 ;., `:
., ~1 ~
~ '.
,'1 .
,~;
I
i, Le A 29 527 ---. .
:' .. . . .
: J ~
1 P~08P~INOCARBo~Y~IC ACID~ CO~AINING ~YDRO~YL ~ND/OR M~RCAPT3 i 5 G~OU~, A ~E~OD FOR T~EIR pR~p~RaTIo~5 ~ND T~EIR ~B
!
,~, The present invention relates to fluorinated carboxylic acid esters of phosphono- and phosphinocarboxylic acids ~ontaining hydroxyl andlor mercapto groups, their use as waterproofing i and/or oil- repellency agents, and a method for their ~`! preparation.
~; .
!~ Compounds containing perfluDroalkyl groups are widely used in ; 15 impregnation agents in industry due to their waterproofing and oil-repellency properties (see Ullmann, ~nzyklopadie der . technischen Chemie, Fourth Edition, 1976, Volume 11, page 644;
~ and ibid, Fi~th ~ditio~, 1988, Volume A11, pages 373-3743.
.IR~`3 Typical applications comprise their use as an impregnation agent for waterproofing and imparting oil-repellency to textiles (see Ullmann, Enzyklopadie der technischen Chemie, ! Fourth Edition~ 1983, Volume 23, page 87), leather (see Ullmann, Enzyklop~die der tschnischen Chemie, ~ourth Edition, -~
1978, Volume 16, page 168) and pap~r (see JoN~ MeuBdoer~er and H. Niederpr~m, Chemikerzeitung 104 (1980) 45-52).
~,~ Examples of proofing agents such as these comprise alcohols and acrylates containing perfluoro groups, or their polymer dispersions (see J.N. MeuBdoerf~er and H. Niederprum, Chemikerzeitung 104 (1980) 45-52; and Ullmann, Enzyklop~die der terhnischen Chemie, Fourth Edition, 1983, Volume Z3, page 87). Routes for their synthesis are described by J~No MeuBdoerf~er and H. ~iederprum in Chemikerzeitung 104 ~1980) ; ~5-52.
-:, Le A_zs 527 - FC
:',''`' :
.,!
... ~ :
~:'~ , .
~ - 2 - 21~323~
The perfluorinated compounds used as starting materials in the above-mentioned ~luorinated surfactants are produced industrially by three different routes:
-,. 5 a) electrochemical fluorination;
j b~ telomerization of perfluorolefines, particularly , tetrafluoroethylene; and 'l 10 c) oligomerization of tetrafluoroethylene.
, i , The above~mentioned methods of preparing per~luorinated i~ starting materials are very expensive on an industrial scale, vhich results in high manufacturing costs for the desired lS chemical compounds containing perfluoro ~roups.
. j ~, The object of the invention is to provide modi~ied organic compounds containing fluoro groups which have watsrproofing and/or oil-repellency properties, and which can be produced simply and inexpensively.
This object is achi~ved by means of the fluorinated carboxylic i acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to the invention.
The present invention relates to fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, of general formula (I):
p Z-C-O-(cH2)n~ (I)m~Ym-~F
H0 0 R~ -Le A 29 527 .' . ` ~
~ - 3 - 2~323~
., ;' where ~, Rl is a hydroxyl group, a methyl group, an ethyl group or a phenyl radical, ~, 5 RF is a linear or branched fluoroalkyl radical with 1 to 18 carbon atoms, or a fluoxinated, branched or linear monomeric ether or polyethler with 1 to 1~ carbon atoms, .,.j I!
10 RH is a linear or branched alkyl radical with 1 to 10 ~i, carbon atoms, `~-! R is a hydroxyl or mercapto group, X represents a linear or branched alkylene radical with 1 .~l to 20 carbon atoms, or a linear or branched alkylene ;~, radical with 1 to 20 carbon atoms and with one or more `~ substituent R groups, where ~ has the same meaning as -~
~, above, ~, Y represents a -:~. o O O
j C=0, ~S ~ , 0 ~S- or -0-C~ group, `1 2 5 / 11 11 :
: ~
,, .
l~ Z represents a linear or branched alkanetriyl radical (trivalent hydrocarbon radical) with 1 to 20 carbon : 30 atoms, or a linear or branched alkanetriyl radical with ~l 1 to 20 carbon atoms, interrupted by amino groups which may themselves contain C1 to C10 alkyl groups or aryl groups as substituents~ or a linear or branched alkanetriyl radical with 1 to 20 carbon atoms with one or more substituant groups of structure -COR2l or a linear or branched alkanetriyl radical with 1 to 20 carbon atoms with one or more substituent groups of Le A 29 527 ~`: 2~3'~9 structure -PO2HR1, where Rl has the same meaning as above, m may be 0 or 1, . 5 ~ n is an integer from 0 to 6, and j'l `~` R2 represents a hydroxyl radical, or a radical of structure ~;,1 ~(C~I2)n (N~m~Ym RF
q~ R~
i,y or a radical of structure 0-X-RI or a linear or branched alkoxy radical with 1 to 30 carbon atoms, where n, m, RHI RF~ R, X and Y have the same meaning as above, .. . . .
~l and their salts.
.
~g 20 The fluorina~d carboxylic acid est~rs of phosphono- or i¦ phosphinocarboxylic acids containing hydroxyl andlor mercapto 1 groups are pre~erably those in which RF is ~ linear cr 3J branched fluoroalkyl radical with 3 to ~0 carbon atoms~
Fluor~nated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, in which RH represent~ an alkyl radical wi~h one or ~ two carbon atoms, are pre~erred.
i. 30 Fluorinated carboxylic acid esters of phosphono- or ` phosphinocarboxylic acids containing hydroxyl and/or mercapto i~ groups, in which n is one or two, are particularly pre~erred.
Fluorinated carboxylic acid esters o~ phosphono or ~; 35 phosphinocarboxylic acids containing hydroxyl and/or mercapto ;j groups, in which m is equal to one, are particularly preferred.
Le A 29 527 I
.. . .
. . , _ - 5 - 2~3~ ff For example, particularly preferred fluorinated carboxylic ~ acid esters of phosphono- or phosphinocarboxylic acids !:', containing hydroxyl and/or mercapto groups have the following structure:
' f O CH2 ~C (O) -O-CH2--CH2-N(CH3) - 5G2- C4Fs \ P - C - C~O~ - o -CH2-CH2-N(CH3~ - 52-C4F9 ~ HO
'i'f I 2 :
''3 15 ~/ CH2~ C(O~ - O~f~H2 -CH2 OH
f'f i 20 ''if O CH C~O) ~f~CH2~ CH2~ N(f~3) ~ SO2- C4Fg ~, 25 / P - C- C(O) -O -CH2-CH2-~(CH3)-502-C4F9 ~3f E~O
`;:f~ I ~2 ,':3330 ,~j CH2--ff''()----CH2--CEi2--H
3';
;~ 35 O CH2 C(O) ~O ~CH2~ CH2~-N (f~H3) - S2- C4~s HO
P -C - C(O) ~ - ~17~37 ~ 40 /
;~ HO -:f C 'H2 f ' I
1 45 CH2- C(o) -O - CH2 CH(OH) - CH2-1 :`
I
`; e A 29 527 f ._ , ~ .
: "
:
:: 6 2~323~
- , The radicals listed below are particularly preferred:
j ,.
Examples of RF
CF3-(CF2)2-CF3-(cF2)3-CF3-(~Fz) 5 -CF3-(CF2) 6 -CF3-(CF2) 7 -f CF3-(CF2)ll-;~' H--(CF2)6--'i: H-(CF2~2-o-, 15 CF2-CF2-CF2-0-CF(CF3)-CF3-CF2-~CF2-0-CF(cF3j]2-CF3-CF2-[~F2-0-CFfcF3?~3-., 1 20 Examples of_Z:
.f ~ CH , C(CH3)-, /
' 25 Z-c:H2--cH-cH2 CH-CH-PO3~2 -CH2-C-CH2-CH2-COOH, Le A 29 527 ., ~ 7 _ 2~32~ ~
.~
i~
A, --cH2-c-cH2--cM2po3H2 l ! -CH2-C-CH(CooH)-CH2-CooH
.~. .
;'! 10 ` / ' -~ .
.; I
-CH2-CH2~C-cH2-cH2-Po3H2~ :
-CH2-C-CH2-CH2-cN ~ ~
: :-ll~ HO-C(CH3~-CH-CH2-!~ 25 ?~ -CH2-N-CH2 ~, CH2 The fluorinated carboxylic acid esters o phosphono- or phosphinocarbo~ylic acids containing hydroxyl and/or mercapto ~':` groups according to the invention may be prepared by multi-stage synthesis for example, employing esterification : reactions of the corresponding phosphono- or )~ phosphinocar~oxylic acids or their salts with alcohols ¦: containing ~luoro groups and polyhydric alcohols or hydro~yfunctional thiols: -'.
) ~
Le A 29 527 ''' , .. .
~ 8 21 ~3239 ; 1 8 U C-O
z I ,P--Z~--ol K~ H0-tCH2)n-( 1 )m~Ym-RF
:J
o _ . O C-O
l~ll I
. ~ . ~z ~ - o- t CH2 ) n ~ ~ I ) m~ Ym RF Ka~ ~ t HO ) aK
`,? O R~ a ~l 15 r 1l 7-,. I o C O
,E~Z~-O- (CH~ ~ t ~ )m~Ym~RFI K
~ 20 '' 11 C Cl X--R
Z 1l~0~ (C~2)n- ( I )m~Ym RF ~ (HO)aK
.l 0 RH
~l~ 25 ;., `:
., ~1 ~
~ '.
,'1 .
,~;
I
i, Le A 29 527 ---. .
:' .. . . .
: J ~
2 1 ~ 3 2 ~ 9 where ,, R1, R, RF ~ RH, X, Y, Z, m and n have the same meaning as above, ~f K is a hydrogenfcation, an a~monium cation or a monovalent ~ -~'f or pol~alent metal cationl and j~ a is an integer which corresponds to the charge of the !; 10 cation K.
., f The present invention also relates to the use o~ the fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to the invention as waterproofing agents ~ and/or oil-repellency agents.
... .
Due to the wate~ roofing and oil-repellency properties o~ thP
compounds according ~o the invention, they may be used as impregnating fayents in various arcf~as o~ application, wherein ~:
, the compounds according to the invention may be applied as j such or in the ~orm of polymer dispersions, for example.
f I.~ 25 For example, the compounds according to the invention may be f used on natural ~nd synthetic fibres (e.fg. for textiles, i carpets or awnings~ to repel water, grease, oil and/or dirt.
The compounds according to the invention may also be used on paper and cardboard (e.g. for packaging or fleeef~es) to - - ~
li~ repel wate-r, grease~ oil and/or dirt.
. .
Moreover, the compounds according to the invention may be used l on leather (e.g. for upholstery, æhoes or clothing) to repel f~ 35 water, grease~ oil and/or dirt.
Le A 29 527 :
r ' ~ ' ~ t ~ >~ . t~ ~ 1 f ~ t ;, i:, . .
^ The compounds according to the invention may also be used on . ceramics (e.g. tiles), o~ natural or artificial stone (e.g.
i sandstone), on wood (e.g. the wooden cladding of facades) and ;' on plastics ~e.g. polyesters) ~o:r impregnation against water, grease, oil, dirt, algae growth and/or weathering.
., , The invention will be described in more detail by means of the following examples.
E~A~PLE8 Exam~le 1 , 15 N-(2 hydroxyethyl)-N-methyl-perfluorobutyl sulphonamide (1.0 j mole/357 g) was dissolved in 4-methyl-pentane-2-one (200 ml) in a three-necked flask ~itted wi~h a stirrer and a water ~i trap, and concentrated sulphuric acid (0.5 ml) was added.
This solution was heated to about 116C. 2-phosphonobutane-i -.
~ 20 1,2,4-tricarboxylic acid (0.5 mole/135 g) dissolved in water i (135 g) was then slowly addedO After the addition was complete, the reaction mixture was re~luxed with stirring ~ until the entire amount o~ water (153 ml~ had bee~ distilled Z o~
Ethanediol (0.5 mole~31 g) was then slowly added, followed by refluxing with stirring until the entire amount of water (9 ml) had been distilled off from the reaction mixture.
, After the reaction was co~plate, the solvent wa~ distilled off at 70C and 70 mbar, and the product obtained was completely dried. The yield of 2-phosphonobutane-1,2,4-tricarboxylic acid which was triple-esteri~ied with two equivalents o~ N-(2-hydroxyethyl)-N-methyl-perfluorobutyl sulphonamide and one equivalent of ethanediol was 491 g (98.9 % theoretical).
Le A 29 527 : ~:
`. 11 21~32~
Example 2 ;~ N-~2-hydroxyethyl)-N-methyl-perfluorobutyl sulphonamide (0.6 mole/214 g) was dissolved in 4-methyl-pentane-2-one (150 ml) in a three~necked flask fitted with a stirrer and a water .; .
i~ trap, and concentrated sulphuric acid (0~5 ml) was added.
This solution was heated to about 116 C. 2-phosphonobutane-1,2,4-tricarboxylic acid (0.3 mole~81 g) dissolved in water -` 10 (81 g) was then slowly addled. After the addition was complete, the reaction mixtuxe was refluxed with stirring .. until the entire amount of wat~r (91.8 ml) had been distilled off.
., ~, 15 Propanetriol (0.3 mole/28 g) was then slowly added, followed by refluxing with stirring until the entire amount o~ watex ~'. (3.6 ml) had been distilled off from the reaction mixture.
i After the reaction was complete, the olvent was distilled off at 70C and 70 mbar, and 4he product obtained was co~pletely driedO The yield o~2-phosphonobutane 1,2,4-tricarboxylic acid which was triple-esterified with ~wo equivalents o~ N~r(2-hydro~yethyl)-N-methyl-perfluorobutyl sulphonamide and one ~i equivalent of propanetriol was 305 g (99.5 % theoratical).
..
Ex~mple 3 N-(2-hydroxyekhyl)-N-methyl-perfluorooctyl sulphonamide (0.1 mole/56 g) was dissolved in 4-methyl pentane-2-one (150 ml) in a three-necked flask fitted wikh a stirrer and ia water trap, and concentrated ~ulphuric acid (0.5 ~1) was added.
This solution was heated to about 116C. 2-phosphonobutane-, 1,2,4-tricarboxylic acid (0Ol ~ole/27 g) dissolved in 27g of j water was then slowly added. After the addition was complete, ~ 35 the reaction mixture was refluxed with stirring , I
, Le A 29 527 ~, ... .
1~ 2~ ~ 3~
until th~ entire amount o~ water (28.8 ml) had been distilled of~.
Octadecanol (0.1 mole/28 g) dissolved in ~0ml of 4-methyl-! 5 pentane-2-one was then slowly added, ~ollowed by re~luxing ~' with stirring until the entire amount of water (1.8 ml) had ;?, been distilled of~ from the reaction mixtureO
;, Ethanediol (0.1 mole/6 g) wa~ then slowly added, and the ~!q~ 10 reaction ~ixture was refluxed with stirring until the entire ' amount o~ water (1.8 ml) had been distilled off.
'! A~ter the reaction was complete, the solvent was distilled off at 70C and 70 mbar, and the product obtained was completely dried. The yield of 2-phosphonobutane-1,2,4 tricarboxylic ~ acid whi~h was triple-esteri~ied with one eguivalent each o~
e, N-(2-hydroxye~hyl)-N-methyl-per~luorooctyl sulphonamide, . octadeca~ol and ethanediol was 109 g (9~.8 % ~heoretical).
'.'' i ? I
.~
,, `:~
~ Le A 29 527
., f The present invention also relates to the use o~ the fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to the invention as waterproofing agents ~ and/or oil-repellency agents.
... .
Due to the wate~ roofing and oil-repellency properties o~ thP
compounds according ~o the invention, they may be used as impregnating fayents in various arcf~as o~ application, wherein ~:
, the compounds according to the invention may be applied as j such or in the ~orm of polymer dispersions, for example.
f I.~ 25 For example, the compounds according to the invention may be f used on natural ~nd synthetic fibres (e.fg. for textiles, i carpets or awnings~ to repel water, grease, oil and/or dirt.
The compounds according to the invention may also be used on paper and cardboard (e.g. for packaging or fleeef~es) to - - ~
li~ repel wate-r, grease~ oil and/or dirt.
. .
Moreover, the compounds according to the invention may be used l on leather (e.g. for upholstery, æhoes or clothing) to repel f~ 35 water, grease~ oil and/or dirt.
Le A 29 527 :
r ' ~ ' ~ t ~ >~ . t~ ~ 1 f ~ t ;, i:, . .
^ The compounds according to the invention may also be used on . ceramics (e.g. tiles), o~ natural or artificial stone (e.g.
i sandstone), on wood (e.g. the wooden cladding of facades) and ;' on plastics ~e.g. polyesters) ~o:r impregnation against water, grease, oil, dirt, algae growth and/or weathering.
., , The invention will be described in more detail by means of the following examples.
E~A~PLE8 Exam~le 1 , 15 N-(2 hydroxyethyl)-N-methyl-perfluorobutyl sulphonamide (1.0 j mole/357 g) was dissolved in 4-methyl-pentane-2-one (200 ml) in a three-necked flask ~itted wi~h a stirrer and a water ~i trap, and concentrated sulphuric acid (0.5 ml) was added.
This solution was heated to about 116C. 2-phosphonobutane-i -.
~ 20 1,2,4-tricarboxylic acid (0.5 mole/135 g) dissolved in water i (135 g) was then slowly addedO After the addition was complete, the reaction mixture was re~luxed with stirring ~ until the entire amount o~ water (153 ml~ had bee~ distilled Z o~
Ethanediol (0.5 mole~31 g) was then slowly added, followed by refluxing with stirring until the entire amount of water (9 ml) had been distilled off from the reaction mixture.
, After the reaction was co~plate, the solvent wa~ distilled off at 70C and 70 mbar, and the product obtained was completely dried. The yield of 2-phosphonobutane-1,2,4-tricarboxylic acid which was triple-esteri~ied with two equivalents o~ N-(2-hydroxyethyl)-N-methyl-perfluorobutyl sulphonamide and one equivalent of ethanediol was 491 g (98.9 % theoretical).
Le A 29 527 : ~:
`. 11 21~32~
Example 2 ;~ N-~2-hydroxyethyl)-N-methyl-perfluorobutyl sulphonamide (0.6 mole/214 g) was dissolved in 4-methyl-pentane-2-one (150 ml) in a three~necked flask fitted with a stirrer and a water .; .
i~ trap, and concentrated sulphuric acid (0~5 ml) was added.
This solution was heated to about 116 C. 2-phosphonobutane-1,2,4-tricarboxylic acid (0.3 mole~81 g) dissolved in water -` 10 (81 g) was then slowly addled. After the addition was complete, the reaction mixtuxe was refluxed with stirring .. until the entire amount of wat~r (91.8 ml) had been distilled off.
., ~, 15 Propanetriol (0.3 mole/28 g) was then slowly added, followed by refluxing with stirring until the entire amount o~ watex ~'. (3.6 ml) had been distilled off from the reaction mixture.
i After the reaction was complete, the olvent was distilled off at 70C and 70 mbar, and 4he product obtained was co~pletely driedO The yield o~2-phosphonobutane 1,2,4-tricarboxylic acid which was triple-esterified with ~wo equivalents o~ N~r(2-hydro~yethyl)-N-methyl-perfluorobutyl sulphonamide and one ~i equivalent of propanetriol was 305 g (99.5 % theoratical).
..
Ex~mple 3 N-(2-hydroxyekhyl)-N-methyl-perfluorooctyl sulphonamide (0.1 mole/56 g) was dissolved in 4-methyl pentane-2-one (150 ml) in a three-necked flask fitted wikh a stirrer and ia water trap, and concentrated ~ulphuric acid (0.5 ~1) was added.
This solution was heated to about 116C. 2-phosphonobutane-, 1,2,4-tricarboxylic acid (0Ol ~ole/27 g) dissolved in 27g of j water was then slowly added. After the addition was complete, ~ 35 the reaction mixture was refluxed with stirring , I
, Le A 29 527 ~, ... .
1~ 2~ ~ 3~
until th~ entire amount o~ water (28.8 ml) had been distilled of~.
Octadecanol (0.1 mole/28 g) dissolved in ~0ml of 4-methyl-! 5 pentane-2-one was then slowly added, ~ollowed by re~luxing ~' with stirring until the entire amount of water (1.8 ml) had ;?, been distilled of~ from the reaction mixtureO
;, Ethanediol (0.1 mole/6 g) wa~ then slowly added, and the ~!q~ 10 reaction ~ixture was refluxed with stirring until the entire ' amount o~ water (1.8 ml) had been distilled off.
'! A~ter the reaction was complete, the solvent was distilled off at 70C and 70 mbar, and the product obtained was completely dried. The yield of 2-phosphonobutane-1,2,4 tricarboxylic ~ acid whi~h was triple-esteri~ied with one eguivalent each o~
e, N-(2-hydroxye~hyl)-N-methyl-per~luorooctyl sulphonamide, . octadeca~ol and ethanediol was 109 g (9~.8 % ~heoretical).
'.'' i ? I
.~
,, `:~
~ Le A 29 527
Claims (12)
1. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, of general formula (I) (I), where:
R1 is a hydroxyl group, a methyl group, an ethyl group or a phenyl radical, RF is a linear or branched fluoroalkyl radical with 1 to 18 carbon atoms, or a fluorinated branched or linear monomeric ether or polyether with 1 to 18 carbon atoms, RH is a linear or branched alkyl radical with 1 to 10 carbon atoms, R is a hydroxyl or a mercapto group, X represents a linear or branched alkylene radical with 1 to 20 carbon atoms, or a linear or branched alkylene radical with 1 to 20 carbon atoms and with one or more substituent R groups, where R has the same meaning as above, Y represents a , , or group, Z represents a linear or branched alkanetriyl radical (trivalent hydrocarbon radical) with 1 to 20 carbon atoms, or a linear or branched alkanetriyl radical with 1 to 20 carbon atoms, interrupted by amino groups which may themselves contain C1 to C10 alkyl groups or aryl groups as substituents, or a linear or branched alkanetriyl radical with 1 to 20 carbon atoms with one or more substituent groups of structure -COR2, or a linear or branched alkanetriyl radical with 1 to 20 carbon a oms with one or more substituent groups of structure -PO2HR1, where R1 has the same meaning as above, m is 0 or 1, n is an integer from 0 to 6, and R2 represents a hydroxyl radical, or a radical of structure , or a radical of structure O-X-R, or a linear or branched alkoxy radical with 1 to 30 carbon atoms, where n, m, RH, Rp, R, X and Y have the same meaning as above, and their salts.
R1 is a hydroxyl group, a methyl group, an ethyl group or a phenyl radical, RF is a linear or branched fluoroalkyl radical with 1 to 18 carbon atoms, or a fluorinated branched or linear monomeric ether or polyether with 1 to 18 carbon atoms, RH is a linear or branched alkyl radical with 1 to 10 carbon atoms, R is a hydroxyl or a mercapto group, X represents a linear or branched alkylene radical with 1 to 20 carbon atoms, or a linear or branched alkylene radical with 1 to 20 carbon atoms and with one or more substituent R groups, where R has the same meaning as above, Y represents a , , or group, Z represents a linear or branched alkanetriyl radical (trivalent hydrocarbon radical) with 1 to 20 carbon atoms, or a linear or branched alkanetriyl radical with 1 to 20 carbon atoms, interrupted by amino groups which may themselves contain C1 to C10 alkyl groups or aryl groups as substituents, or a linear or branched alkanetriyl radical with 1 to 20 carbon atoms with one or more substituent groups of structure -COR2, or a linear or branched alkanetriyl radical with 1 to 20 carbon a oms with one or more substituent groups of structure -PO2HR1, where R1 has the same meaning as above, m is 0 or 1, n is an integer from 0 to 6, and R2 represents a hydroxyl radical, or a radical of structure , or a radical of structure O-X-R, or a linear or branched alkoxy radical with 1 to 30 carbon atoms, where n, m, RH, Rp, R, X and Y have the same meaning as above, and their salts.
2. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to claim 1, wherein Rp is a linear or branched fluoroalkyl radical with 3 to 10 carbon atoms.
3. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to claim 1, wherein RH represents an alkyl radical with one or two carbon atoms.
4. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to claim 1, wherein n is one or two.
5. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to claim 1, wherein m is equal to one.
6. A method of preparing the fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to claim 1, wherein said method comprises a multi-stage synthesis and further wherein the corresponding phosphono- or phosphinocarboxylic acids of formula (II) (II), or their salts, where K is a hydrogen cation, an ammonium cation or a monovalent or polyvalent metal cation, a is an integer which corresponds to the charge of the cation K, and R1 and Z have the same meaning as in claim 1, are esterified in a first step with the corresponding alcohols, containing fluoro groups and of formula (III) (III), where n, m, RH, Y and Rp have the same meaning as in claim 1, and, in a further step, the ester formed in the first step is esterified with the corresponding polyhydric alcohols or hydroxyfunctional thiols of formula (IV) HO-X-R (IV), where X and R have the same meaning as in claim 1.
7. A method of using the fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, or their salts, according to claim 1, wherein said esters or salts are applied to at least one of natural fibers, synthetic fibers, paper, cardboard, leather, ceramics, stone, wood and plastics as waterproofing and/or oil-repellency agents.
8. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to claim 1, wherein said esters have the following formula:
9. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to claim 1, wherein said esters have the following formula:
10. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to claim 1, wherein said esters have the following formula:
11. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to claim 1, wherein Rp is a radical selected from the group consisting of:
CF3-(CF2)2-CF3-(CF2)3-CF3-(CF2)5-CF3-(CF2)6-CF3-(CF2)7-CF3-(CF2)11-H-(CF2)6-H-(CF2)2-O-CF2-CF2-CF2-O-CF(CF3)-CF3-CF2-[CF2-O-CF(CF3)]2- , and CF3-CF2-[CF2-O-CF(CF3)]3-.
CF3-(CF2)2-CF3-(CF2)3-CF3-(CF2)5-CF3-(CF2)6-CF3-(CF2)7-CF3-(CF2)11-H-(CF2)6-H-(CF2)2-O-CF2-CF2-CF2-O-CF(CF3)-CF3-CF2-[CF2-O-CF(CF3)]2- , and CF3-CF2-[CF2-O-CF(CF3)]3-.
12. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing hydroxyl and/or mercapto groups according to claim 1, wherein Z is a radical selected from the group consisting of , , , , , , , , , , , , , and .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4300800A DE4300800C2 (en) | 1993-01-14 | 1993-01-14 | Hydroxy and / or mercapto group-containing fluorinated carboxylic acid esters of phosphono- and phosphinocarboxylic acids, a process for their preparation and their use |
| DEP4300800.3 | 1993-01-14 |
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| Publication Number | Publication Date |
|---|---|
| CA2113239A1 true CA2113239A1 (en) | 1994-07-15 |
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|---|---|---|---|
| CA002113239A Abandoned CA2113239A1 (en) | 1993-01-14 | 1994-01-11 | Fluorinated carboxylic acid esters of phosphono-and phosphinocarboxylic acids containing hydroxyl and/or mercapto groups, a method for their preparation, and their use |
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|---|---|
| US (1) | US5424474A (en) |
| EP (1) | EP0606831B1 (en) |
| JP (1) | JP3310439B2 (en) |
| KR (1) | KR940018390A (en) |
| CN (1) | CN1042634C (en) |
| CA (1) | CA2113239A1 (en) |
| DE (2) | DE4300800C2 (en) |
| ES (1) | ES2133422T3 (en) |
| TW (1) | TW271447B (en) |
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| US6646088B2 (en) | 2000-08-16 | 2003-11-11 | 3M Innovative Properties Company | Urethane-based stain-release coatings |
| DE10101190A1 (en) * | 2001-01-12 | 2002-08-01 | Clariant Gmbh | Organo-silicon-free hydrophobicizing agents for building materials comprise powders containing a carboxylic acid ester, the powder preferably being re dispersible and polymer-containing |
| US6753380B2 (en) | 2001-03-09 | 2004-06-22 | 3M Innovative Properties Company | Water-and oil-repellency imparting ester oligomers comprising perfluoroalkyl moieties |
| US6803109B2 (en) | 2001-03-09 | 2004-10-12 | 3M Innovative Properties Company | Water-and oil-repellency imparting urethane oligomers comprising perfluoroalkyl moieties |
| US6890360B2 (en) | 2001-12-17 | 2005-05-10 | 3M Innovative Properties Company | Fluorochemical urethane composition for treatment of fibrous substrates |
| US20040147188A1 (en) * | 2003-01-28 | 2004-07-29 | 3M Innovative Properties Company | Fluorochemical urethane composition for treatment of fibrous substrates |
| US20070014927A1 (en) * | 2005-07-15 | 2007-01-18 | Buckanin Richard S | Fluorochemical urethane composition for treatment of fibrous substrates |
| US7459186B2 (en) | 2005-08-05 | 2008-12-02 | Wacker Chemical Corporation | Masonry sealing compositions comprising semi-crystalline ethylene-vinyl acetate polymer emulsions |
| WO2008147796A1 (en) * | 2007-05-23 | 2008-12-04 | 3M Innovative Properties Company | Aqueous compositions of fluorinated surfactants and methods of using the same |
| EP2444428B1 (en) * | 2007-06-06 | 2013-07-24 | 3M Innovative Properties Company | Fluorinated compositions and surface treatments made therefrom |
| JP5453250B2 (en) * | 2007-06-06 | 2014-03-26 | スリーエム イノベイティブ プロパティズ カンパニー | Fluorinated ether composition and method of using fluorinated ether composition |
| JP2010530445A (en) * | 2007-06-08 | 2010-09-09 | スリーエム イノベイティブ プロパティズ カンパニー | Blend of fluoroalkyl-containing ester oligomer and polydicarbodiimide (s) |
| CN101679229A (en) * | 2007-06-08 | 2010-03-24 | 3M创新有限公司 | Water- and oil-repellency imparting ester oligomers comprising perfluoroalkyl moieties |
| EA201100053A1 (en) * | 2008-07-18 | 2011-08-30 | 3М Инновейтив Пропертиз Компани | FLUORINATED ESSENTIAL COMPOUNDS AND METHODS OF THEIR APPLICATION |
| WO2010062843A1 (en) * | 2008-11-25 | 2010-06-03 | 3M Innovative Properties Company | Fluorinated ether urethanes and methods of using the same |
| CN102317403A (en) | 2008-12-18 | 2012-01-11 | 3M创新有限公司 | Method of contacting hydrocarbon-bearing formations with fluorinated ether compositions |
| WO2010080353A2 (en) | 2008-12-18 | 2010-07-15 | 3M Innovative Properties Company | Method of contacting hydrocarbon-bearing formations with fluorinated phosphate and phosphonate compositions |
| CN117004122A (en) * | 2023-09-04 | 2023-11-07 | 吴江市拓研电子材料有限公司 | High-temperature-resistant oil-resistant teflon ribbon and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2424243A1 (en) * | 1974-05-18 | 1975-11-27 | Bayer Ag | PERFLUORALKANE SULFONAMIDOALKANE PHOSPHONIC ACID OR - PHOSPHIC ACID DERIVATIVES |
| DE2439281A1 (en) * | 1974-08-16 | 1976-02-26 | Henkel & Cie Gmbh | Trifluoromethyl phosphono-butyric acid and derivs - for use as flame retardants,lubricant additives, hydrophobing agents, etc. |
| US4602092A (en) * | 1983-09-19 | 1986-07-22 | E. R. Squibb & Sons, Inc. | Method for making phosphinic acid intermediates |
| DE3605800A1 (en) * | 1986-02-22 | 1987-08-27 | Bayer Ag | 2-PHOSPHONOBUTAN-1,2,4-TRICARBONIC ACID DERIVATIVES AS EMULSIFIERS |
-
1993
- 1993-01-14 DE DE4300800A patent/DE4300800C2/en not_active Expired - Fee Related
- 1993-12-17 TW TW082110701A patent/TW271447B/zh active
- 1993-12-23 US US08/172,274 patent/US5424474A/en not_active Expired - Fee Related
-
1994
- 1994-01-03 ES ES94100003T patent/ES2133422T3/en not_active Expired - Lifetime
- 1994-01-03 EP EP94100003A patent/EP0606831B1/en not_active Expired - Lifetime
- 1994-01-03 DE DE59408219T patent/DE59408219D1/en not_active Expired - Fee Related
- 1994-01-10 JP JP01205594A patent/JP3310439B2/en not_active Expired - Fee Related
- 1994-01-11 CA CA002113239A patent/CA2113239A1/en not_active Abandoned
- 1994-01-13 KR KR1019940000456A patent/KR940018390A/en not_active IP Right Cessation
- 1994-01-14 CN CN94100611A patent/CN1042634C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR940018390A (en) | 1994-08-16 |
| US5424474A (en) | 1995-06-13 |
| TW271447B (en) | 1996-03-01 |
| DE4300800A1 (en) | 1994-07-21 |
| CN1042634C (en) | 1999-03-24 |
| CN1096788A (en) | 1994-12-28 |
| EP0606831A1 (en) | 1994-07-20 |
| JPH06279469A (en) | 1994-10-04 |
| ES2133422T3 (en) | 1999-09-16 |
| DE4300800C2 (en) | 1996-09-19 |
| DE59408219D1 (en) | 1999-06-17 |
| EP0606831B1 (en) | 1999-05-12 |
| JP3310439B2 (en) | 2002-08-05 |
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Legal Events
| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |