CA1129429A - Fluorinated nonionic surfactants - Google Patents
Fluorinated nonionic surfactantsInfo
- Publication number
- CA1129429A CA1129429A CA317,372A CA317372A CA1129429A CA 1129429 A CA1129429 A CA 1129429A CA 317372 A CA317372 A CA 317372A CA 1129429 A CA1129429 A CA 1129429A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- oxide
- perfluoroalkyl
- formula
- straight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3342—Polymers modified by chemical after-treatment with organic compounds containing sulfur having sulfur bound to carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Silicon Polymers (AREA)
- Lubricants (AREA)
Abstract
Abstract Perfluoroalkylthio-substituted half esters and amides of succinic acid having the formula or its isomer, wherein Rf is perfluoroalkyl, R1 alkylene, optionally interrupted with oxygen, sulfur or nitrogen atoms, X is oxygen or NH, y is zero or 1, Q is a polyether or polyester diradical moiety having a molecular weight of 300 to 5000 or a polysiloxane having 5 to 90 re-peating units and A is hydrogen, hydroxyl, amino, alkoxy, phenoxy, al-kylphenoxy, dialkylamino, the group or its isomer.
Said compounds being prepared by reacting e.g. maleic anhydride with a polyether, polyester, diamine or a polysiloxane derivative of an alcohol or a primary amine and then reacting the product with a per-fluoroalkyl alkylene thiol. The novel compounds are useful as surfac-tants with specific applications as wetting agents in coatings waxes, emulsions, paints and resins.
Said compounds being prepared by reacting e.g. maleic anhydride with a polyether, polyester, diamine or a polysiloxane derivative of an alcohol or a primary amine and then reacting the product with a per-fluoroalkyl alkylene thiol. The novel compounds are useful as surfac-tants with specific applications as wetting agents in coatings waxes, emulsions, paints and resins.
Description
United States Patent 3,621,059 (Bartlett), issued November 1971, describes amides derived from hexafluoropropylene oxide polymer acids and poly-alkylene oxide having the formula RfO[CF(CF3)CF2O]n(CF3)CFCON-R O(CHR2CHR3O)yR
wherein Rf is a perfluoroalkyl radical having one to eight carbon atoms, n is an integer of zero to 100; Rl is an alkylene radical having tWD to 12 carbon atoms;
R2 is hydrogen or an alkyl radical having one to four carbon atoms; R3 is hydro-gen or an alkyl radical having one to four carbon atoms, at least one of R2 and R3 in each repeating unit being hydrogen; y is an integer of one to 60; R4 is hydrogen or an alkyl radical having one to four carbon aboms, and R5 is hydrogen or an alkyl radical having one to six carbon atams. These amides function effic-iently as surfactants and emulsifying agents. All these surfactants are derived from hexafluoropropylene oxide.
United States Patent Specification No. 2,915,554 (Ahlbrecht et al) issued December 1959, discloses perfluoro alkanesulfonamides having the formula
wherein Rf is a perfluoroalkyl radical having one to eight carbon atoms, n is an integer of zero to 100; Rl is an alkylene radical having tWD to 12 carbon atoms;
R2 is hydrogen or an alkyl radical having one to four carbon atoms; R3 is hydro-gen or an alkyl radical having one to four carbon atoms, at least one of R2 and R3 in each repeating unit being hydrogen; y is an integer of one to 60; R4 is hydrogen or an alkyl radical having one to four carbon aboms, and R5 is hydrogen or an alkyl radical having one to six carbon atams. These amides function effic-iently as surfactants and emulsifying agents. All these surfactants are derived from hexafluoropropylene oxide.
United States Patent Specification No. 2,915,554 (Ahlbrecht et al) issued December 1959, discloses perfluoro alkanesulfonamides having the formula
(2) RfS2-N-R
in which Rf is a perfluoroalkyl group having fram four to twelve carbon atoms;
R6 ls a member of the group consisting of hydrogen, lower alkyl radicals and R6 an~ R7 is a polyoxyalkyl group having the formula Rl"
in which Rf is a perfluoroalkyl group having fram four to twelve carbon atoms;
R6 ls a member of the group consisting of hydrogen, lower alkyl radicals and R6 an~ R7 is a polyoxyalkyl group having the formula Rl"
(3) -(OEl2)m (OCH2CH)n O R"
in which m is an integer fram 2 to 3, n is a number from 2to about 20, and each R"
is hydrogen or a methyl radical.
These sulfonamides serve as surface-active agents. The presence of an SO2 group is required in all cases.
.;j ~ ~
~9429 Other nonionic fluorochemical surfactants have been described in German Offenlegungsschriften 2215388 (Houghton et al) and 2261681 (Naik et al), . published March 1972 and December 1972, respectively.
It has now been found that a large variety of useful nonionic fluorinated surfactants can easily be prepared without the necessity of an aIkylation reaction and without the need for preparing an inter-- 2a -ll~9~Z9 mediate perfluoroalkyl substituted acid, by base cataly~ed addition of an Rf-substituted thiol to the maleic or fumaric half ester or half amide containing a hydrocarbon, polyethylene oxide or polysiloxane group in the ester or amide moiety. It is a further advantage, and contributing to the superiority of these no-Jel compounds, that they can be especially tailored for specific systems, that is, their compa-tibility with a given system, be it aqueous or organic, can be optimi-zed, and even structural elements can be matched, by selecting the proper nonionic derivative for the synthesis.
Synthesis of these novel surfactants is conveniently carried out in two steps: the first involves the ring-opening reaction of maleic anhydride with a polyether, polyester diol, diamine or polysiloxane derivative which may be either an alcohol or a primary amine [and may also contain hydrophobic segments such as aliphatic or aromatic hydro-carbon groups or polypropylene oxide segments]. The second step con-sists of a base catalyzed addition of a perfluoroalkyl substituted thiol onto the maleic double bond, carried out in a suitable solvent or in bulk.
The novel surfactants contain a carboxy group and are soluble in dilute mineral acid solution and thus behave like non-ionic surfac-tants. At basic pH, the carboxy groups contribute to increased solu-bility.
This invention is directed to the perfluoroalkyl substituted half esters and amides having the formula (4a) Rf-Rl-s(cH2)ycH-co-x-Q-A
or ~4b) Rf-Rl-S(CH2)yCH~COOH
CH2-co-~-Q-A
wherein Rf is straight or branched chain perfluorcalkyl of A to 18 carbon atoms or said ~e~fluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, Rl is branched or straight chain alXylene cf 1 to 12 carbon atoms, alkylenethioalkylene of 2 to 12 carbon atoms, al-
in which m is an integer fram 2 to 3, n is a number from 2to about 20, and each R"
is hydrogen or a methyl radical.
These sulfonamides serve as surface-active agents. The presence of an SO2 group is required in all cases.
.;j ~ ~
~9429 Other nonionic fluorochemical surfactants have been described in German Offenlegungsschriften 2215388 (Houghton et al) and 2261681 (Naik et al), . published March 1972 and December 1972, respectively.
It has now been found that a large variety of useful nonionic fluorinated surfactants can easily be prepared without the necessity of an aIkylation reaction and without the need for preparing an inter-- 2a -ll~9~Z9 mediate perfluoroalkyl substituted acid, by base cataly~ed addition of an Rf-substituted thiol to the maleic or fumaric half ester or half amide containing a hydrocarbon, polyethylene oxide or polysiloxane group in the ester or amide moiety. It is a further advantage, and contributing to the superiority of these no-Jel compounds, that they can be especially tailored for specific systems, that is, their compa-tibility with a given system, be it aqueous or organic, can be optimi-zed, and even structural elements can be matched, by selecting the proper nonionic derivative for the synthesis.
Synthesis of these novel surfactants is conveniently carried out in two steps: the first involves the ring-opening reaction of maleic anhydride with a polyether, polyester diol, diamine or polysiloxane derivative which may be either an alcohol or a primary amine [and may also contain hydrophobic segments such as aliphatic or aromatic hydro-carbon groups or polypropylene oxide segments]. The second step con-sists of a base catalyzed addition of a perfluoroalkyl substituted thiol onto the maleic double bond, carried out in a suitable solvent or in bulk.
The novel surfactants contain a carboxy group and are soluble in dilute mineral acid solution and thus behave like non-ionic surfac-tants. At basic pH, the carboxy groups contribute to increased solu-bility.
This invention is directed to the perfluoroalkyl substituted half esters and amides having the formula (4a) Rf-Rl-s(cH2)ycH-co-x-Q-A
or ~4b) Rf-Rl-S(CH2)yCH~COOH
CH2-co-~-Q-A
wherein Rf is straight or branched chain perfluorcalkyl of A to 18 carbon atoms or said ~e~fluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, Rl is branched or straight chain alXylene cf 1 to 12 carbon atoms, alkylenethioalkylene of 2 to 12 carbon atoms, al-
4~9 kyleneoxyalkylene of 2 to 12 carbon atoms or slkyleneiminoalkylene of 2 to 12 carbon atoms where tke nitrogen atom contains as a third sub-stituent, hydrogen or alkyl of 1 to 6 carbon atoms, X is oxygen or NH, y is 1 or zero, Q is a polyether or polyester diradicalmoiety having a molecular weight of 300 to 5000 or a polysiloxane having 5 to 80 re-peating units, and A is hydrogen, hydroxyl, alkoxy of 1 to 21 carbon atoms, phenoxy, alkylphenoxy of 7 ~o 24 carbon atoms, preferably of 7 to 20 carbon atoms, or the group of the formula (5a) Rf-Rl-s(cH2)ycH-co-x-or (5b) Rf-Rl-S(CH2)yCH~COOH
wherein Rf, Rl, X and y have the indicated meanings.
The phenoxy radical (A) may contain one or more than one alkyl substituent, and is e.g. methylphenoxy, octylphenoxy, nonylphenoxy or dinonylphenoxy.
Preferably Rf is a straight or branched chain perfluoroalkyl of 4, preferably 6 to 12 carbon atoms, Rl is alkylene of 1 to 6 car-bon atoms and most preferably ethylene, y is zero, Q is polyalkylene oxide moiety having from 10 to 50 repeating units, such as polyethyle-ne oxide, A is hydroxyl, methoxy or alkylphenoxy of 7 to 15 carbon atoms and X is -O- or -NH- most preferably -O-.
The compounds of this invention can be conveniently prepared by a two-step method. The first step consists of a condensation reac-tion of an alcohol, diol, amine or a diamine of the formula A-Q-X-H, wherein A, Q and X have the indicated meanings with maleic or itaco-nic anhydride to yield intermediates of formulae (6) A-Q-X-CO-CH=CH-COOH
or (7) A-Q-x-co-6-cH2-cooH
\
112~4Z~
Said intermediates can also be prepared through transesterifica-tion with lower-alkyl esters of maleic, fumaric or itaconic esters such as mono- and dimethyl esters of maleic fumaric or itaconic acids.
The most useful starting material for the intermediate of formula (6) is maleic anhydride. Methyl-maleic acid and chloromaleic acid deriva-tives can be used in the process of this invention, but give unprac-tically low yields of the desired end-~roduct.
In the second step a base catalyzed addition reaction of a per-fluoroalkyl alkylene thiol of the formula Rf-Rl-SH and an intermedia-te of formula (6) or (7) is carried out.
The group Q is a polyether, polyester or siloxane diradical. Fol-lowing are illustrative examples of polyether diradicals:
~-~cH2cH2o]ncH2cH2 n = 4 - 100 ----~CH-CH2-0] ~[CH2CH2-] [CH2-CH_o]~ CH2CH_ ~ + ~1= 2 - 40 CH3 CH3 n = 4 - 50 tCH2CH20] n[CH2CH-O]~ -[CH2CH20]n CH2CH2- n + nl= 2 - 20 3 i~ = 4 - 40 R3-N~ CH2CH2-o) nC~2CH2--~2 n = 2 - 20 R3 = alkyl of C-atoms --tCH2CH-O)m-CH2CH- m = e - 50 [CH2CH2C~2ca20] xCH2CH2CH2 ~ x = 2 _ cO
Examples of polyester-diol diradicals are those derived from diacids and diols, for instance alkylene glycol polyadipate, polyse-bacate, polyisopthalate, polyorthopthalate, polyterephthalate, poly-maleate, polyglutarate and the like; such polyester diOlâ may be ba-sed on a mixture of several diols and diacids and are commercially availalbe as polyurethane prepolymers in a molecular welsht range f~om 400 - ~000.
.
112~42~
Examples of pol~ ~siloxanes are such o formulae (8) la3 IH3 IH3 22 Y'l ;Si~ 0 1 2 2 y y + yl = 26 CH3 ~CH3 CH3 ~ CH ~
(9) ~ Si(CH3)3 f ~ I IH3 ~ 1 3 1 3 H ~ HCH~ O Si 0 ¦ 2 )1 4 1-4 CH3 ~, ¦ ~CH ~
0 ~Si-~ - Si(CH3)3 C~3 X3 Xl + X2 + X3 about 8 Examples of the alcohols, diols and amines useful in the prepara-tion of intermediates (6) and (7) are listed below:
- polyethylene oxide, MW 200 - 5000, preferably 400 - 2000;
- polypropylene oxide, MW 200 - 5000, preferably 400 - 2000;
- methoxy polyethylene oxide, MW 400 - 25000, prererably 400 - 2000;
- poly-tetramethylene oxide, MW 3000 - 6000;
- poly(ethylene-co-propylene oxide) block polymers, such as polypropoxy-(10-50 repeating units)-bispolyethoxy-(10-20) diol or polyethoxy-(10-50)-bis-polypropoxy (10-50)-diol;
- ethoxylated alkyl phenol where alkyl is octyl or monyl and the etho-xylated group contains from 5 to 50 ethylene oxide units, - ethoxylated primary and secondary amLnes of 8 to 20 carbons, - ethoxylated fatty acids and amides of 8 to 20 c~rbons, alkoxylated alcohols and diols of 8 to 20 carbons, bis(2-amino pr~pyl)ethers o.~
polyethylene oxide and poly~ropylene oxide, - Siloxane diols and triols, etkoxylated merca~tans of 8 .o 20 carbor.s.
4Z~
The p~rfluoroalkyl thiols employed in the preparation of the com-pounds of this invention are well known in the prior art. For example, thiols of the formula Rf-Rl-SH have been described in a number of United States patents in-cluding United States Patents 2,894,991 issued July 1959 to Barr et al, 2,961,470 issued November 1960 to Sheppard, 2,965,677 issued December 1960 to Harris, 3,088,849 issued May 1963 to Friedlaender, 3,172,910 issued March 1965 to Brace, 3,544,663 issued December 1970 to Hauptschein et al, and 3,655,732 issued April 1972 to Rondestvedt.
Thus, United States Patent 3,655,732 discloses mercaptans of formula (10) R Rl SH
where R is alkylene of 1 to 16 carbon atoms and Rf is perfluoroalkyl and teaches that halides of formula Rf-Rl-hal are well known; reaction of RfI with ethylene under free-radical conditions gives Rf(CH2CH2)aI while reaction of RfCH2I with ethylene gives RfCH2(CH2CH2)aI as is further taught in United States Patent 3,088,849, United States Patent 3,145,222 issued August 1964 to Brace, United States Patent 2,965,659 issued December 1960 to Tiers, and United States Patent 2,972,638 issued February 1961 to Tiers.
United States Patent 3,655,732 further disclo æs compounds of fonmula (11) R_Rl_X_Rll_SH
where R and Rll are alkylene of 1 to 16 carbon atoms, with the sum of the carbon atoms of Rl and Rll being not greater than 25; Rf is perfl~oroalkyl of 4 through 14 carbon atoms ar.d X is -S- or NR"'- where R"' is hydrogen or alkyl of 1 through 4 carbon atoms.
United States Patent 3,544,663 teaches that the mercaptans of formula (12) RfCH2OEI2SH
where Rf is perfluoroalkyl of 5 to 13 carbon atcms, can be prepared by reacting the perfluoroalkyl alkylene iodide with thiourea or by adding H2S to a perfluoro-alkyl substituted ethylene (Rf-CH-CH2), which in turn can be prepared by dehydro-hylogenation of the halide Rf-CH2CH2-hal.
The reaction of the iodide Rf-Rl-I with thiourea followed by hydro-lysis to obtain the mercaptan Rf-R -SH is the preferred synthetic route. The reaction is applicable to both linear and branched chain iodides. Many useful perfluoroalkoxyalkyl iodides are described in United States Patent 3,S14,487 (Anello et al), issued May 1970 of general fonmula (13) (CF3)2CFCcF2cF2(cH2cH2)m where m is 1 - 3.
Particularly preferred herein are the thiols of formula (14) RfCH2CH2SH
where Rf is perfluoroalkyl of 6 to 12 carbon atoms. These Rf-thiols can be pre-pared from RfCH2CH2I and thiourea in very high yield.
Illustrative examples of preferred perfluoroalkylalkylenethiols are:
CloF21CH2CH2SH
CF3 ~
CFO(CH2CH2)l_3-cH2c~l2s Especially preferred perfluoroalkylalkylenethiols are:
CloF21CH2CH2SH
and ~uxtures thereof.
, 4~
Synthesis of the novel nonionic surfactants is most conveniently carried out in tWD steps: the first step consists of reacting the eyclie anhydride, most commonly maleic anhydride, with the hydroxy or amlno substituted nonionic com~ound either in bulk or in a ccmmon dry and aprotie solvent; useful solvents include ketones, such as acetone - 8a -c, g and methylethyl ketone; ethers, such as diethylether or ethylene gly-col - dimethylether, or tetrahydrofuran; esters, such as ethyl acetate or methyl cellosolve acetate; amides, such as dimethylformamide or N-methyl pyrrolidone. While amines react rapidly at room temperature, hydroxy compounds have to be heated for several hours to 50 - 100 c.
The second step involves addition of the perfluoroalkyl alkylene thiol to the intermediate maleic half ester or half amide in the presence of basic catalysts, such as triethylamine, pyridine, or tetramethyl ammo-nium hydroxide. Addition of the thiol to the mixture often leads to he-terogeneous, 2-phase system, which will turn into a homogeneous solu-tion, as the reaction proceeds. This reaction step is preferably car-ried out between 30 and 75 C under a nitrogen blanket and with good stirring.
The compounds of this invention can also be prepared by rever-sing the order of reactions described above; that is, first carry out the base catalyzed addition of a perfluoro substituted thiols to ma-leic anhydride followed by the ring opening with the hydroxy or amino substitute nonionic compound.
Such fluorochemical surfactants are useful to improve or im-part properties such as: wetting, penetration, spreading, levelling, foam stability, flow properties, emulsification, dispersion, and oil and water repellency. Based on these unique properties are numerous applications, some of which follow. Although applications are sugges-ted for a particular use area, the general applicability of each con-cept is inferred for other applications.
PLASTICS AND RUBBER INDUSTRY
- Emulsifying agent for polymerization, particularly fluoromonomers - As a latex stabilizer - To aid in the preparation of agglomerates of powdered fluorocarbon polymers - In synergistic mixtures with hydrocarbon surfactants to wet low energy surfaces including natural anc synthetic rubbers,resins, plastics - As an adjuvant for foam applications and as foaming agents to aid in t4Z~
leak detection - As a foam additive to control spreacing, crawling, edge buildup - As mound release agents, for silicones, etc.
- In refractory processes - As an anti-mist film former - Additive for elimination of trapped air in plastic laminates - Wetting agent for resin molds for definition, strength - ~ot-melt additive for oil and grease repellency - Resin additive for improved wetting of and bonding with fillers - ~low modifier for extruding hot melts: spreading, uniformity, anti-cratering - ~djuvant for resin etchant - Mold release agent, demoulding agent - Retarder for plasticizer migration or evaporation - Internal antistatic agent for polyolefins - Antiblocking agent for polyolefins PETROLEUM INDVSTR~
- As a film evaporation inhibitor for gasoline, jet fuel, solvents, hy-drocarbons - In extreme pressure lubricants TEXTILE AND LEAT~ER INDUSTRIES
- Soil release and soil proofing agent - OiL/water repellent textile and leather treatment - Wetting agent to improve coverage and penetration of pores of sub-strates - Anti-foaming agent in textile treatment baths - Wetting agent for finish-on-yarn uniformity - Penetrating agent for finishes on tow, heavy denier fibers - Emulsifying agen V lubricant/for fiber finishes - Cleaner/metal treating agent for polymerization equipment - Flow modifier for spinning of hot melts, sol~7tions .
- Additive for fabric finishes for spreading, uniformity - Wetting agent for dyeing - Penetration aid for bleaches - Wetting agent for binder in nonwoven fabrics PAINT, PIGMENT AND FINIS~ING INDUSTRI~S
- Levelling, anti-catering adjuvant for finishes and paints - Adjuvant for control of soiling - Agent to control differential evaporation of solvents - Levelling agent for floor waxes - Adjuvant for waxes to improve oil and water repellency - Adhesion improver for oily or greasy surfaces - To combat pigment flotation problems - Improver for automotive finishes, based on water-based coatings in which the pigments are rendered non reactive - Pigment grindlng aid to promote wetting, dispersion, color develop-ment - Foam generator substance for the application of dyes, nks - Electrolytic conversion coatings MINING AND METALWORKING INDUS~RIES
- In cleaning agents for property improvement - Additive for solvent cleaning - Additive for metal pickling baths to increase bath life and acid runoff - Additive for chrome electroplating: surface tension reduction, foaming - Additive for ~oldering flux, especLally ror electronic circuitry - Protective agent for coatings (tarnish resistance, grease repellen-cy) - Corrosion inhibitor - Additive for etchant solution for improved definition - Plastic preplate and silicon etchant technology - In soldering flux for microelectronics to reduce foaming - In chemical roughing agent solutions, prior to galvznization - As a colloidal dispersion aid for magnetic solids - Protective coatings ror aluminum ar.d as an anti-blocking agent 1~2~29 - Wetting agent for leaching copper ores and as a fresh flotation agent- To promote ore wetting:and quicker breaking of the protective oxide layer P~A2MACEUTICAL INDUSTRY
_ _ - Improve the properties and penetration of anti-microbial agents - Improve the properties of biochemicals, biocides, algicides, bacte-riocides, and bacteriostats - Improve the strength, homogeneity, and reduce the permeability of encapsulated materials - Emulsify fluorochemical blood substituted AGRICULTURE AND FORESTRY
- Wetting agent for herbicides, fungicides, weed killers, hormone growth regulators, parasiticides, insecticides, germicides, bacte-ricides, nematocides, microbiocides, defolients and fertilizers - As an ingredient in chemosterilents, insect repellents and toxicants - For wettable powder pesticides and chemical powders - Corrosion inhibitor for chemical applicators - Wetting agent for foliage - Wetting additive for live stoc~ dips, or to wet sheep skins during desalination - Wetting ad~uvant for manufacture of pl~wood veneer - Penetrant for preservative impregnation - Pulping aid - For cleaning tubes in paper making, dyeing - Grease~oil repellents for paper FIRE FIGHTING
_ __ __ - Wetting agent for fighting forest fires - Ingredlent of AFFF (aqueous film forming foams) extinguishing agents - Component of fluoroprotein foams - Additives to dry chemical extinguishing agents - Agent in aerosol-type extinguishers - Wetting agent for sprinkler water AUTOMOTIVE, BUILDING MAINTENANDE AND CLEANING
- Wetting agent for cleaning composi~ions - Additive for alkaline cleaners 1~2~425~
- Glass cleaner - Wetting agent for automobile waxes - Adjuvant to improve oiL/water repellency of wax - Lubrican Vcorrosion inhibitor for antifreeze - Rinse-aid for car washes - In dry cleaning compositions and solvent cleaners, for water displa-cement and foaming. May improve soil suspension and decrease redepo-sition - Foaming agents for pipe cleaning - Anti-mist film foamer for glass and plastics - In _oams for dust supression - For acidic concrete cleaners - Bubble foamer for air tracing, in ventilating systems HOUSEHOLD, COSMETIC AND PERSONAL PRODUCTS
- Rinse-aid for dishwashing - Liquid polishing compositions - Floor polish leveling ~gent - Additive for alkaline oven cleaners - Synergistic improver for disinfectants - Carpet cleaners - Synergistic wetting agent in detergent formulations - Additive for protective coatings on metals (tarnish resistance, grease resistance) - Gloss and antistatic improver - ~air shampoo ingredient - Shaving form Lngredient - Oil and water repellent cosmetic powders ingredient - Ingredient of lotions or creams for skin or hair - Ingredient of skin protection creams PHOTOGRAPHY AND GRAPHIC ARTS
- Printing ink additive for ink flow and levelling, both aqueous and solvent based - Wetting asent for writing inks - To combat pigment flooding and flotation in printing inks - To form ink repellent surfaces for waterless litnoplates, or elec-trographic coatings - Prevent reticulation of gelatin layers and improve uniformity - Assist in film drying - Improve film coatings and reduce "contraction flec.~s"
- Wetting, levelling, anti-cratering assi,t agent - Surfactant for developer solutions - Photoemulsion stabilizer - Prevent photo-lubricant agglomera~ion - Coating aid in the preparation of multiple layer film elements - Antistatic wetting agent for film coatings - Antifogging agent for films - Bonding agent for fillers and fluoropolymer films - In coatings for nematic liquid crystal cells The examples below are presented for ill~strative purposes only and do not limit the scope of the invention. In the examples the surface tension was measured with a DuNouy tensiometer at 0.1 ~ con-centration in water at 25 C.
~' ~r-~J~
Example 1 Synthesis of compounds of the formulae (lOla) RfCH2CH2S-CH-COOH
CH2-COO(cH2c~20)22 and B (lOlb) RfCH2CH2S-CH-~X~(CH2CH20)~2 2.5 g (0.0255 mol) maleic anhydride in 2.5 g methyl-ethyl ke-tone were added to 25 g (0.025 mol) polyethylene oxide of molecula~
weight 1000 (number of ethyleneoxide units between about 15 and 30) and stirred ~or 12 hours at 75 C under a nitrogen blanket. At this time, infrared analysis showed no anhydride bands left at 1780 cm and 1850 cm 1.
11.8 g perfluoroalkyl-ethylmercaptan* (0.025 mol) of average molecular weight 478 were added together with o.2 g triethylamine as catalyst (0.002 mol) and the mixture stirred for 12 hours at 50 C.
The initially opaque white mixture turned clear after three hours.
~he clear solution was dried in vacuo at 80 C for 5 hours. The pro-duct is a soft wax which is soluble in water.
Elemental Analysis: C H F
Calc.: 47.6 6.3 19.7 Found: 46.0 6.3 18.1 *The perfluoroalkyl moiety Rf has a distribution of 27 ~ (- 5 ~) C6, 50 ~ (~ 5 ~) C8 and 23 ~ (- 5 ~) C10.
E~amples 2 - 12 Using the procedure of Example 1, compounds of structure (lOOa) RfCH~CH2S-CH-COOH
CH2-coo-Q-A
112~25~
and (lOOb) R~cH2cH2s-cH-coo-Q-A
were prepared with hydroxy compounds listed in Table 1.
Surface tension was measured for each sample, including Exam-ple 1 for a 0.1 ~ solution in water.
Table 1 Example Nonionic Moiety HO-Q-A Elemental 1) Analysis [Dynes ]
C ~ F 0.1 % in H20 .
1 Polyethyleneoxide 47.6 6.3 19.7 27.1 MW 1000 46.0 6.3 18.1 2 N-stearyl-dipolyethoxy 48.9 6.9 20.6 28.0 (15) amine 50.9 7.5 19.4 3 Polypropoxy (31) bis- 54.3 8.4 9.0 23.7 polyethoxy (26) diol 54.7 9.4 6.7 4 Polyethoxy (23) bis- 53.6 8.6 9.9 21.2 polypropoxy (29) diol 53.7 8.3 8.3 ~ethoxy polyethylene 43.3 5.8 23.4 19.7 oxlde 44.5 6.3 20.4 6 Nonylphenoxy poly- 49.3 6.6 19.2 25.9 ethylene oxide 50.7 7.1 16.2 7 octylphenoxy poly- 50.2 7.1 14.5 18.4 ethylene oxide 50.2 7.2 14.3 8 Polysiloxane diol 41.1 7.0 11.1 28.4 40.6 6.9 10.4 9 Polypropylene oxide 49.5 7.1 19.9 not soluble 4g.7 7.3 18.' Poly-n-butylene oxide 51.4 7.2 19.7 not soluble 54.0 7.9 17.8 112~4~
Table 1 continue Example Nonionic Moiety ~0-Q-A Elemental 1) nes-Analysis [ ]
rs cm C H F 0.1 % in ~2 .. . ... ...
11 Polysiloxane triol; - - 12 not soluble MW 6000 11.~
12 Polysiloxane diol; -- 31.8 not soluble MW 800 31.9 1) Calculated Found Examples_13 - 16 Using the procedure of Example 1, compounds of structure:
t200a) RfCH2CH2S-CH-COOH
and t200b) RfCH2CH2S-cH-cONH-Q-A
CH2 -COOl~
were prepared with the amlno compound listed in Table 2.
Table 2 -, Example Elemental Analysis 1) [ ~ynes ]
rs cm C H F 0.1 %
13 Polyoxdiamine Mh~ 600 2) 45.2 6.4 20.3 31.3 (ED) 44.5 6.4 21.0 14 Polyoxdiamine MW 1000 42.1 5.6 27.4 31.3 (ED) 43.7 6.o 25.4 . .
4~
Table 2 continue Example Elemental Analysis 1) ys [ cm ]
C H F 0.1 %
Polyoxdiamine MW 2000 48.87.5 12.0 36.0 (ED) 49.5 8.o11.0 16 Polypropylene oxide 53.98.4 12.0 not soluble B diamine ~ C A 54.7 8.811.7 (D) 1) Calculated Found 2) Bis-3-aminopropyl ethers of polyethylene oxide (ED) and polypropy-lene oxide (D) Example 17 Reaction Products ~f Polyethyleneoxide 600, ~aleic Anhydride and 1,1,2,2-Tetrahydroperfluoroctyl Mercaptan (102a) C6Fl3cH2cH2s-cHcooH
CH2COO- (CH2CH20) 13H
and (102b) C6Fl3cH2cH25-cHcoo(cH2c~l2 )13 Maleic anhydride (0.0255 moles, 2.5 g) dissolved in 10 g ace-tone was added to Polyehtyleneoxide (MG = 600) (0.0255 moles, 15.3 g~
and stirred overnight with triethylamine catalyst (2.5 mole ~).
Infrared spectrum showed no anhydride bands left at 1780 cm and 1850 cm 1,1,2,2-tetrahydroperfluorooctyl mercaptan (0.0255 moles, 9.64g) was added and the reaction was stirred at room temperature for 2 days berore TLC showed no unreacted mercaptan. The clear solution was dr~ed under vacuum t~ glve 23.o g of a clear white cil (83.8 % yield).
, .
112~4~
Infrared analysis was consistent for the structure.
Elemental analysis for C38 ~60 E13017 S
C H F
Calc.: 42.84 5.69 22.93 Found: 42.56 5.84 22.08 Surface tension of a 0.1 % solution in water was 27.7[dynes] .
cm Example 18 Reaction Product of bis-3-aminopropyl ether of polyethylene oxide (MW-1000), Maleic Anhydride and 1,1,2,2-Tetrahydrooerfluorooctyl Mercaptan C6F13C~2C~2SCHCOOH H00C-CHSc~2c~2c6 13 CE12CNH CH-C~[20--(C~2CH20) 18-CH2CH-NE~C-Ca2 (103) CH3 CH3 0 and its isomer.
Maleic anhydride (0.0255 moles, 2.5 g) was added to bis-3-ami-nopropyl ether of polyethylene oxide (MW = 1000) (0.0127~ moles, 11.86g) in 10 g acetone and the reaction was stirred for 24 hours (IR shows no anhydride bands at 1780 cm 1 and 1850 cm 1).
1,1,2,2-tetrahydroperfluorooctyl mercaptan was added and the reaction was stirred overnlght at room temperature. TLC showed no tra-ces of unreacted mercaptan.
The clear yellow solution was dried under vacuum to give 26.17 g of a clear yellow vlscous oil (99.7 ~ yield).
Infrared analysis was conslstent for the structure.
Elemental analysls for C66Hlo~F26N2025S
C H N F
Calc: 42.16 5.47 1.49 26.18 Found: 42.62 6.o4 1.56 24.26 0.1 ~ solution in water together with 0.1 %
C8H17C6 ~ O(C2H40)1oH had a surface tension of 23.~3[dynes].
SL cm 4~9 Examples 19 to 23 2.55 g of maleic anhydride and 2.55 g of sulfolane as solvent are added to 36.45 g of the dinonyl phenol of the formula (104) Cg~l9 \~ ~
~ / (CH2c~2~)24 H
g 19 and stirred for 20 hours at 60 C, to form a reaction mixture contai-ning a half ester of the formula (105) COOH
HC
Il HC
Il 2 2 24 \
and its isomer.
To this reaction mixture there is then added 0.1 gram of tri-ethylamine and 11.63 grams of RfCH2CH2SH und a nitrogen blanket and the mixture stirred at 60 C for about 7 hours. The product has the formula RfCH2CH2S-CH-COOH , . _ .~ 9 19 tlO6a) CH2-c(OcH2cH2)024 \. .~
CgHlg and C H
Il ._.~ 9 19 Rfc~2cH2s-cHc(oc~2c~2)o24 \ ~
(106b) CH2COOH 9 19 4~
Rf- distribution: 0.9 % C4Fg, 32.9 ~ C6Fl3, 37.5 ~ C8F17 22.9 ~ CloF21 and 5-3 ~ 12 25 Examples 20 to 23 are prepared in the same manner.
Surface tension is measured for each sample for a 0.1 ~ solu-tion in water.
Table 3 Compounds of formula (300a) RfC~2CH2S-CH-COOH
2 2 2 l (300b) RfCH2CH2S-CHCO(OCH2CH2)1- OR
Example Value of OR Surface tension s (Dynes~cm) _ 19 24 ~---3~C9~19 29.2 \ = ~ Cg}Ilg C18~37 27.1 21 15 \ _ / 9 l9 24.2 22 1) 20 ~ 26.3 =-23 5 -0--\ ~--CgH19 24.5 1) Rf-distribution 25 ~ C6F13, 50 ~ C8P17, 10 21 112~}Z9 Example24 Example 1 is repeated using the following Rf-thiols:
CF3\
O (CF2-CF2 ) 2-C~2C~2S~
~CF-O-CF2CF2-C~2CH2S~
C8F17-C~2C~2-SH
to give the corresponding water soluble surfactants.
wherein Rf, Rl, X and y have the indicated meanings.
The phenoxy radical (A) may contain one or more than one alkyl substituent, and is e.g. methylphenoxy, octylphenoxy, nonylphenoxy or dinonylphenoxy.
Preferably Rf is a straight or branched chain perfluoroalkyl of 4, preferably 6 to 12 carbon atoms, Rl is alkylene of 1 to 6 car-bon atoms and most preferably ethylene, y is zero, Q is polyalkylene oxide moiety having from 10 to 50 repeating units, such as polyethyle-ne oxide, A is hydroxyl, methoxy or alkylphenoxy of 7 to 15 carbon atoms and X is -O- or -NH- most preferably -O-.
The compounds of this invention can be conveniently prepared by a two-step method. The first step consists of a condensation reac-tion of an alcohol, diol, amine or a diamine of the formula A-Q-X-H, wherein A, Q and X have the indicated meanings with maleic or itaco-nic anhydride to yield intermediates of formulae (6) A-Q-X-CO-CH=CH-COOH
or (7) A-Q-x-co-6-cH2-cooH
\
112~4Z~
Said intermediates can also be prepared through transesterifica-tion with lower-alkyl esters of maleic, fumaric or itaconic esters such as mono- and dimethyl esters of maleic fumaric or itaconic acids.
The most useful starting material for the intermediate of formula (6) is maleic anhydride. Methyl-maleic acid and chloromaleic acid deriva-tives can be used in the process of this invention, but give unprac-tically low yields of the desired end-~roduct.
In the second step a base catalyzed addition reaction of a per-fluoroalkyl alkylene thiol of the formula Rf-Rl-SH and an intermedia-te of formula (6) or (7) is carried out.
The group Q is a polyether, polyester or siloxane diradical. Fol-lowing are illustrative examples of polyether diradicals:
~-~cH2cH2o]ncH2cH2 n = 4 - 100 ----~CH-CH2-0] ~[CH2CH2-] [CH2-CH_o]~ CH2CH_ ~ + ~1= 2 - 40 CH3 CH3 n = 4 - 50 tCH2CH20] n[CH2CH-O]~ -[CH2CH20]n CH2CH2- n + nl= 2 - 20 3 i~ = 4 - 40 R3-N~ CH2CH2-o) nC~2CH2--~2 n = 2 - 20 R3 = alkyl of C-atoms --tCH2CH-O)m-CH2CH- m = e - 50 [CH2CH2C~2ca20] xCH2CH2CH2 ~ x = 2 _ cO
Examples of polyester-diol diradicals are those derived from diacids and diols, for instance alkylene glycol polyadipate, polyse-bacate, polyisopthalate, polyorthopthalate, polyterephthalate, poly-maleate, polyglutarate and the like; such polyester diOlâ may be ba-sed on a mixture of several diols and diacids and are commercially availalbe as polyurethane prepolymers in a molecular welsht range f~om 400 - ~000.
.
112~42~
Examples of pol~ ~siloxanes are such o formulae (8) la3 IH3 IH3 22 Y'l ;Si~ 0 1 2 2 y y + yl = 26 CH3 ~CH3 CH3 ~ CH ~
(9) ~ Si(CH3)3 f ~ I IH3 ~ 1 3 1 3 H ~ HCH~ O Si 0 ¦ 2 )1 4 1-4 CH3 ~, ¦ ~CH ~
0 ~Si-~ - Si(CH3)3 C~3 X3 Xl + X2 + X3 about 8 Examples of the alcohols, diols and amines useful in the prepara-tion of intermediates (6) and (7) are listed below:
- polyethylene oxide, MW 200 - 5000, preferably 400 - 2000;
- polypropylene oxide, MW 200 - 5000, preferably 400 - 2000;
- methoxy polyethylene oxide, MW 400 - 25000, prererably 400 - 2000;
- poly-tetramethylene oxide, MW 3000 - 6000;
- poly(ethylene-co-propylene oxide) block polymers, such as polypropoxy-(10-50 repeating units)-bispolyethoxy-(10-20) diol or polyethoxy-(10-50)-bis-polypropoxy (10-50)-diol;
- ethoxylated alkyl phenol where alkyl is octyl or monyl and the etho-xylated group contains from 5 to 50 ethylene oxide units, - ethoxylated primary and secondary amLnes of 8 to 20 carbons, - ethoxylated fatty acids and amides of 8 to 20 c~rbons, alkoxylated alcohols and diols of 8 to 20 carbons, bis(2-amino pr~pyl)ethers o.~
polyethylene oxide and poly~ropylene oxide, - Siloxane diols and triols, etkoxylated merca~tans of 8 .o 20 carbor.s.
4Z~
The p~rfluoroalkyl thiols employed in the preparation of the com-pounds of this invention are well known in the prior art. For example, thiols of the formula Rf-Rl-SH have been described in a number of United States patents in-cluding United States Patents 2,894,991 issued July 1959 to Barr et al, 2,961,470 issued November 1960 to Sheppard, 2,965,677 issued December 1960 to Harris, 3,088,849 issued May 1963 to Friedlaender, 3,172,910 issued March 1965 to Brace, 3,544,663 issued December 1970 to Hauptschein et al, and 3,655,732 issued April 1972 to Rondestvedt.
Thus, United States Patent 3,655,732 discloses mercaptans of formula (10) R Rl SH
where R is alkylene of 1 to 16 carbon atoms and Rf is perfluoroalkyl and teaches that halides of formula Rf-Rl-hal are well known; reaction of RfI with ethylene under free-radical conditions gives Rf(CH2CH2)aI while reaction of RfCH2I with ethylene gives RfCH2(CH2CH2)aI as is further taught in United States Patent 3,088,849, United States Patent 3,145,222 issued August 1964 to Brace, United States Patent 2,965,659 issued December 1960 to Tiers, and United States Patent 2,972,638 issued February 1961 to Tiers.
United States Patent 3,655,732 further disclo æs compounds of fonmula (11) R_Rl_X_Rll_SH
where R and Rll are alkylene of 1 to 16 carbon atoms, with the sum of the carbon atoms of Rl and Rll being not greater than 25; Rf is perfl~oroalkyl of 4 through 14 carbon atoms ar.d X is -S- or NR"'- where R"' is hydrogen or alkyl of 1 through 4 carbon atoms.
United States Patent 3,544,663 teaches that the mercaptans of formula (12) RfCH2OEI2SH
where Rf is perfluoroalkyl of 5 to 13 carbon atcms, can be prepared by reacting the perfluoroalkyl alkylene iodide with thiourea or by adding H2S to a perfluoro-alkyl substituted ethylene (Rf-CH-CH2), which in turn can be prepared by dehydro-hylogenation of the halide Rf-CH2CH2-hal.
The reaction of the iodide Rf-Rl-I with thiourea followed by hydro-lysis to obtain the mercaptan Rf-R -SH is the preferred synthetic route. The reaction is applicable to both linear and branched chain iodides. Many useful perfluoroalkoxyalkyl iodides are described in United States Patent 3,S14,487 (Anello et al), issued May 1970 of general fonmula (13) (CF3)2CFCcF2cF2(cH2cH2)m where m is 1 - 3.
Particularly preferred herein are the thiols of formula (14) RfCH2CH2SH
where Rf is perfluoroalkyl of 6 to 12 carbon atoms. These Rf-thiols can be pre-pared from RfCH2CH2I and thiourea in very high yield.
Illustrative examples of preferred perfluoroalkylalkylenethiols are:
CloF21CH2CH2SH
CF3 ~
CFO(CH2CH2)l_3-cH2c~l2s Especially preferred perfluoroalkylalkylenethiols are:
CloF21CH2CH2SH
and ~uxtures thereof.
, 4~
Synthesis of the novel nonionic surfactants is most conveniently carried out in tWD steps: the first step consists of reacting the eyclie anhydride, most commonly maleic anhydride, with the hydroxy or amlno substituted nonionic com~ound either in bulk or in a ccmmon dry and aprotie solvent; useful solvents include ketones, such as acetone - 8a -c, g and methylethyl ketone; ethers, such as diethylether or ethylene gly-col - dimethylether, or tetrahydrofuran; esters, such as ethyl acetate or methyl cellosolve acetate; amides, such as dimethylformamide or N-methyl pyrrolidone. While amines react rapidly at room temperature, hydroxy compounds have to be heated for several hours to 50 - 100 c.
The second step involves addition of the perfluoroalkyl alkylene thiol to the intermediate maleic half ester or half amide in the presence of basic catalysts, such as triethylamine, pyridine, or tetramethyl ammo-nium hydroxide. Addition of the thiol to the mixture often leads to he-terogeneous, 2-phase system, which will turn into a homogeneous solu-tion, as the reaction proceeds. This reaction step is preferably car-ried out between 30 and 75 C under a nitrogen blanket and with good stirring.
The compounds of this invention can also be prepared by rever-sing the order of reactions described above; that is, first carry out the base catalyzed addition of a perfluoro substituted thiols to ma-leic anhydride followed by the ring opening with the hydroxy or amino substitute nonionic compound.
Such fluorochemical surfactants are useful to improve or im-part properties such as: wetting, penetration, spreading, levelling, foam stability, flow properties, emulsification, dispersion, and oil and water repellency. Based on these unique properties are numerous applications, some of which follow. Although applications are sugges-ted for a particular use area, the general applicability of each con-cept is inferred for other applications.
PLASTICS AND RUBBER INDUSTRY
- Emulsifying agent for polymerization, particularly fluoromonomers - As a latex stabilizer - To aid in the preparation of agglomerates of powdered fluorocarbon polymers - In synergistic mixtures with hydrocarbon surfactants to wet low energy surfaces including natural anc synthetic rubbers,resins, plastics - As an adjuvant for foam applications and as foaming agents to aid in t4Z~
leak detection - As a foam additive to control spreacing, crawling, edge buildup - As mound release agents, for silicones, etc.
- In refractory processes - As an anti-mist film former - Additive for elimination of trapped air in plastic laminates - Wetting agent for resin molds for definition, strength - ~ot-melt additive for oil and grease repellency - Resin additive for improved wetting of and bonding with fillers - ~low modifier for extruding hot melts: spreading, uniformity, anti-cratering - ~djuvant for resin etchant - Mold release agent, demoulding agent - Retarder for plasticizer migration or evaporation - Internal antistatic agent for polyolefins - Antiblocking agent for polyolefins PETROLEUM INDVSTR~
- As a film evaporation inhibitor for gasoline, jet fuel, solvents, hy-drocarbons - In extreme pressure lubricants TEXTILE AND LEAT~ER INDUSTRIES
- Soil release and soil proofing agent - OiL/water repellent textile and leather treatment - Wetting agent to improve coverage and penetration of pores of sub-strates - Anti-foaming agent in textile treatment baths - Wetting agent for finish-on-yarn uniformity - Penetrating agent for finishes on tow, heavy denier fibers - Emulsifying agen V lubricant/for fiber finishes - Cleaner/metal treating agent for polymerization equipment - Flow modifier for spinning of hot melts, sol~7tions .
- Additive for fabric finishes for spreading, uniformity - Wetting agent for dyeing - Penetration aid for bleaches - Wetting agent for binder in nonwoven fabrics PAINT, PIGMENT AND FINIS~ING INDUSTRI~S
- Levelling, anti-catering adjuvant for finishes and paints - Adjuvant for control of soiling - Agent to control differential evaporation of solvents - Levelling agent for floor waxes - Adjuvant for waxes to improve oil and water repellency - Adhesion improver for oily or greasy surfaces - To combat pigment flotation problems - Improver for automotive finishes, based on water-based coatings in which the pigments are rendered non reactive - Pigment grindlng aid to promote wetting, dispersion, color develop-ment - Foam generator substance for the application of dyes, nks - Electrolytic conversion coatings MINING AND METALWORKING INDUS~RIES
- In cleaning agents for property improvement - Additive for solvent cleaning - Additive for metal pickling baths to increase bath life and acid runoff - Additive for chrome electroplating: surface tension reduction, foaming - Additive for ~oldering flux, especLally ror electronic circuitry - Protective agent for coatings (tarnish resistance, grease repellen-cy) - Corrosion inhibitor - Additive for etchant solution for improved definition - Plastic preplate and silicon etchant technology - In soldering flux for microelectronics to reduce foaming - In chemical roughing agent solutions, prior to galvznization - As a colloidal dispersion aid for magnetic solids - Protective coatings ror aluminum ar.d as an anti-blocking agent 1~2~29 - Wetting agent for leaching copper ores and as a fresh flotation agent- To promote ore wetting:and quicker breaking of the protective oxide layer P~A2MACEUTICAL INDUSTRY
_ _ - Improve the properties and penetration of anti-microbial agents - Improve the properties of biochemicals, biocides, algicides, bacte-riocides, and bacteriostats - Improve the strength, homogeneity, and reduce the permeability of encapsulated materials - Emulsify fluorochemical blood substituted AGRICULTURE AND FORESTRY
- Wetting agent for herbicides, fungicides, weed killers, hormone growth regulators, parasiticides, insecticides, germicides, bacte-ricides, nematocides, microbiocides, defolients and fertilizers - As an ingredient in chemosterilents, insect repellents and toxicants - For wettable powder pesticides and chemical powders - Corrosion inhibitor for chemical applicators - Wetting agent for foliage - Wetting additive for live stoc~ dips, or to wet sheep skins during desalination - Wetting ad~uvant for manufacture of pl~wood veneer - Penetrant for preservative impregnation - Pulping aid - For cleaning tubes in paper making, dyeing - Grease~oil repellents for paper FIRE FIGHTING
_ __ __ - Wetting agent for fighting forest fires - Ingredlent of AFFF (aqueous film forming foams) extinguishing agents - Component of fluoroprotein foams - Additives to dry chemical extinguishing agents - Agent in aerosol-type extinguishers - Wetting agent for sprinkler water AUTOMOTIVE, BUILDING MAINTENANDE AND CLEANING
- Wetting agent for cleaning composi~ions - Additive for alkaline cleaners 1~2~425~
- Glass cleaner - Wetting agent for automobile waxes - Adjuvant to improve oiL/water repellency of wax - Lubrican Vcorrosion inhibitor for antifreeze - Rinse-aid for car washes - In dry cleaning compositions and solvent cleaners, for water displa-cement and foaming. May improve soil suspension and decrease redepo-sition - Foaming agents for pipe cleaning - Anti-mist film foamer for glass and plastics - In _oams for dust supression - For acidic concrete cleaners - Bubble foamer for air tracing, in ventilating systems HOUSEHOLD, COSMETIC AND PERSONAL PRODUCTS
- Rinse-aid for dishwashing - Liquid polishing compositions - Floor polish leveling ~gent - Additive for alkaline oven cleaners - Synergistic improver for disinfectants - Carpet cleaners - Synergistic wetting agent in detergent formulations - Additive for protective coatings on metals (tarnish resistance, grease resistance) - Gloss and antistatic improver - ~air shampoo ingredient - Shaving form Lngredient - Oil and water repellent cosmetic powders ingredient - Ingredient of lotions or creams for skin or hair - Ingredient of skin protection creams PHOTOGRAPHY AND GRAPHIC ARTS
- Printing ink additive for ink flow and levelling, both aqueous and solvent based - Wetting asent for writing inks - To combat pigment flooding and flotation in printing inks - To form ink repellent surfaces for waterless litnoplates, or elec-trographic coatings - Prevent reticulation of gelatin layers and improve uniformity - Assist in film drying - Improve film coatings and reduce "contraction flec.~s"
- Wetting, levelling, anti-cratering assi,t agent - Surfactant for developer solutions - Photoemulsion stabilizer - Prevent photo-lubricant agglomera~ion - Coating aid in the preparation of multiple layer film elements - Antistatic wetting agent for film coatings - Antifogging agent for films - Bonding agent for fillers and fluoropolymer films - In coatings for nematic liquid crystal cells The examples below are presented for ill~strative purposes only and do not limit the scope of the invention. In the examples the surface tension was measured with a DuNouy tensiometer at 0.1 ~ con-centration in water at 25 C.
~' ~r-~J~
Example 1 Synthesis of compounds of the formulae (lOla) RfCH2CH2S-CH-COOH
CH2-COO(cH2c~20)22 and B (lOlb) RfCH2CH2S-CH-~X~(CH2CH20)~2 2.5 g (0.0255 mol) maleic anhydride in 2.5 g methyl-ethyl ke-tone were added to 25 g (0.025 mol) polyethylene oxide of molecula~
weight 1000 (number of ethyleneoxide units between about 15 and 30) and stirred ~or 12 hours at 75 C under a nitrogen blanket. At this time, infrared analysis showed no anhydride bands left at 1780 cm and 1850 cm 1.
11.8 g perfluoroalkyl-ethylmercaptan* (0.025 mol) of average molecular weight 478 were added together with o.2 g triethylamine as catalyst (0.002 mol) and the mixture stirred for 12 hours at 50 C.
The initially opaque white mixture turned clear after three hours.
~he clear solution was dried in vacuo at 80 C for 5 hours. The pro-duct is a soft wax which is soluble in water.
Elemental Analysis: C H F
Calc.: 47.6 6.3 19.7 Found: 46.0 6.3 18.1 *The perfluoroalkyl moiety Rf has a distribution of 27 ~ (- 5 ~) C6, 50 ~ (~ 5 ~) C8 and 23 ~ (- 5 ~) C10.
E~amples 2 - 12 Using the procedure of Example 1, compounds of structure (lOOa) RfCH~CH2S-CH-COOH
CH2-coo-Q-A
112~25~
and (lOOb) R~cH2cH2s-cH-coo-Q-A
were prepared with hydroxy compounds listed in Table 1.
Surface tension was measured for each sample, including Exam-ple 1 for a 0.1 ~ solution in water.
Table 1 Example Nonionic Moiety HO-Q-A Elemental 1) Analysis [Dynes ]
C ~ F 0.1 % in H20 .
1 Polyethyleneoxide 47.6 6.3 19.7 27.1 MW 1000 46.0 6.3 18.1 2 N-stearyl-dipolyethoxy 48.9 6.9 20.6 28.0 (15) amine 50.9 7.5 19.4 3 Polypropoxy (31) bis- 54.3 8.4 9.0 23.7 polyethoxy (26) diol 54.7 9.4 6.7 4 Polyethoxy (23) bis- 53.6 8.6 9.9 21.2 polypropoxy (29) diol 53.7 8.3 8.3 ~ethoxy polyethylene 43.3 5.8 23.4 19.7 oxlde 44.5 6.3 20.4 6 Nonylphenoxy poly- 49.3 6.6 19.2 25.9 ethylene oxide 50.7 7.1 16.2 7 octylphenoxy poly- 50.2 7.1 14.5 18.4 ethylene oxide 50.2 7.2 14.3 8 Polysiloxane diol 41.1 7.0 11.1 28.4 40.6 6.9 10.4 9 Polypropylene oxide 49.5 7.1 19.9 not soluble 4g.7 7.3 18.' Poly-n-butylene oxide 51.4 7.2 19.7 not soluble 54.0 7.9 17.8 112~4~
Table 1 continue Example Nonionic Moiety ~0-Q-A Elemental 1) nes-Analysis [ ]
rs cm C H F 0.1 % in ~2 .. . ... ...
11 Polysiloxane triol; - - 12 not soluble MW 6000 11.~
12 Polysiloxane diol; -- 31.8 not soluble MW 800 31.9 1) Calculated Found Examples_13 - 16 Using the procedure of Example 1, compounds of structure:
t200a) RfCH2CH2S-CH-COOH
and t200b) RfCH2CH2S-cH-cONH-Q-A
CH2 -COOl~
were prepared with the amlno compound listed in Table 2.
Table 2 -, Example Elemental Analysis 1) [ ~ynes ]
rs cm C H F 0.1 %
13 Polyoxdiamine Mh~ 600 2) 45.2 6.4 20.3 31.3 (ED) 44.5 6.4 21.0 14 Polyoxdiamine MW 1000 42.1 5.6 27.4 31.3 (ED) 43.7 6.o 25.4 . .
4~
Table 2 continue Example Elemental Analysis 1) ys [ cm ]
C H F 0.1 %
Polyoxdiamine MW 2000 48.87.5 12.0 36.0 (ED) 49.5 8.o11.0 16 Polypropylene oxide 53.98.4 12.0 not soluble B diamine ~ C A 54.7 8.811.7 (D) 1) Calculated Found 2) Bis-3-aminopropyl ethers of polyethylene oxide (ED) and polypropy-lene oxide (D) Example 17 Reaction Products ~f Polyethyleneoxide 600, ~aleic Anhydride and 1,1,2,2-Tetrahydroperfluoroctyl Mercaptan (102a) C6Fl3cH2cH2s-cHcooH
CH2COO- (CH2CH20) 13H
and (102b) C6Fl3cH2cH25-cHcoo(cH2c~l2 )13 Maleic anhydride (0.0255 moles, 2.5 g) dissolved in 10 g ace-tone was added to Polyehtyleneoxide (MG = 600) (0.0255 moles, 15.3 g~
and stirred overnight with triethylamine catalyst (2.5 mole ~).
Infrared spectrum showed no anhydride bands left at 1780 cm and 1850 cm 1,1,2,2-tetrahydroperfluorooctyl mercaptan (0.0255 moles, 9.64g) was added and the reaction was stirred at room temperature for 2 days berore TLC showed no unreacted mercaptan. The clear solution was dr~ed under vacuum t~ glve 23.o g of a clear white cil (83.8 % yield).
, .
112~4~
Infrared analysis was consistent for the structure.
Elemental analysis for C38 ~60 E13017 S
C H F
Calc.: 42.84 5.69 22.93 Found: 42.56 5.84 22.08 Surface tension of a 0.1 % solution in water was 27.7[dynes] .
cm Example 18 Reaction Product of bis-3-aminopropyl ether of polyethylene oxide (MW-1000), Maleic Anhydride and 1,1,2,2-Tetrahydrooerfluorooctyl Mercaptan C6F13C~2C~2SCHCOOH H00C-CHSc~2c~2c6 13 CE12CNH CH-C~[20--(C~2CH20) 18-CH2CH-NE~C-Ca2 (103) CH3 CH3 0 and its isomer.
Maleic anhydride (0.0255 moles, 2.5 g) was added to bis-3-ami-nopropyl ether of polyethylene oxide (MW = 1000) (0.0127~ moles, 11.86g) in 10 g acetone and the reaction was stirred for 24 hours (IR shows no anhydride bands at 1780 cm 1 and 1850 cm 1).
1,1,2,2-tetrahydroperfluorooctyl mercaptan was added and the reaction was stirred overnlght at room temperature. TLC showed no tra-ces of unreacted mercaptan.
The clear yellow solution was dried under vacuum to give 26.17 g of a clear yellow vlscous oil (99.7 ~ yield).
Infrared analysis was conslstent for the structure.
Elemental analysls for C66Hlo~F26N2025S
C H N F
Calc: 42.16 5.47 1.49 26.18 Found: 42.62 6.o4 1.56 24.26 0.1 ~ solution in water together with 0.1 %
C8H17C6 ~ O(C2H40)1oH had a surface tension of 23.~3[dynes].
SL cm 4~9 Examples 19 to 23 2.55 g of maleic anhydride and 2.55 g of sulfolane as solvent are added to 36.45 g of the dinonyl phenol of the formula (104) Cg~l9 \~ ~
~ / (CH2c~2~)24 H
g 19 and stirred for 20 hours at 60 C, to form a reaction mixture contai-ning a half ester of the formula (105) COOH
HC
Il HC
Il 2 2 24 \
and its isomer.
To this reaction mixture there is then added 0.1 gram of tri-ethylamine and 11.63 grams of RfCH2CH2SH und a nitrogen blanket and the mixture stirred at 60 C for about 7 hours. The product has the formula RfCH2CH2S-CH-COOH , . _ .~ 9 19 tlO6a) CH2-c(OcH2cH2)024 \. .~
CgHlg and C H
Il ._.~ 9 19 Rfc~2cH2s-cHc(oc~2c~2)o24 \ ~
(106b) CH2COOH 9 19 4~
Rf- distribution: 0.9 % C4Fg, 32.9 ~ C6Fl3, 37.5 ~ C8F17 22.9 ~ CloF21 and 5-3 ~ 12 25 Examples 20 to 23 are prepared in the same manner.
Surface tension is measured for each sample for a 0.1 ~ solu-tion in water.
Table 3 Compounds of formula (300a) RfC~2CH2S-CH-COOH
2 2 2 l (300b) RfCH2CH2S-CHCO(OCH2CH2)1- OR
Example Value of OR Surface tension s (Dynes~cm) _ 19 24 ~---3~C9~19 29.2 \ = ~ Cg}Ilg C18~37 27.1 21 15 \ _ / 9 l9 24.2 22 1) 20 ~ 26.3 =-23 5 -0--\ ~--CgH19 24.5 1) Rf-distribution 25 ~ C6F13, 50 ~ C8P17, 10 21 112~}Z9 Example24 Example 1 is repeated using the following Rf-thiols:
CF3\
O (CF2-CF2 ) 2-C~2C~2S~
~CF-O-CF2CF2-C~2CH2S~
C8F17-C~2C~2-SH
to give the corresponding water soluble surfactants.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Perfluoroalkyl substituted half esters and amides having the formula or wherein Rf is straight or branched chain perfluoroalkyl of 4 to 18 car-bon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, R1 is branched or straight chain alkylene of 1 to 12 carbon atoms, alkylenethioalkylene of 2 to 12 carbon atoms, alkyle-neoxyalkylene of 2 to 12 carbon atoms or alkyleneiminoalkylene of 2 to 12 carbon atoms where the nitrogen atom contains as a third substi-tuent, hydrogen or alkyl of 1 to 6 carbon atoms, X is oxygen or NH, y is 1 or zero, Q is a polyether or polyester diradical moiety having a molecular weight of 300 to 5000 or a polysiloxane having 5 to 80 re-peating units, and A is hydrogen, hydroxyl, alkoxy of 1 to 21 carbon atoms, phenoxy, alkylphenoxy of 7 to 24 carbon atoms, the group or wherein Rf, R1, X and y have the indicated meanings.
2. A compound according to claim 1, wherein A is alkylphenoxy of 7 to 20 carbon atoms.
3. A compound according to claim 1 wherein Rf is a straight or branched chain perfluoroalkyl of 4 to 12 carbon atoms, R1 is alkylene of 1 to 6 carbon atoms, y is zero, Q is a polyoxyalkylene oxide having 10 to 50 repeating units, A is hydroxyl, methoxy or alkylphenoxy of 7 to 24 carbon atoms, and X is -0- or -NH-.
4. A compound according to claim 1 wherein Rf is a straight or branched chain perfluoroalkyl of 6 to 12 carbon atoms and Q is a polyethylene oxide moiety.
5. A compound according to claim 1 wherein Rf is a straight or branched chain perfluoroalkyl of 6 to 12 carbon atoms, R1 is ethylene, y is zero, X is oxygen and A-Q- is derived from the group selected from polyethyleneoxide of MW 400 - 2000; polypropoxy-(having 10 - 50 repeating units)-bis-polyethoxy-(10-20) diol; poly-ethoxy-(10-50)-bis-polypropoxy-(10-50) diol; methoxy-polyethylene oxide of MW 400 - 2000;and nonylphenoxy polyethylene (5-50) oxide or octylphenoxy polyethylene (5-50) oxide.
6. A compound according to claim 1 wherein A is a group of the formula or wherein Rf, R1 and Y have the meanings indicated in claim 1, X is -NH- and -Q-X- is derived from a bis-(2-aminopropylether) of poly-ethylene oxide of MW 400 to 2000 or polypropylene oxide of MW
400 to 2000.
400 to 2000.
7. A mixture of compounds according to claim 1 having the formulae and wherein Rf has a distribution of 27% C6, 50% C8 and 23 % C10.
8. A mixture of compounds according to claim 1 having the formula and its isomer, wherein Rf has a distribution of 27% C6, 50% C8 and 23% C10.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/858,218 US4171282A (en) | 1977-12-07 | 1977-12-07 | Fluorinated nonionic surfactants |
| US94482078A | 1978-09-22 | 1978-09-22 | |
| US944,820 | 1978-09-22 | ||
| US858,218 | 1986-04-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1129429A true CA1129429A (en) | 1982-08-10 |
Family
ID=27127449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA317,372A Expired CA1129429A (en) | 1977-12-07 | 1978-12-05 | Fluorinated nonionic surfactants |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5484524A (en) |
| AU (1) | AU519243B2 (en) |
| BR (1) | BR7808012A (en) |
| CA (1) | CA1129429A (en) |
| DE (1) | DE2852593A1 (en) |
| FR (1) | FR2411212A1 (en) |
| GB (1) | GB2010874B (en) |
| IT (1) | IT1106947B (en) |
| NL (1) | NL7811945A (en) |
| NO (1) | NO150683C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5935573B2 (en) * | 1980-06-28 | 1984-08-29 | シ−アイ化成株式会社 | agricultural cladding |
| JPS6028860B2 (en) * | 1981-09-29 | 1985-07-06 | アキレス株式会社 | Eggplant cultivation film |
| JPS5856959A (en) * | 1981-09-29 | 1983-04-04 | Nissin Kogyo Kk | Booster of negative pressure type |
| DK435881A (en) * | 1981-10-01 | 1983-04-02 | Niels Ole Vesterager | WASHING ACTIVE DOSAGE UNIT, METHOD OF PREPARING IT AND THE USE OF IT |
| JPS5889360A (en) * | 1981-11-24 | 1983-05-27 | アキレス株式会社 | Agricultural film |
| DE3903005A1 (en) * | 1989-02-02 | 1990-08-16 | Pfersee Chem Fab | METHOD FOR THE PRODUCTION OF MODIFIED POLYSILOXANES, THE POLYSILOXANES SO MANUFACTURED, THE USE THEREOF AND THE MATERIALS SO TREATED |
| US5266724A (en) * | 1990-09-04 | 1993-11-30 | Matsushita Electric Industrial Co., Ltd. | Fluorine-containing compounds |
| US5188747A (en) * | 1990-09-04 | 1993-02-23 | Matsushita Electric Industrial Co., Ltd. | Fluorine-containing lubricant compounds |
| DE4244951C2 (en) * | 1992-12-01 | 1998-08-06 | Minnesota Mining & Mfg | New poly:siloxane cpd(s) and carboxylic acid derivs., prepn. and use |
| DE4240274B4 (en) * | 1992-12-01 | 2004-02-12 | Minnesota Mining And Manufacturing Co., Saint Paul | Polysiloxanes with fluoroaliphate and carboxyl-containing terminal groups, their preparation and their use in the treatment of fiber substrates |
| US5612431A (en) * | 1994-09-21 | 1997-03-18 | Minnesota Mining And Manufacturing Company | Leaching of precious metal ore with fluoroaliphatic surfactant |
| KR20060113907A (en) | 2003-09-29 | 2006-11-03 | 에테나 헬스케어 인코포레이티드 | - high alcohol content gel-like and foaming compositions |
| DE102004062775A1 (en) * | 2004-12-21 | 2006-06-29 | Stockhausen Gmbh | Alcoholic pump foam |
| US8263098B2 (en) | 2005-03-07 | 2012-09-11 | Deb Worldwide Healthcare Inc. | High alcohol content foaming compositions with silicone-based surfactants |
| JP6198058B2 (en) * | 2013-12-19 | 2017-09-20 | Dic株式会社 | Surfactant composition, coating composition, and resist composition |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4075237A (en) * | 1968-04-10 | 1978-02-21 | Geigy Chemical Corporation | Perfluorinated esters of fumaric acid and certain other ethylenically unsaturated poly-basic acid and soil repellant polymers thereof |
| NL7204067A (en) * | 1971-03-29 | 1972-10-03 | ||
| GB1354138A (en) * | 1971-10-15 | 1974-06-05 | Ici Ltd | Fluorocarbon surfactants |
| GB1410328A (en) * | 1971-12-21 | 1975-10-15 | Unilever Ltd | Alkoxylation process |
| DE2238740C3 (en) * | 1972-08-05 | 1981-07-16 | Bayer Ag, 5090 Leverkusen | Polyethers containing perfluoroalkyl groups and processes for their preparation and their use |
| US3794672A (en) * | 1973-07-05 | 1974-02-26 | Dow Corning | Perfluoroalkyl silicon compounds containing sulfur |
| CH628247A5 (en) * | 1975-01-03 | 1982-02-26 | Ciba Geigy Ag | Aqueous, film-forming concentrates for extinguishing or preventing fire with a content of non-anionic compounds containing perfluoroalkylalkylenethio groups |
| US4081399A (en) * | 1975-09-22 | 1978-03-28 | Ciba-Geigy Corporation | Process for the preparation of concentrated solutions of fluorinated amphoteric surfactants |
| FR2328070A1 (en) * | 1975-10-17 | 1977-05-13 | Ugine Kuhlmann | ANTI-STAIN PRODUCTS ALLOWING THE EASY REMOVAL OF SOIL IN WASHING |
-
1978
- 1978-12-05 JP JP14975878A patent/JPS5484524A/en active Granted
- 1978-12-05 GB GB7847286A patent/GB2010874B/en not_active Expired
- 1978-12-05 DE DE19782852593 patent/DE2852593A1/en active Granted
- 1978-12-05 CA CA317,372A patent/CA1129429A/en not_active Expired
- 1978-12-06 BR BR7808012A patent/BR7808012A/en unknown
- 1978-12-06 NO NO784108A patent/NO150683C/en unknown
- 1978-12-06 IT IT52206/78A patent/IT1106947B/en active
- 1978-12-06 FR FR7834422A patent/FR2411212A1/en active Granted
- 1978-12-06 AU AU42255/78A patent/AU519243B2/en not_active Expired
- 1978-12-07 NL NL7811945A patent/NL7811945A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| BR7808012A (en) | 1979-08-07 |
| GB2010874B (en) | 1982-10-06 |
| IT7852206A0 (en) | 1978-12-06 |
| FR2411212A1 (en) | 1979-07-06 |
| NO784108L (en) | 1979-06-08 |
| FR2411212B1 (en) | 1983-12-16 |
| DE2852593C2 (en) | 1988-04-14 |
| NO150683C (en) | 1984-11-28 |
| NO150683B (en) | 1984-08-20 |
| JPS632951B2 (en) | 1988-01-21 |
| NL7811945A (en) | 1979-06-11 |
| DE2852593A1 (en) | 1979-06-13 |
| IT1106947B (en) | 1985-11-18 |
| GB2010874A (en) | 1979-07-04 |
| AU4225578A (en) | 1979-06-14 |
| JPS5484524A (en) | 1979-07-05 |
| AU519243B2 (en) | 1981-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4171282A (en) | Fluorinated nonionic surfactants | |
| CA1129429A (en) | Fluorinated nonionic surfactants | |
| US4266080A (en) | Perfluoroalkylthioethyl ether derivatives | |
| EP0231927B1 (en) | Water and oil repellant having excellent desoiling properties | |
| US4089804A (en) | Method of improving fluorinated surfactants | |
| DE68904479T2 (en) | NEOPENTYL GLYCOLS WITH FINAL PERFLUOROALKYL GROUPS CONTAINING A HETEROATOM AND THEIR POLYMERS. | |
| US4788287A (en) | High performance water and oil repellant | |
| DE69216707T2 (en) | Perfluoroalkyl halides and derivatives | |
| US4239915A (en) | Perfluoroalkyl carboxylic acids | |
| US4098811A (en) | Perfluoroalkylthioamido amine and ammonium compounds | |
| DE69107134T2 (en) | Surfactants based on perfluoroalkylpolyoxyalkyl polysiloxanes. | |
| JPH06200073A (en) | Fluorochemical aminoalcohol | |
| EP0002004B1 (en) | Process for the manufacture of fluorinated cationic compounds and their use as surfactants | |
| US7638650B2 (en) | Fluoroalkyl surfactants | |
| US4102916A (en) | Perfluoroalkylthioaminimide derivatives | |
| EP0363094A1 (en) | Fluorochemical surfactants and process for preparing same | |
| DE69317438T2 (en) | FLUORALIPHATIC RESIDUAL ANIONIC SULFONAMIDO COMPOUNDS AS A SURFACTANT | |
| GB1591293A (en) | Method of improving fluorinated surfactants | |
| EP2346923B1 (en) | Fluorinated polyoxyalkylene glycol diamide surfactants | |
| US3573095A (en) | Epoxidized perfluoroalkylamide water-and oil-repellency agents | |
| JP2002241441A (en) | Water-dispersive type fluorine-containing copolymer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |