Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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
R5
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
R6
(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"
(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
-- 3 --
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
- 4 -
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-
CH2-COOH
or
(5b) Rf-Rl-S(CH2)yCH~COOH
CH2CO-X
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
H2
\
112~4Z~
-- 5 --
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
1 - 18
C-atoms
--tCH2CH-O)m-CH2CH- m = e - 50
CH3 CH3
[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~
-- 6 --
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:
C4F9CH2CH2SH
C6F13CH2CH2SH
8 17C 2OEI2SH
CloF21CH2CH2SH
C12F25CH2CH2SH
CF3 ~
CFO(CH2CH2)l_3-cH2c~l2s
CF3
Especially preferred perfluoroalkylalkylenethiols are:
C6F13CH2CH2SH
C8F17CH2CH2SH
CloF21CH2CH2SH
and ~uxtures thereof.
-- 8 --
,
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,
4Z9
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~
-- 10 --
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-
425
- 14 -
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~
29
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
CH2COOH
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~
- 16 -
and
(lOOb) R~cH2cH2s-cH-coo-Q-A
CH2-COOH
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~
- 17 -
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
CH2 -CONH-Q-A
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~
- 18 -
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
CH2COOH
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~
-- 19 --
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
- 20 -
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~
- 21 -
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
CH2COOH
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
- 22 -
Example24
Example 1 is repeated using the following Rf-thiols:
CF3\
O (CF2-CF2 ) 2-C~2C~2S~
CF3
CF3
~CF-O-CF2CF2-C~2CH2S~
CF3
C8F17-C~2C~2-SH
to give the corresponding water soluble surfactants.
