CA2113238A1 - Fluorinated carboxylic acid esters of phosphono-and phosphinocarboxylic acids containing acrylate and/or methacrylate groups, a method for their preparation, and their use - Google Patents
Fluorinated carboxylic acid esters of phosphono-and phosphinocarboxylic acids containing acrylate and/or methacrylate groups, a method for their preparation, and their useInfo
- Publication number
- CA2113238A1 CA2113238A1 CA002113238A CA2113238A CA2113238A1 CA 2113238 A1 CA2113238 A1 CA 2113238A1 CA 002113238 A CA002113238 A CA 002113238A CA 2113238 A CA2113238 A CA 2113238A CA 2113238 A1 CA2113238 A1 CA 2113238A1
- Authority
- CA
- Canada
- Prior art keywords
- radical
- carbon atoms
- linear
- groups
- branched
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 19
- 150000001733 carboxylic acid esters Chemical class 0.000 title claims abstract description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 6
- MEUIIHOXOWVKNP-UHFFFAOYSA-N phosphanylformic acid Chemical class OC(P)=O MEUIIHOXOWVKNP-UHFFFAOYSA-N 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000004078 waterproofing Methods 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 101150047265 COR2 gene Proteins 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 101100467189 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) QCR2 gene Proteins 0.000 claims 1
- 239000002253 acid Substances 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 13
- -1 perfluoro groups Chemical group 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 239000004519 grease Substances 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920000642 polymer Polymers 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
- 239000004753 textile Substances 0.000 description 2
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000385654 Gymnothorax tile Species 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005886 esterification 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
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 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
- 239000000123 paper Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- RYYVLZVUVIJVGH-UHFFFAOYSA-N trimethylxanthine Natural products CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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
- D06M13/322—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 nitrogen
- D06M13/44—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 nitrogen containing nitrogen and phosphorus
- D06M13/447—Phosphonates or phosphinates containing nitrogen 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
-
- 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
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
- D06M13/298—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing halogen atoms
Abstract
FLUORINATED CARBOXYLIC ACID ESTERS OF PHOSPHONO- AND
PHOSPHINOCARBOXYLIC ACIDS CONTAINING ACRYLATE AND/OR
METHACRYLATE GROUPS, A METHOD FOR THEIR PREPARATION, AND THEIR
USE
ABSTRACT
The present invention relates to fluorinated carboxylic acid esters of phosphonocarboxylic acids containing acrylate and/or methacrylate groups, their use as waterproofing or oil-repellency agents, and a method for their preparation.
PHOSPHINOCARBOXYLIC ACIDS CONTAINING ACRYLATE AND/OR
METHACRYLATE GROUPS, A METHOD FOR THEIR PREPARATION, AND THEIR
USE
ABSTRACT
The present invention relates to fluorinated carboxylic acid esters of phosphonocarboxylic acids containing acrylate and/or methacrylate groups, their use as waterproofing or oil-repellency agents, and a method for their preparation.
Description
- 1 - 2~,132~
:1 i, FLIJOE~INP.~ED CARBOXYLIC ACID E8TER8 OF PH08P~O~O~
il PIIOE~PIII~OCARBOXYLI~ AC!ID8 CO~lrAINING AC~YI.Aq!E A~TD/OR
~ETHACRYL.ATE GROtlPS, A NBq~lOD l?OR ~ IEIR PREPA~ATIVlil, AND T~
The present invention relates to fluorinated carboxylic acid esters of phosphonocarboxylic acidr,containing acrylate and/or :
methacrylate groups~ their use ac waterproofing and/or oil-repellency agents, and a method for their preparation.
Compounds containing perfluoroalkyl groups are widely used in impregnation agents in industry due to their waterproofing and oil-repellency properties (see Ullmann, Enzyklopadie dar technischen Chemie, Fourth Edition, ~976, Volume 11, page 644;
and ibid, Fifth ~dition, 1988, Volume A1~, pages 373-374).
Typical applications comprise their use as an impregnation agent ~or waterproofing and imparting oil-repellency to textiles (see Ullmann, Enzyklopadie der technischen Chemie, Fourth Edition~ 1983, Volume 23, page ~7), leather ~see Ullmann, Enzyklopadie der technischen Chemie, Fourth Edition, 1978, Volume 16, page 168) and paper (see J~No MeuBdoerffer and H. Niederpr~m, Chemikerzeitung 104 (1980~ 45-52).
Examples of proofing agents such as these comprise alcohols and acrylates containing per~luoro groups, or their polymer dispersions (see J.N. MeuBdoerffer and H. Niederpr~m,--Chemikerzeitung 104 (1980) 45-52; and Ullmann, Enzyklopadie der technischen Chemie, Fourth Edition, 1983, Volume 23, page 87). Routes for their synthesis are described by J.N.
:~ MeuBdoerffer and H. Niederpr~m in Chemikerzeitung 104 (1980) 45-52.
Le A 29 528 - FC
~" i ;''. ~ .
':
~323~
,, .
The perfluorinated compounds used as starting materials in the above-mentioned fluorinated surfactants are produced ~l industrially by three different routes:
a) electrochemical ~luorination;
., :~ b) telomerization of perfluorolefines, particularly ~ tetrafluoroethylene; and ~-., ~, 10 c~ oligomerization of tetra~luo:roethyl~ne.
! The above-mentioned methods of preparing perfluorinated : starting materials are very expensive on an industrial scale, ; which results in high manufacturing costs for the desired chemical compounds containing perfluoro groups.
;1 The object of the invention is to provide modified organic compounds containing fluoro groups which have waterproofing ` and/or oil-repellency properti~s, and which can be produced simply and inexpensiYely.
This object is achieved by means of the fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing acrylate and/or methacrylate groups according to the invention.
The present invention relates to fluorinated carboxylic acid esters o~ phosphono- or phosphinocarboxylir acids containing acrylate and/or methacrylate groups, of general formula (I):
O
O C~ ~ CH2 ) O--R ( I ), 3 5 / P--Z--C~ ( CH2 ) n--( ~ ) m--lrm~RF
HO O RH
' Le A 29 52~
', .
.
~ 3 - 2~132~8 . :
, where ~ A
:J, R1 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 1~
'l carbon atoms, or a ~luorinated, branched or linear `~ monomeric ether or polyether with 1 to 18 carbon atoms, , !
10 RH is a linear or branched alkyl radical with 1 to 10 carbon atoms, :, R is an acrylate group of structure ~-0-C--CH=CH~
1l 15 ll 'I o :1, ~! or a methacrylate group of structure , --o-C--cH=cH2 ji'`~ 20 ll l , Y represents a `I O O O
': C=O, S- , -V--S- or -~-C - group, , O :
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 . themsalves contain Cl to C10 alkyl groups or aryl groups as substituents, or Le A 29 528 : `
'~' : :.
,~,',~ , "~. :
.
4 _ 2~ L3238 .! 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 atoms with one or more substituent groups of ~i structure -PO2HR1, where R1 has the same meaning as above, . .
~ m may be 0 or 1, ,, 10 n is an integer from 0 to 6, o is an integer from 0 to 6, and , 15 R2 represents a hydroxyl radical, or a radical of structure O----(CH2)n--(N)m--Ym RF
, I
RH
~9 or a radical of structure O-(CH2)o~R, or , :
a linear or branched alkoxy radical with 1 to 30 carbon atoms, where n, m, o, R~, RF~ R and Y have the same 3 25 - meaning as above, and their salts.
The fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing acrylate and/or methacrylate groups are preferably those in which RF is a ! linear or branched fluoroalkyl radical with 3 to 10 carbon j atoms.
Fluorinated carboxylic acid esters of phosphono- or l~ phosphinocarboxylic acids containing acrylate and/or ¦ methacrylate groups, in which RH represents an alkyl radical j with one or two carbon atoms, are preferred.
~ Le A 29 528 ., _, . ~ .
.
,::
.
2113'~8 Fluorinated carboxylic acid esters of phosphono- or b phosphinocarboxylic acids containing acrylatA and/or methacrylate groups, in which n is one or two, are particularly pre~erred.
.~
Fluorinated carboxylic acid esters of phosphono or phosphinocarboxylic acids containing acrylate and/or methacrylate groups, in which o is one or two, are particularly preferred.
Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing acrylate and/or methacrylate groups, in which m is equal to -one , are particularly preferred.
, For example, particularly preferred fluorinated carboxylic acid esters o~ phosphono- or phosphinocarboxylic acids - containing acrylate and/or methacrylate groups have the ` following structure:
CH2--C ( ) ~CH2--CH2--N ( CH3 )--S2--C8F17 HO
/ P ~C - C(O)--O--~H2--CH2-N(CH3) - S2--~8F17 HO
1 ~
C~2--~C(O)----O----CH2----CH2----O----C(O)----CH=CH~
' .- ~
Le A 29 528 :.
! ' 6 2 l ~ 3 2 3 8 ... .
O CH2--C(O)----S----CH2--CH2--N(CH3)--S02--~C4Fg HO ll l P__C--C(O)--O--ClsH37 ,1 EIO/
~, fH2 `,'' 10 i CH2 -c(o~--o--cH2--cH2--o--c(o)--c(cH3)=cH2 ,~
., .
The radicals listed below are particularly preferred:
ExamPles of ~F
CF3-(CF2)2 !~; CF3-(CF2)3 j CF3-(CF2)5 :: 20 CF3-(CF2)6 CF3- ( CF2 ) 7 : C~3-(CF~
i~ CF3C6F4 H-(CF2)6 -(~F2)2-o-j : CF3-CF2-CF2-0-~F(CF3)-~; CF3-CF2-tCF2-O-cFlcF31]2-CF3-cF2-[cF2-o-cF(cF3~]
~: ExamELles of Z:
~: 35 CH-, C(CH3)-~
CH-CH2-, Le A_29 528 ., .
~r ~ }~
;3 ~ 7 - 2 1 ~ 3 ~ 3 ~
'' --CH2-CH--CH2- , ' 5 CH2-cH2-lH CH2-`;' \
lo CH--CH--P3H2 1 :1 1 ,, -CH2-C-CH2 CH2-COOH, , 15 1 :
!/ -CH2-C-cH2-cH2Po3H2r i 20 ;~ -CH2-C-CH~COOH)-CH2-COOH, , 25 ¦~ C~-cH ~-cH2- ~ :
3 30 -CH2-CH2-C-cH2~cH2-po3H2~ -~ . I I
C~2-C-CH2-CH2-CN , : 35 1 ~-,; HO-C(CH3)-ClH-cH2~ , ; .
I~ 40 --C~H2--N--CH2 ~: The fluorinated carboxylic acid esters of phosphono- or ~: phosphinocarboxylic a~ids containing acrylate and/or ~ethacrylate g:roups according to the invention may be prepared by multi-stage synthesis, employing esterification reactions of the corresponding phosphono- or phosphinocarboxylic acids Le A 29 528 :
'i,, ~ ` -` 21~3238 or their salts with alcohols containing fluoro groups and , hydroxy~unctional acrylic acid or methacrylic acid derivatives:
~,1 5 O 2-i O 11 5 `J 10 2 R~ AX+ + x HO~ ( CH2 ) n--~ N ) m Ym--RF
P--Z--C--O RH
HO O l 'l 15 X/2 O ~
3 20 ll ~1 O C--O
,~ p Z---c--o--(cH2)n- ~I)m Ym ~ A
~." H0 O R~
i :~ x ' 30 + (H)xA
'~' , ' ' -.
:
' ~ Le A 29 528 ~, . ...
3 2 ~ 8 .. j _ _ o .. 11 , 5 O C--O
P Z--C--O----( CH2 ~ n~~ ( N ) m~Ym~~RF AX+ .1 .l, / 11 1 1 :' HO O R~
-- J
'i .
+ X HO- (CH2~ o~R
`i 15 ,1 .~ O .
iY 11 . .
1 ~ O C O--(CH2)0 R
:1 i, FLIJOE~INP.~ED CARBOXYLIC ACID E8TER8 OF PH08P~O~O~
il PIIOE~PIII~OCARBOXYLI~ AC!ID8 CO~lrAINING AC~YI.Aq!E A~TD/OR
~ETHACRYL.ATE GROtlPS, A NBq~lOD l?OR ~ IEIR PREPA~ATIVlil, AND T~
The present invention relates to fluorinated carboxylic acid esters of phosphonocarboxylic acidr,containing acrylate and/or :
methacrylate groups~ their use ac waterproofing and/or oil-repellency agents, and a method for their preparation.
Compounds containing perfluoroalkyl groups are widely used in impregnation agents in industry due to their waterproofing and oil-repellency properties (see Ullmann, Enzyklopadie dar technischen Chemie, Fourth Edition, ~976, Volume 11, page 644;
and ibid, Fifth ~dition, 1988, Volume A1~, pages 373-374).
Typical applications comprise their use as an impregnation agent ~or waterproofing and imparting oil-repellency to textiles (see Ullmann, Enzyklopadie der technischen Chemie, Fourth Edition~ 1983, Volume 23, page ~7), leather ~see Ullmann, Enzyklopadie der technischen Chemie, Fourth Edition, 1978, Volume 16, page 168) and paper (see J~No MeuBdoerffer and H. Niederpr~m, Chemikerzeitung 104 (1980~ 45-52).
Examples of proofing agents such as these comprise alcohols and acrylates containing per~luoro groups, or their polymer dispersions (see J.N. MeuBdoerffer and H. Niederpr~m,--Chemikerzeitung 104 (1980) 45-52; and Ullmann, Enzyklopadie der technischen Chemie, Fourth Edition, 1983, Volume 23, page 87). Routes for their synthesis are described by J.N.
:~ MeuBdoerffer and H. Niederpr~m in Chemikerzeitung 104 (1980) 45-52.
Le A 29 528 - FC
~" i ;''. ~ .
':
~323~
,, .
The perfluorinated compounds used as starting materials in the above-mentioned fluorinated surfactants are produced ~l industrially by three different routes:
a) electrochemical ~luorination;
., :~ b) telomerization of perfluorolefines, particularly ~ tetrafluoroethylene; and ~-., ~, 10 c~ oligomerization of tetra~luo:roethyl~ne.
! The above-mentioned methods of preparing perfluorinated : starting materials are very expensive on an industrial scale, ; which results in high manufacturing costs for the desired chemical compounds containing perfluoro groups.
;1 The object of the invention is to provide modified organic compounds containing fluoro groups which have waterproofing ` and/or oil-repellency properti~s, and which can be produced simply and inexpensiYely.
This object is achieved by means of the fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing acrylate and/or methacrylate groups according to the invention.
The present invention relates to fluorinated carboxylic acid esters o~ phosphono- or phosphinocarboxylir acids containing acrylate and/or methacrylate groups, of general formula (I):
O
O C~ ~ CH2 ) O--R ( I ), 3 5 / P--Z--C~ ( CH2 ) n--( ~ ) m--lrm~RF
HO O RH
' Le A 29 52~
', .
.
~ 3 - 2~132~8 . :
, where ~ A
:J, R1 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 1~
'l carbon atoms, or a ~luorinated, branched or linear `~ monomeric ether or polyether with 1 to 18 carbon atoms, , !
10 RH is a linear or branched alkyl radical with 1 to 10 carbon atoms, :, R is an acrylate group of structure ~-0-C--CH=CH~
1l 15 ll 'I o :1, ~! or a methacrylate group of structure , --o-C--cH=cH2 ji'`~ 20 ll l , Y represents a `I O O O
': C=O, S- , -V--S- or -~-C - group, , O :
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 . themsalves contain Cl to C10 alkyl groups or aryl groups as substituents, or Le A 29 528 : `
'~' : :.
,~,',~ , "~. :
.
4 _ 2~ L3238 .! 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 atoms with one or more substituent groups of ~i structure -PO2HR1, where R1 has the same meaning as above, . .
~ m may be 0 or 1, ,, 10 n is an integer from 0 to 6, o is an integer from 0 to 6, and , 15 R2 represents a hydroxyl radical, or a radical of structure O----(CH2)n--(N)m--Ym RF
, I
RH
~9 or a radical of structure O-(CH2)o~R, or , :
a linear or branched alkoxy radical with 1 to 30 carbon atoms, where n, m, o, R~, RF~ R and Y have the same 3 25 - meaning as above, and their salts.
The fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing acrylate and/or methacrylate groups are preferably those in which RF is a ! linear or branched fluoroalkyl radical with 3 to 10 carbon j atoms.
Fluorinated carboxylic acid esters of phosphono- or l~ phosphinocarboxylic acids containing acrylate and/or ¦ methacrylate groups, in which RH represents an alkyl radical j with one or two carbon atoms, are preferred.
~ Le A 29 528 ., _, . ~ .
.
,::
.
2113'~8 Fluorinated carboxylic acid esters of phosphono- or b phosphinocarboxylic acids containing acrylatA and/or methacrylate groups, in which n is one or two, are particularly pre~erred.
.~
Fluorinated carboxylic acid esters of phosphono or phosphinocarboxylic acids containing acrylate and/or methacrylate groups, in which o is one or two, are particularly preferred.
Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing acrylate and/or methacrylate groups, in which m is equal to -one , are particularly preferred.
, For example, particularly preferred fluorinated carboxylic acid esters o~ phosphono- or phosphinocarboxylic acids - containing acrylate and/or methacrylate groups have the ` following structure:
CH2--C ( ) ~CH2--CH2--N ( CH3 )--S2--C8F17 HO
/ P ~C - C(O)--O--~H2--CH2-N(CH3) - S2--~8F17 HO
1 ~
C~2--~C(O)----O----CH2----CH2----O----C(O)----CH=CH~
' .- ~
Le A 29 528 :.
! ' 6 2 l ~ 3 2 3 8 ... .
O CH2--C(O)----S----CH2--CH2--N(CH3)--S02--~C4Fg HO ll l P__C--C(O)--O--ClsH37 ,1 EIO/
~, fH2 `,'' 10 i CH2 -c(o~--o--cH2--cH2--o--c(o)--c(cH3)=cH2 ,~
., .
The radicals listed below are particularly preferred:
ExamPles of ~F
CF3-(CF2)2 !~; CF3-(CF2)3 j CF3-(CF2)5 :: 20 CF3-(CF2)6 CF3- ( CF2 ) 7 : C~3-(CF~
i~ CF3C6F4 H-(CF2)6 -(~F2)2-o-j : CF3-CF2-CF2-0-~F(CF3)-~; CF3-CF2-tCF2-O-cFlcF31]2-CF3-cF2-[cF2-o-cF(cF3~]
~: ExamELles of Z:
~: 35 CH-, C(CH3)-~
CH-CH2-, Le A_29 528 ., .
~r ~ }~
;3 ~ 7 - 2 1 ~ 3 ~ 3 ~
'' --CH2-CH--CH2- , ' 5 CH2-cH2-lH CH2-`;' \
lo CH--CH--P3H2 1 :1 1 ,, -CH2-C-CH2 CH2-COOH, , 15 1 :
!/ -CH2-C-cH2-cH2Po3H2r i 20 ;~ -CH2-C-CH~COOH)-CH2-COOH, , 25 ¦~ C~-cH ~-cH2- ~ :
3 30 -CH2-CH2-C-cH2~cH2-po3H2~ -~ . I I
C~2-C-CH2-CH2-CN , : 35 1 ~-,; HO-C(CH3)-ClH-cH2~ , ; .
I~ 40 --C~H2--N--CH2 ~: The fluorinated carboxylic acid esters of phosphono- or ~: phosphinocarboxylic a~ids containing acrylate and/or ~ethacrylate g:roups according to the invention may be prepared by multi-stage synthesis, employing esterification reactions of the corresponding phosphono- or phosphinocarboxylic acids Le A 29 528 :
'i,, ~ ` -` 21~3238 or their salts with alcohols containing fluoro groups and , hydroxy~unctional acrylic acid or methacrylic acid derivatives:
~,1 5 O 2-i O 11 5 `J 10 2 R~ AX+ + x HO~ ( CH2 ) n--~ N ) m Ym--RF
P--Z--C--O RH
HO O l 'l 15 X/2 O ~
3 20 ll ~1 O C--O
,~ p Z---c--o--(cH2)n- ~I)m Ym ~ A
~." H0 O R~
i :~ x ' 30 + (H)xA
'~' , ' ' -.
:
' ~ Le A 29 528 ~, . ...
3 2 ~ 8 .. j _ _ o .. 11 , 5 O C--O
P Z--C--O----( CH2 ~ n~~ ( N ) m~Ym~~RF AX+ .1 .l, / 11 1 1 :' HO O R~
-- J
'i .
+ X HO- (CH2~ o~R
`i 15 ,1 .~ O .
iY 11 . .
1 ~ O C O--(CH2)0 R
2 0 R~
;I P--Z--C--O----(CH2)n--(N)m--Ym--RF
,1 HO O RE~ :
:~ 2 5 ~ + (EO)~A
.~ :
i where 30 R1~ R~ RF~ R~, Y, Z, m, n and o have the ~ame meaning ~s above, 1 ::
A is a hydrogen cation, an ammonium cation or a monovalent or polyvalent metal cation, and i: .
~'~: 35 x is an integer which corresponds to the charge of the cation j; A.
The present invention also relates to the use of the .-fluorinated carboxylic acid esters of phosphono- or phosphinocarhoxylic acids containing acrylate and/or methac~ylate groups according to the invention as : waterproo~ing agents and~or oil-repellency agents.
Le A 29 528 ;~}
21~323~
.~ -- 10 --ue to the waterproofing and oil-repellency properties of the - compounds according to the invention, they may be used as impregnating agents in various areas of application, whereby the compounds according to the invention may be applied as such or in the form of polymer dispersions, for example.
~' , For example, the compounds according to the invention may beused on natural and synthetic fibres (e.g. for textiles, carpets or awnings) to repel water, grease, oil and/or dirt.
;, 10 The compounds according to the invention may also be used on paper and cardboard (e.g. for packaging or fleeces)to repel water, grease, oil and/or dirt.
Moreover, the compounds according to the invention may be used ; on leatner (e.g. for upholstery, shoes or clothing) to repel water, grease, oil and/or dirt.
The compounds according to the invention may also be used on ceramics (e.g. tiles), on natural or artificial stone (e.g.
, sandstone), on wood ~e.~. the wooden cladding of facades) and `~ on plastics (e.gO polyesters) for impregnation against water, ~ grease, oil, dirt, algae gxowth and/or weathering.
ii 25 The invention will be described in more detail by means of the il~ following examples.
I
PIES '' ,.
1 x~mplel ¦ N-(2-hydroxyethyl~N-methyl-perfluorooctyl sulphonamide (0~4 mole/223 g) was dissolved in 150 ml 4-methyl-pentane-2-one in a three-necked flask fitted with a stirrer and a water trap, and 0.5 ml concentrated sulphuric acid was added.
Le A 29 528 2~3238 This solution was heated to about 116C. 2-phosphonobutane-i 1,2,4-tricarboxylic acid (0.2 mole/54 g) dissolved in 54 g water was then slowly added. A~ter the addition was complete, ~ the reaction mixture was refluxed with stirring until the ;~ 5 entire amount of water (~1.2 ml~ had been distilled off.
~1 .~ Hydroxyethyl acrylate (0.2 mole/23.2 g) was then slowly added, followed by stirring under reflux until the entire amount of , water (3O6 ml) had been disti.Lled o~f from the reaction `~i 10 mixture~
,, After the reaction was complete,-the solvent was distilled off il at 70C and 70 mbar, and the product obtained was completely ; driedO The yield of2-phosphonobutane-1,2,4-tricarboxylic acid which was triple-esterified with two equivalents of N-(2-hydroxyethyl)~N-methyl-perfluorooctyl sulphonamide and one equivalent o~ hydro~yethyl acrylate was 277 g (95.8 %
theoretical).
' : 20 Example 2 :
N-(2-hydroxyethyl)-N-methyl-perfluorobutyl sulphonamide (0.~
mole/71 g~ was dissolved in 150 ml 4-methyl pentane-2-on~ in a three-necked flask fitted with a stirrer and a water trap, and concentrated sulphuric acid ~0OS ml) was added. This solution was heated to about 116C. 2-phosphonobutane-1,2,4-tricarboxylic acid (0.2 mole/54 g) dissolved in 54 g water was then slowly added. After the addition was complete, the reaction mixture was refluxed with ~tirring until the entire amount of water (57.6 ml~ had been distilled off.
~' Octadecanol (0.2 mole/54 g~ dissolved in 50 ml 4-methyl-pentanQ-2-one was thein slowly added, followed by stirrin~
under Le A ~9 528 :i ~ :~
- 12 ~ 32 )~
reflux until the entire amount of water (3.6 ml) had been distilled off from the reaction mixture.
Hydroxyethyl methacrylate (0.2 mole/26 g) was then slowly added, followed by stirring under reflux until the entire amount of water (3.6 ml) had been distilled off from the reaction mixture.
After the reaction was complete, the solvent was distilled off ~;` 10 at 70C and 70 mbar, and the procluct obtained was completely dried. The yield of 2-phosphonobutane-1,2,4-tricarboxylic acid which was triple-estQrified with one equivalent each of N-(2-~' hydroxyethyl)-N-methyl-perfluorobutyl sulphonamide, octadecanol and hydroxyethyl methacrylate was 180 g (92.5 %
~ 15 theoretical).
i .1 .
Le A 29 528
;I P--Z--C--O----(CH2)n--(N)m--Ym--RF
,1 HO O RE~ :
:~ 2 5 ~ + (EO)~A
.~ :
i where 30 R1~ R~ RF~ R~, Y, Z, m, n and o have the ~ame meaning ~s above, 1 ::
A is a hydrogen cation, an ammonium cation or a monovalent or polyvalent metal cation, and i: .
~'~: 35 x is an integer which corresponds to the charge of the cation j; A.
The present invention also relates to the use of the .-fluorinated carboxylic acid esters of phosphono- or phosphinocarhoxylic acids containing acrylate and/or methac~ylate groups according to the invention as : waterproo~ing agents and~or oil-repellency agents.
Le A 29 528 ;~}
21~323~
.~ -- 10 --ue to the waterproofing and oil-repellency properties of the - compounds according to the invention, they may be used as impregnating agents in various areas of application, whereby the compounds according to the invention may be applied as such or in the form of polymer dispersions, for example.
~' , For example, the compounds according to the invention may beused on natural and synthetic fibres (e.g. for textiles, carpets or awnings) to repel water, grease, oil and/or dirt.
;, 10 The compounds according to the invention may also be used on paper and cardboard (e.g. for packaging or fleeces)to repel water, grease, oil and/or dirt.
Moreover, the compounds according to the invention may be used ; on leatner (e.g. for upholstery, shoes or clothing) to repel water, grease, oil and/or dirt.
The compounds according to the invention may also be used on ceramics (e.g. tiles), on natural or artificial stone (e.g.
, sandstone), on wood ~e.~. the wooden cladding of facades) and `~ on plastics (e.gO polyesters) for impregnation against water, ~ grease, oil, dirt, algae gxowth and/or weathering.
ii 25 The invention will be described in more detail by means of the il~ following examples.
I
PIES '' ,.
1 x~mplel ¦ N-(2-hydroxyethyl~N-methyl-perfluorooctyl sulphonamide (0~4 mole/223 g) was dissolved in 150 ml 4-methyl-pentane-2-one in a three-necked flask fitted with a stirrer and a water trap, and 0.5 ml concentrated sulphuric acid was added.
Le A 29 528 2~3238 This solution was heated to about 116C. 2-phosphonobutane-i 1,2,4-tricarboxylic acid (0.2 mole/54 g) dissolved in 54 g water was then slowly added. A~ter the addition was complete, ~ the reaction mixture was refluxed with stirring until the ;~ 5 entire amount of water (~1.2 ml~ had been distilled off.
~1 .~ Hydroxyethyl acrylate (0.2 mole/23.2 g) was then slowly added, followed by stirring under reflux until the entire amount of , water (3O6 ml) had been disti.Lled o~f from the reaction `~i 10 mixture~
,, After the reaction was complete,-the solvent was distilled off il at 70C and 70 mbar, and the product obtained was completely ; driedO The yield of2-phosphonobutane-1,2,4-tricarboxylic acid which was triple-esterified with two equivalents of N-(2-hydroxyethyl)~N-methyl-perfluorooctyl sulphonamide and one equivalent o~ hydro~yethyl acrylate was 277 g (95.8 %
theoretical).
' : 20 Example 2 :
N-(2-hydroxyethyl)-N-methyl-perfluorobutyl sulphonamide (0.~
mole/71 g~ was dissolved in 150 ml 4-methyl pentane-2-on~ in a three-necked flask fitted with a stirrer and a water trap, and concentrated sulphuric acid ~0OS ml) was added. This solution was heated to about 116C. 2-phosphonobutane-1,2,4-tricarboxylic acid (0.2 mole/54 g) dissolved in 54 g water was then slowly added. After the addition was complete, the reaction mixture was refluxed with ~tirring until the entire amount of water (57.6 ml~ had been distilled off.
~' Octadecanol (0.2 mole/54 g~ dissolved in 50 ml 4-methyl-pentanQ-2-one was thein slowly added, followed by stirrin~
under Le A ~9 528 :i ~ :~
- 12 ~ 32 )~
reflux until the entire amount of water (3.6 ml) had been distilled off from the reaction mixture.
Hydroxyethyl methacrylate (0.2 mole/26 g) was then slowly added, followed by stirring under reflux until the entire amount of water (3.6 ml) had been distilled off from the reaction mixture.
After the reaction was complete, the solvent was distilled off ~;` 10 at 70C and 70 mbar, and the procluct obtained was completely dried. The yield of 2-phosphonobutane-1,2,4-tricarboxylic acid which was triple-estQrified with one equivalent each of N-(2-~' hydroxyethyl)-N-methyl-perfluorobutyl sulphonamide, octadecanol and hydroxyethyl methacrylate was 180 g (92.5 %
~ 15 theoretical).
i .1 .
Le A 29 528
Claims (8)
1. Fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing acrylate and/or methacrylate groups, of formula (I) (I), wherein:
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 an acrylate group of structure or a methacrylate group of structure 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 atoms 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, o is an integer from 0 to 6, and R2 represents a hydroxyl radical or a radical of structure or a radical of structure O-(CH2)o-R, or a linear or branched alkoxy radical with 1 to 30 carbon atoms, where n, m, o, RH, RF 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 an acrylate group of structure or a methacrylate group of structure 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 atoms 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, o is an integer from 0 to 6, and R2 represents a hydroxyl radical or a radical of structure or a radical of structure O-(CH2)o-R, or a linear or branched alkoxy radical with 1 to 30 carbon atoms, where n, m, o, RH, RF and Y have the same meaning as above, and their salts.
2. Compounds according to claim 1, wherein RF is a linear or branched fluoroalkyl radical with 3 to 10 carbon atoms.
3. Compounds according to claim 1, wherein RH represents an alkyl radical with one or two carbon atoms.
4. Compounds according to claim 1, wherein n is one or two.
5. Compounds according to claim 1, wherein o is one or two.
6. Compounds according to claim 1, wherein m is equal to one.
7. A method of preparing the fluorinated carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing acrylate and/or methacrylate groups according to claim 1 in a multi-stage synthesis, comprising esterifying in a first step a phosphono- or phosphinocarboxylic acid of formula (II) (II) or its salt, wherein A is a hydrogen cation, an ammonium cation or a monovalent or a polyvalent metal cation, X is an integer which corresponds to the charge of the cation A, and R1 and Z are as defined in claim 1 with an alcohol containing fluoro groups of formula (III) (III), wherein n, m, RH, Y and RF have the meanings defined in claim 1, and is reacted in a further step with a hydroxyfunctional acrylic or methacrylic acid derivative of formula (IV) HO(CH2)o-R (IV) wherein R and o have the meanings defined in claim 1.
8. A waterproofing or oil-repelling agent comprising the carboxylic acid esters of phosphono- or phosphinocarboxylic acids containing acrylate and/or methacrylate groups as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4300799.6 | 1993-01-14 | ||
| DE4300799A DE4300799C2 (en) | 1993-01-14 | 1993-01-14 | Fluorinated carboxylic acid esters of phosphono- and phosphinocarboxylic acids containing acrylate and / or methacrylate groups, a process for their preparation and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2113238A1 true CA2113238A1 (en) | 1994-07-15 |
Family
ID=6478181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002113238A Abandoned CA2113238A1 (en) | 1993-01-14 | 1994-01-11 | Fluorinated carboxylic acid esters of phosphono-and phosphinocarboxylic acids containing acrylate and/or methacrylate groups, a method for their preparation, and their use |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5414102A (en) |
| EP (1) | EP0606833B1 (en) |
| JP (1) | JP3310438B2 (en) |
| KR (1) | KR940018391A (en) |
| CN (1) | CN1042635C (en) |
| CA (1) | CA2113238A1 (en) |
| DE (2) | DE4300799C2 (en) |
| ES (1) | ES2110123T3 (en) |
| TW (1) | TW280830B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6646088B2 (en) | 2000-08-16 | 2003-11-11 | 3M Innovative Properties Company | Urethane-based stain-release coatings |
| 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 |
| WO2007146875A2 (en) * | 2006-06-15 | 2007-12-21 | Dow Global Technologies Inc. | Functionalized olefin interpolymers, compositions and articles prepared therefrom, and methods for making the same |
| US8338517B2 (en) * | 2007-05-23 | 2012-12-25 | 3M Innovative Properties Company | Aqueous compositions of fluorinated surfactants and methods of using the same |
| WO2008154345A1 (en) * | 2007-06-06 | 2008-12-18 | 3M Innovative Properties Company | Fluorinated ether compositions and methods of using the same |
| CN101679548B (en) | 2007-06-06 | 2012-07-18 | 3M创新有限公司 | Fluorinated compositions and surface treatments made therefrom |
| US8993116B2 (en) * | 2007-06-08 | 2015-03-31 | 3M Innovative Properties Company | Blends of fluoroalkyl-containing ester oligomers with polydicarbodiimide(S) |
| JP2010529263A (en) * | 2007-06-08 | 2010-08-26 | スリーエム イノベイティブ プロパティズ カンパニー | Water- and oil-repellent ester oligomers containing perfluoroalkyl moieties |
| EA201100053A1 (en) * | 2008-07-18 | 2011-08-30 | 3М Инновейтив Пропертиз Компани | FLUORINATED ESSENTIAL COMPOUNDS AND METHODS OF THEIR APPLICATION |
| CN102282191A (en) * | 2008-11-25 | 2011-12-14 | 3M创新有限公司 | Fluorinated ether urethanes and methods of using the same |
| US9057012B2 (en) | 2008-12-18 | 2015-06-16 | 3M Innovative Properties Company | Method of contacting hydrocarbon-bearing formations with fluorinated phosphate and phosphonate compositions |
| 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 |
| CN102311455A (en) * | 2011-05-19 | 2012-01-11 | 张春华 | Radiation-curable polyfunctional (meth)acrylic ester combination containing phosphonic group and preparation method thereof |
| US8859098B2 (en) * | 2012-05-18 | 2014-10-14 | Lord Corporation | Acrylic adhesion promoters |
| CN103695578B (en) * | 2013-12-30 | 2017-01-11 | 青昊环保科技（上海）有限公司 | Leather water-proof curing agent and preparing method thereof |
| US10167356B2 (en) | 2014-12-18 | 2019-01-01 | 3M Innovative Properties Company | Fluorinated polymers comprising phosphonic moieties |
| CN105986344B (en) * | 2015-02-02 | 2019-02-15 | 福建省泉州海丝船舶评估咨询有限公司 | A kind of production method of waterproof and breathable monofilament fabric |
| CN116063207A (en) * | 2022-12-22 | 2023-05-05 | 浙江大学 | Amphiphilic lipid containing N-tertiary amine oxide group, liposome drug delivery system and application |
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| 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 DE4300799A patent/DE4300799C2/en not_active Expired - Fee Related
- 1993-12-17 TW TW082110694A patent/TW280830B/zh active
- 1993-12-27 US US08/172,751 patent/US5414102A/en not_active Expired - Fee Related
-
1994
- 1994-01-03 DE DE59404795T patent/DE59404795D1/en not_active Expired - Fee Related
- 1994-01-03 EP EP94100005A patent/EP0606833B1/en not_active Expired - Lifetime
- 1994-01-03 ES ES94100005T patent/ES2110123T3/en not_active Expired - Lifetime
- 1994-01-10 JP JP01205494A patent/JP3310438B2/en not_active Expired - Fee Related
- 1994-01-11 CA CA002113238A patent/CA2113238A1/en not_active Abandoned
- 1994-01-13 KR KR1019940000457A patent/KR940018391A/en not_active IP Right Cessation
- 1994-01-14 CN CN94100612A patent/CN1042635C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06279468A (en) | 1994-10-04 |
| US5414102A (en) | 1995-05-09 |
| CN1042635C (en) | 1999-03-24 |
| CN1097762A (en) | 1995-01-25 |
| EP0606833A1 (en) | 1994-07-20 |
| DE59404795D1 (en) | 1998-01-29 |
| TW280830B (en) | 1996-07-11 |
| JP3310438B2 (en) | 2002-08-05 |
| ES2110123T3 (en) | 1998-02-01 |
| KR940018391A (en) | 1994-08-16 |
| DE4300799A1 (en) | 1994-07-21 |
| DE4300799C2 (en) | 1996-09-19 |
| EP0606833B1 (en) | 1997-12-17 |
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