CA1066842A - Perfluoroalkylthio groups containing polyurethanes, process for their manufacture and their use - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Perfluoroalkylthio glycols and esters thereof which can be prepared by the free-radical catalyzed addition of a perfluoroalkylthiol to an acetylenic alcohol or ester thereof reacted with a dissocya?ate to obtain a polyurethane containing perfluoroalkylthiol groups, which polyurethanes are useful as coating to provide oil and water repellence to textiles and as additive to plastics to provide mold-release and when combined with a quaternary ammonium salt containing at least one long hydrocarbon chain the treated materials show an additional dry soil repellent effect.

Description

" ~66~z ,:`
Tbis invention relates to a process for the manu~acture of polyurethanes which comprises reacting at tempera~ures of 20 to 120C
in the presence of non-reactive anhydrous organic solvents or without any solvent : ~ , .
a~ an organic isocyanate or an isocyanate polymer ~ and b) at least one of :, : i) an Rf-glycol of formula j HO - R2 ~ C~ - CH - R - OH
:! I I .''~ S S
Rl 1 r T~
! ~f Rf j .
;y ~ or :~ ii) a hydroxyl-terminated polymer containing at least oneresidue of formula I :.
'~ .
O - R2 ~ CH - CH - R3 - O - ~ .
S S

~' I ' I '.
Rf Rf : where Rf is perfluoroalkylof l to 18 carbon atoms or said perfluoro-alkyl:substituted~by perfluoroaIkoxy of 2 to 6 carbon atoms; ~ :
: ~ :
Rl is branched or straight chaln alkylene of 1 to 12 carbon :
atoms, alkylenethioalkylene of 2 to 12 carbon atoms, :alkyleneoxyalkyleneof 2:to 12 carbon atoms, or alkylene- :
imlnoalkylene of 2 to:12 carbon atoms where ths nitrogen : atom contains as a~third substituent hydrogen or alkyl of I to~6 carbon atoms;

- 3 ~ %

R2 and R3 independently are stralght or branched chain alkylene of 1 to 12 carbon atoms, said alkylene substitu~ed by 1 or 2 of phenyl or cyclohe~yl, or R2 and R3 are a group of formula CmH2m(Ck~2k)r where m is an integer from 1 to 12, k is an integer from 2 to 6, r is an integer from 1 to-40.
. .
It relates further to urethane compositions containing at leas~
one ~nit of the formula

2 CH ~ R3 C N
S S
.,, I I
Rf R~
where Rl, R2, R3 and Rf have the meanings indicate~above, and to the use of the urethanes, optionally combined with quaternary ammonium salts contsining at least one long hydrocarbon chain, e.g. as coatings to provide oil and water repellence, and optionally a dry soil re-pellent effect to textiles.

The Rf-glycols and derivatiYes thereof ha~e the general formula: ;
f 1 1 2 4 Rl S - CH - R3 - 0 - R4 where Rf is straight or branched chain perfluoroalkyl of 1 to 1~
carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, ::~ ~ . . : .
; ~ : . ..
.
::.: ~ ::: ~

_ 4 - ~ ~ 6 ~ 8 ~ 2 Rl is branched or straight chain alkylene of 1 to 12 carbon atoms, alkylenethioalkylene of 2 to 12 carbon atoms, alkyleneoxy-alkylene of 2 to 12 carbon atoms or alkyleneiminoalkylene of 2 to 12 carbon atoms where the nitrogen atom contains as a third substituent, hydrogen or alkyl of 1 to 6 carbon atoms, R2 and R3 each independently is straight: or branched chain alkylene of 1 to 12 carbon atoms or alkylene ~polyoxyalkylene) of formula m 2m( k 2k)r where m is an integer from 1 to 12, k is an integer from 2 to 6, i r is an integer from 1 to 40, . .
R4 is hydrogen alkyl of 1 to 24 carbon atoms or acyl where :.
said acyl is derived from an aliphatic or aromatic carboxylic acid of up to 24 carbon atoms. Thus, R4 can be hydrogen, alkyl of 1 to 24 carbon atoms, alkanoyl of 1 to 24 carbon atoms, alkenoyl of 1 to 24 :~
: ~ carbon atoms or said alkanoyl or alkenoyl substituted by 1 to 3 of :: ; chloro, bromo and carboxyl, or said alkanoyl substituted by phenyl or ~.
naphthyl, said:phenyl or naphthyl being ~.
unsubstituted or substitu~ed by 1 to 3 or chloro, bPomo, alkyl of 1 to 6 carbon atoms, alkoxy of l to 6 carbon atoms, : or said alkanoyl substituted by lower acyl or lower acylamino where lower acyl means alkanoyl~or~alkenoyl of 2;to 6 carbon ato=s~ :
:and the mono- or di-chl.oro or bromo derivative thereof;
or ~4:. is benzoyl or ben~zoyl substituted by 1 to 3 : ; of chloro, bromo, alkyl of l to 18 carbon atoms, - 5 - ~ ~6~

alkosy of 1 to 8 carbon a~oms or lower acyl or acylamino where lower acyl means alkanoyl or alkenoyl of 2 to 6 carbon atoms, and the mono- or di-chloro or bromo derivative thereof.

Some preferred members of "lower scyl" are:
chloroacetyl, bromoacetyl, ~-chloropropionyl, ~-bromopropionyl, ~ dichlorpropionyl, a,~- :
dibromopropionyl, acryl, methacryl, a-chloro-acryl, a~bromoacryl, ~ or ~ dichloro- or dibromoacryl, ~-chlorocrotonyl, -chlorocrotonyl, ~-bromocrotonyl, and ~-bromocrotonyl.
.' . .
: Vseful compounds are those where Rf is perfluoroalkyl of 6 to 12 carbon atoms or said perfluoro-alkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, .
~' : ' : Rl is branched or straigh~ chain alkylene of 2 to 8 carbon atoms, alkylenethioalkylene of 2 to 8 carbon atoms, alkyleneoxy-alkylene of 2 ~o 8 carbon atoms or alkyleneiminoalkylene of 2 to 8 carbon atoms where the nitrogen atoms contains hydrogen or methyl as a thirdsubstituent, R2 and R3 are each independently straight or branched chain alkylene of 1 to 4 carbon atoms or alkylene ~polyoxyalkylene~ of ~ .
:: : the formula . .
C H (OC ~ ) -where m is an integer from 1 to 4, k is an integer ~rom 2 to 4, and r is an integer from 1 to 20, and - 6 ~ ~ oG~84~

R4 is bydrogen, alkyl of 1 to 24 carbon atoms, alkanoyl of 1 to 24 carbon atoms,'alkanoyl of 1 to 6 carbon atoms substi~utad by phenyI, ben~oyl, benzoyl substituted by alkyl of 1 to 6 carbon atoms, or R4 i9 selected from chloroacetyl, bromoacetyl, ~-chloropropionyl, ~-bromo-propionyl, ,~-dichloropropionyl, ~,~-dibromopropionyl, acryl, ~ethacryl, a-chloroacryl, a-bromoacryl, a,~- or ~,~-dichloro or dibromoacryl, ~-chlo:rocrotonylj a-chloro- ..
crotonyl, ~-bromocrotonyl, or ~-bromocrotonyl.

Particularly preferred are those compounds where R~ is perfluoroalkyl of 6 to 12 carbon atoms, ~.
Rl is alkylene of 2 to 4 carbon atoms, R2 and R3 are both alkylene of 1 or 2 carbon atoms, and R4 is hydrogen alkyl of 6 to 18~carbon atoms or alkanoyl of 6 to 18 carbon atoms.

One group of preferred compounds have the foD~ula : ~ .
Rf - CH2CH2 - S ICH CH20 Rf CH2CH2 S CH CH20H
where : .
Rf is perfluoroalkyl of 6 to 12 carbon at s or where ` Rf~is perfluoroalko~yperfluoroalkyl of 4 to 12 carbon atoms, and especially where , (cF3)2cFo(cF2cp2)y : where y is an inte8er from 1 to 6.

Another group of pref rred compounds h~ve the formula ~ 7 ~ ~1~66~

Rf (CH2)w ~ S - CH ~ CH20~
R - (CH ) ~ S - CH - CH OH

where Rf is perfluoroalkyl of 6 to 12 carbon ato~s and w is an integer from 1 to 8.

A preferred group of alkylene (polyoxyalkylene)-containing ~ Rf-glcols,have the formula : : Rf - (CH2)n - S - CH - CmH2~(0CkH2k~r Rf - (CH2)n - S - CH - CmH2m(CkH2k)r ` where Rf is perfluoroalkyl of 6 to 12 carbon atoms, n is an integer from 1 to 12, m ls an integer from 1 to 4, k is an integer from 2 to 4 and ~: r is an integer from 1 to 20. ~ :

The novel Rf-glycols and es~ers described herein can be:ob-tained by the free~radical~catalyzed addition reaction of a p~rfluoro-: alkylthiol of formula Rf - Rl - SH
to an acetylenic diol or ester of formula :
:
: R4~ 0 R2 C C R3 0 R4 where R2 and R3 each~is straight or branched chain alkylene or :ta 12~carbon:a~oms; said alkyiene substituted by ane or two of phenyl, cyclohexyl; or an alkylene (polyoxyalkylene) group of formula ~ - 8 - ~ ~66~

CmH2~(Ck~i2k)r where m is an integer from 1 to 12, ~ k is an integer from 2 to 6, ; r is an integer from 1 to 40, and Rl~and R4 are as previously defined.

R2 and R3 each preferably is a straight or branched chain ` alkylene of 1 ~o 6 carbon atoms; said alkylene substituted by one or two of phenyl and cyclohexyl;)or an alkylene (polyoxyalkylene) group of formula -~: --CmH2 (OCk~I2k) r where m is an integer from 1 to 4, k is an integer from 2 to 4j r i8 an integer from 1 to 20, an,d R4 is preferably hydrogen.

In one embodiment, the acetylenic compounds have the formula oa ~ OH
R5 - C -~C _ C~-~C R8 where R5, R6j R7 and R8 are selected from hydrogen, alkyl of l to 4 carbon atoms, cyclohexyl, and phenyl.

Although~R2 and R3 can contain such u~saturated groups as vinyl,~allyl or styryl, such~groups are not preferred since th~y compete for the Rf-~thiol and result in undesirable perfluoroalkyl by-pro~ducts. ~ ;~

, .. . . . . . . . . . .. . ..

9- ~6~3~Z

In a particularly praferred embodiment, R5, R6, R7, and R8 are each hydrogen or alkyl of 1 to 4 carbon atoms. Especially pre-ferred is the case where R5, R6, R7~ and R8 are selected from hydrogen, and alkyl of 1 to 3 carbon atoms.

In another preferred embodiment R6 and R7 are each hydrogen and R5 and R8 are selected from hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl and phenyl.

Physical constants for some of the compounds described above are as follows:

~ , _ _ _ _ , .: .

CH3 H H CH3 BP 126 12~ at 18 mm (CH8)2C~ H H tCH3~2CH MP 69 (CH3)2CH-CH2 H H (CH3)2CH-CH2 BP 158-160 at 15 mm C6H13 H H C6H13 BP 205 at 18 mm C6~5 H H C6H5 MP 12 CH2=CH~ H E CH2=CH BP 146 at 15 mm CH3-CH=CH- H H CH3-CH=CH- MP 90-92 C6H5-CH=CH- H H C6H5-CH=CH- MP 162 CH3 CH3 CH3` CH3 MP 95 C2H5 CH3 CH3 C2H5 BP 155-160 at 18 mm C2H5 C2H5 C2H5~ C2X5 MP 74 C3H7 CH3 CR3 ~ C3H~j~ MP 56-58 C3H7 C3H7 C3H7 C3Hj MP 1200 C6H5 CH3 CH3 C6H5~ ~ MP 163 _ C6R5 C6R5 ~ C6H5 - __-~ ~, : Cj _ ;. . ' :
: ~

~0616~Z

Reference: "Acetylene FLomologs and Derivatives" by Prof. Pierre Piganiol, Pages 295 - 300, Mapleton House P~lblishers, Brooklyn, N.Y., Copyright 1950.

R -glycols where R2 and R~ are CmH2m(0CkH2k)r converting the original acetylenic diol to the hydroxyalkyl ether, followed by free radical addition of the thiol RfR'-SH. In like fashion the alkyl ethers, where R4 is alkyl, can be prepared, using the Williamson synthesis and known variations thereof.

The Rf-esters can be made by alternate routes. Rf-glycols can be esterified by well-known synthetic organic methods, such as treatment of the alcohol with a carbo~ylic acid anhydride, an acyl halide or a carboxylic acid. Alternatively, the ~hiol Rf-Rl-SH can be added to the acetylenic ester.

The following acetylenic diols and esters are commercially available:
2~b~ltyn-1,4-diol

3,4-dimethyl-1-pentyn-3,4-diol 2,5-dimethyl-3-hexyn-2,5-diol 3-hexyn-2,5-diol 3,6-diethyl-4-octyn-3,6-diol 2,6-dimethyl-4-octyn-3,6-diol 2,3,6,7-tetramethyl-4-octyn-3,6-diol

4,7-dime~hyl-5-decyn-4,7-diol 2,4,7,9-tetramethyl-5 decyn-4,6-diol 2-butynediol diacetate.

Perfluoroalkyl thiols useful herein are well documented in the prior art. For example, thiols of the formula R~Rl-S~ ha~e bee~
described in a number of U.S. patents including 2,894,991; 2,961,470;
2,965,677; 3,088,849; 3,172,190; 3,544,663 and 3,655,732.

~ ,........................................................................ .

(36~ Z

Thus, U.S. Patent 3,655,732 discloses mercaptans af Eormula R - Rl - SH
where R is alkylene of 1 to 16 carbon atoms and R~ is perfluoro-alkyl and teaches that halides of formula R~-Rl-hal are well-known;
reaction of RfI with ethylene under free-radical conditions gives Rf(CH2CH2)aI while reaction of RfCH2I with e~hylene gives RfCH2~CH2CH2) I as is further taught in U,S.Patents 3,088,849, 3,145,222, 2~,965,659 and 2,~72,638.. .

U~S. Patent 3,655,732 further discloses compounds of formula R~-R X~R"-SH
where R and R" are alkylene of 1 to 16:carbon atom~s, with the sum of the carbon atoms of Rl and R" being no greater than 25; Rf is per-fluoroalkyl of 4~thr'ough 14 carbon atoms and X is -S- or -R"' - where R" ' is hydrogen or alkyl of 1 through 4 carbon atoms. . ~
,:
U.S. Patent 3,544,663 teaches that the mercaptan f 2 2 where Rf is perfluoroalkyl of 5 to 13 carbon atoms, can be pre-pared by reacting the perfluoroalkyl alkylene iodide with thiourea ~ .
or~by adding H2S:to a perfluoroalkyl substituted ethyle~e :: (Rf-CH=CH2), which in~turn can be prepared by dehydrohalogenation of ; :
the halide Rf-CH2CH2-hal.

The reaction of the iodide Rf-Rl-l with thiourea followed by . . :~ :
hydrolysis to obtain the mercapto ~f-Rl-SH is the preferred synthetic : route and the reaction is ilIustrated in Examples 64 to 65. The : reaction is applicable to both linear and branched chain iodides.
any useful perfluoroalkoxyalkyl iodides are described in US-PS
3~514,487 of general formula ~ -- 12 - ~66~

(CF3)2cFcF2cF2(cH2cH2) I

where m is 1-3.

Particularly preferred herein are the thiols of formula Rf CH2CH2SH
whe~e Rf is perfluoroalkyl of 6 to 12 carbon atoms. These Rf-thiols can be prepared from RfCH2CH2I and thiourea in very high yield.

The formation of the Rf-glycols and esters proceeds via the formation of intermediates which may be present as by-product in the Rf-glycols and esters. These intermediates have the formula Rf - Rl - SC - R2 o - R4 and l SC - R3 - O - R4 C~ - R2 _ o R4 Such intermediate formation is considered consistent with the general pathway for the free-radical addi~ion of thiols to acetylenes (Acetylenes and Allenes; T.F~ Rutledge, Reinhold Book Corporation, 196~, page 142). That th addition of the thiol to the triple bond is a stepwise reaction proceeding through the intermediates can be shown by reac~ing~the thiol with an excess of the acetylenic diols or esters~whereby is obtained the intermediates in high yields~ -In the synthesis of the R-glycols and derivatives thereof described above, it m~lst be emphasized that the addition of . ~ :

13 - ~ 0 6 684Z

Rf-thiols to acetylenic alcohols and esters is not equivalent to the reactions described in the literature for the addition of a non-fluorinated thiol to an acetylenic alcohol. When the conventional prior art conditions are employed, it has beerl found that, although some Rf-glycol or ester is produced, the yield i9 unacceptably low, wbile the proportions of intermediates (mono-adducts) and disulfides ;~ (of the type (Rf-Rl-S-)~) are unacceptably hi.gh. Such reaction con-ditions as described by A.T. Blomquist and J. Wolinsky, J. Org.
Chemistry, 23, 551 (1958), utilizing W radiation and peroxides at room temperature, and requiring reaction periods of 1 to 4 weeks are beyond the limits of commercial acceptability.

The improved process of this invention in~olves the combi-nation of a) from 0.5 to 20 percent of a mole of an azo-type free-radical catalyst9preferably from 1 to 10 percent of a mole of catalyst;
b) moderate reaction temperatures, on the order of 40 to about 100C
` and c) a mole ratio of Rf-thiol to acetylenic diol or es~er of from 2.0 to 2.5 moles of thiol per mole of acetylenic compound.

~ ~ The reaction temperature and choice of azo~type free-radical - catalyst are considered to be mutually dependent. Thé temperatuse i~ range of 40 to 100C is one wherein the for~ation of undesirable by-products is ~inimized and wherein ~he reaction products are stable.
In order to achieve a reaso~able reaction rate of these temperatures, it is desirable to use an azo-type catalyst that is reactive to a reasonable extent in this temperature range. It is therefore, pre-erred to use an azo-type free-radical catalyst having a l-hour half-life temperature of 40 to about 100C. These compounds are listed belo~.

- 14 - ~Q~ 2 .
Compound 1 Hr.Half-Life Temperature C
_ _ 2-t-butylazo-2-hydroperoxy-4-methylpentane 45C
2-t-butylazo-2-cyano-4-methoxy 74C
4-methylpentane Di-t-butyl-4,4'-aæobis- (4-cyano- 80 C. (azo) peroxyvalerate) azobisisobutryonitrile 81C
2-t-butylazo-2-cyano-4-methylpentane 88C
4-t-butylazo-4-cyanovaleric acid ¦ 93C (trichlorobenzene, 1,3-dimethyl-3-(t-butylperoxy)-butyl-94C (azo) 4-t-butylazo-4-cyanovalerate 1 t-butyl peroxy-4-t-butylazo-4-cyano-94C (azo) valerate ethylene bis(4-t-butylazo-4-cyano- 94C
valerate) 2-(t-butylazo) isobutyronitrile 97C.
4-(4-t-butylazo-4-cyanovaleryloxy)- 100C :
2-hydroxybenzophenone 2-t-butylazo-2-cyanobutane 104C
. ~
Source: Commercial Development Department, LucidolChemicals, Buffalo, N.Y.
. .
Other aæo-type free~radical catalysts are known and ean be ~ used but, because of their higher l-hour half-life temperatures, are : less preferred.

It is preferred to use an azo compound havi~g a l-hour half life of from about 75C.to about 90C.and a reaction temperature of from about 6QC to about 80C. Because of the case of availability, : - .
:~ it is preferred to use azobisisobutyronitrile as the catalyst.

~' ' ' ~-' :

- 15 - ~ ~6~8~Z

The reaction can be carried out in bulk or in a suitable inert medium ~hich acts to disperse or dissolve the reactants. The bulk re-action, without a solvent medium, is usually preferred. However, if solvents are used, useful solvents include ketones, such as acetone, methyl ethyl ketone and methylisobutyl ketone; esters such as ethyl aceta~e~ butyl acetate, 2-ethylhexyl acetate; hydrocarbons such as he~ane, heptane, octane and higher homologs, cyclohexane~ benzene, toluene, xylene or blends of aliphatic, cycloaliphatic or aromatic hydrocarbons; alcohols such as ethanol, n-propanol, isopropanol, t-butanol and methyl cellosolve;; ethers, both aliphatic and alicyclic including di-n-propyl ether, di-butyl ether and tetrahydrofuran. In addition, chlorinated solvents such/ as di-chloroethyl ether, ethylene dichloride, perchloroethylene and carbon tetrachloride can be em-ployed. -Preferred so1vents are the hydrocarbon solvents. Of ~he hydro-carbon solvents~ the alkanes of 6 to 10 carbon atoms, the benzene hydrocarbons of 6 to 8 carbon atoms and mixtures thereof are pre-ferred. Carbon tetrachloride and ethylene dichloride are useful chlorinated solvents. The data provided in Examples 17-29 indicates that yields are increased and by-product formation decreased when the alkane solvents are used. Commercially available mixtures of paraffinic, naphthenic and benzene hydrocarbon solvents can also be used successfully.

Using the reaction parameters described above, and continuing ; until reaction is comple~e, usually after 6 to 10 hours azobisiso-butyronitrile at 75~C, there can be effected an 85 to 95% convèrsion of the Rf-thiol to ~he desired Rf-glycol ether or ester. The overall yield can be increased to greater than 95% because unreacted Rf-thiol can be recovered and recycled. The Rf~glycols ethers and esters are generally insoluble in aliphatic and aroma~ic hydrocarbon solvents, while the Rf-thiols are soluble in these matèrials; the :: :

~ .... . .. . .... . . . .

- 16 - ~ ~6~

unreacted Rf~thiol can be readily recovered by washing the reaction product with a suitable hydrocarbon such as heptane or benzene.
Alternately9 the Rf-thiols can be recovered by passing the crude reaction product through a molecular distillation apparatus under conditions such that the Rf-glycols and esters pass through while the Rf-tbiols are volatilized, and recovered.

As indicated above, the Rf glycols can be used to make Rf-containing urethane compositions. These urethane compositions have extremely low free surface ènergies and therefore, possess oil and water repellent properties, as well as mold release and other pro-perties associated with low free surface energy. It should be noted that the urethane compositions of this invention are characterized by the presence of two perfluoroalkylthio groups on adjacent carbon atoms, a characteristic which provides improved oil and water re-pellent properties over the fluorinated urethane compositions of the prior art. Using the Rf-compounds and compositions describedi -herein, it is possible to manufacture molds that display the excellent release properties characteristic of the silicone polymers.

In addition, the compounds where R4 is CmH~m(OCkH2k)r are useful as nonionic surfactants, especially where r is an integer from about 5 to 30.

The esters, where R4 is acyl and the ethers, where R~ is alkyl are useful as additives to synthetic and natural polymers to reduce the surface energy and to provide mold release characteristics.

The~diols, where R4 is hydrogen can be used to make a varie~y of condensation products such as polyesters, polyamides, polycarbonates, polyurethanes and the like. The polyurethanes are particularly preferred.

,.

.

- l7 ~ ~ ~6~2 As used herein the term "urethane composition" means compounds and compositions which contain the characteristic O

- N - C -linkage and at least one Rf~containing group of formula H O O H
a) - N - C - O - R2 ~ CH - CH - R - O - C - N -S S
Rl Rl :
Rf R
or O H
b) R4 - O - R2 ~ C~ - C~ - R3 C N
S S
. :.
IRl Rll Rf Rf -where Rf, Rl, R2, R3 and R4 are as previously described.

Preferred urethane compositions include those where Rf, Rl, R~ -R3 and R4 have the configurations previously described as being pre-ferred.
: , :~ .
The Rf-glycols can be used to make a wide variety of urethane intermediates and end products including hydroxyl and isocyanate-terminated prepoiymers, low molecular weight urethane composi~ions useful to render plastics soil repellent, and high molecular weight compositions useful as elastomers, foams, paints and varnishes, and textiIe treating~compositions. It is also possible to modify these Rf-containing urethane compositions so that they are water soluble or self-emulsifiable, a property that is particularly useful in connection with the textile treating co~positions.

- 18 ~668~

Polyurethane elastomers generally have remarkable resistance to most solvents including gasoline, aliphatic hydrocarbons, and to some degree, aroma~ic hydrocarbons. They also exhibit excellent abrasion resistance. By inclusion of Rf-glycol in an elastomer for-mulation, it is possible to increase the solvent resistance of ure-thane elastomers. The elastomers generally in~olve the reaction pro-duct of a diisocyanate, a linaar long chain dlol and a low molecular weight chain eætender such as a glycol, diamine or polyol. Today, elastomers are generally prepared by a prepolymer technique whereby a diisocyanate is reacted with a hydroxyl-ter~ina~ed polyester or polyether to form an isocyanate-terminated prepolymer. This prepoly-mer is then further reacted (chain extended) with a glycol, diamine or polyfunctional polyol (e.g. trimethylolpropane). Following the chain extension step, the liquid material solidiies and is re-moved from a mold and cured at elevated temperatures.
:` `
Urethane foams are usually prepared from diisocyanates and hydroxyl-terminated polyethers or polyesters. Linear or slightly branched polymers are used to provide flexible foams while more highly branched polymers produce rigid foams . Foaming is often accomplished by including water in the system, the reaction between isocyanate and~water providing carbon dioxide for foaming. For rigid foams a low-boiling liquid such as trichlorofluoromethane has been used as a blowing agent. p Appropriate selection of catalysts~ stabilizers, surfactans and other additives-controls the foam formation, cell size and type, density, cure and the like. By incorporating the Rf-glycol into urethane foams, especially moldedfoa~s, lt is possible to achieve improved mold release properties in rigid, semi-rigid and flexible fo~ms. It is also possible to improve the water and solvent resistance of foams used as insulation.

g .
~ ~ `' '."' - 19 - ~684~

Incorporation of the R~-glycols lnto polyurethane coatings such as paints and varnishes improves the water and solvent resistance thereof. Widely used systems include the two-component coatings where-in a non-volatile isocyanate derived Erom the reaction of tolylene diisocyanate with a polyal such as tri~ethylolpropane, is reacted with polyfunctional polyester. Another system in use involves the one-component polyurethane coatings which are based on stable isocyanate-terminated prepolymers obtained fro~ a diisocyanate such as tolylene diisocyante and a polyfunctional polyether. Such coatings dry by the reaction of the free isocyanate groups with water or a~mospheric moisture. The reaction proceeds through the unstable carbamic acid, with C02 being eliminated, to give primary amine groups which further react with isocyanate groups to form ureas.

Treatment of a textile with a fluorine-containing composition, notably a fluorine-containing polyurethane, provides oil and water-repellent characteristics thereto. Polyurethane compositions con-taining the residue of the Rf-glycol display improved oil and water repellence on textile substrates.

Of the higher molecular weight urethane compositions, linear polymers, obtained by reacting an Rf-glycol wi~h an organic diiso-cyanate, having recurring structural units of formula O H H O
~: : 11 1 1 11 ' ~ S` S ,.
, ~1 ~Rl ~Rf :: _ Y I _ wher , ~
Rf, Rl, R2, and R3 are as previously defined and A is a divalent organic radical, preferably alkylene of 2 to 16 . ~ .
.

~ .

- ~o- ~O~B~Z

carbon atoms, unsubstituted or substituted phenylene or naphthylene or unsubstituted or substituted biphenylene or bisphenylene are useful as plastics, fibers, coatings and the like.

However, most urethane compositions that are used commercially to any great extent are copolymers that contairl only a relatively small number of urethane linkages. These copolymers are prepared from a variety of segments, typically based on polyethers and polyesters and can have a molecular weight of from 200 to 10,000, generally from about 200 to about 4,Q00. By the inclusion of an appropriate al~ount of Rf-glycol in the starting materials, it is possible to prepare prepolymers that, when incorporated as part of a urethane composition fa~orably effect the properties thereof. It is similarly possible to incorporate a desired amount of Rf-glycol into the reaction mixture of a conventional prepolymer and an isocyanate so as to obtain con-ve~tional urethane compositions containi~g the divalent residue of the Rf-glycol. In the same way, there can be added an Rf-con-taining prepolymer together with F instead of the Rf-glycol.

The Rf-containing prepolymers can be hydroxy-terminated or isocyanate-terminated and, as indicated, can have a molecular weight as high as 10,000 although a molecular weight of 200 to about 4,000 is more usual.

Hydroxy-terminated prepolymers can be prepared by rea ting an excess of a polyhydroxy component with a poly-functlonal hydroxy-reactive component such as a polyisocyanate; an isocyanate-terminated prepolymer; a polybasic carboxylic acid, anhydride or acyl halide, or a bischloroformate.

.

. . .

- 21 - ~ 0 6 ~ ~ 4 2 The polyhydroxy component can be a polyol, all Rf-glycol, a polyether, a polyester, an Rf-containing polyether9 an Rf-contaiining polyester or mixture thereof.

The polyols are well-known in the urethane art and include Ethylene glycol 1,3-propanediol 1,4-butanediol 1,5-pentanediol 1 9 6-hexanediol 1,9-nonanediol l,10-decanediol di-, tri-, tetra- and pentaethylene gylcol bis(4-hydroxybutyl)-ether bis(-2-hydroxyethyl) thioether bis(4-hydroxybutyl) ~hioether 1,4-bis(3-hydroxypropyl) benæene glycerol `
j trimethylolpropane 1,2,6-hexanetriol sorbitol mannitol pentaerythritol, 2-ethyl-1,3-butylene glycol octamethylene~glycol 2-ethyl-1,3-hexanediol ~
dodecane~ethylene glycol tetradecamethylene glycol haxadecamethylene glycol ; octadecamethylene glycol The polyol can also contain cycloalipha~ic groups, e.g~ 1,4-cyclohexane-diol, 1,4-bis(hydroxy~ethyl) cyclohexane, 4,4'-dihydroxyl-:

22 ~ 6~

l,l'-dicyclohexyl and the like~ If desired, mixtures of polyols can be used.

Polyols in addition to those described abo~e, that are con-sidered especially useful, are those containing tertiary nitrogen atoms wbich can be qua~ernized with acids, the:reby converting a water-insoluble urethane composition into one that is water soluble or emulsifiable. Generally, an isocyanate-term:inated prepolymer having a molecular weight of 200 to 10,000, preferably 400 to 4,000, is reacted with a difunctional tertiary amine to provide a segmented polymer containing tertiary nitrogen atoms. The nitrogen atoms can be quaternized, for example, by alkylation with methyl chloride or dimethyl sulfate to yield a composition that in polar media yields a dispersion in water. The polyam~oniu~ polyurethane compositions are obtained even more readily by neutralization of the basic poly -urethane composition in a polar organic solvent such as acetone, methyl ethyl ketone, tetrahydrofuran, with a strong (HCl) or pre-ferably weak (pK ~4) acid such as the Cz-C7 alkanoic acids. Acetic acid is especially preferred because the acetic acid evaporates with . .
the water on drying to leave tXe water-insoluble hydrophobic starting polyurethane composition. .

The neutralized polyurethane composition in a polar solvent spontaneously forms a dispersion when water is sti.rred in. The solvent can thereafter be distilled off to give a solvent-free late~
whose film-for~ing qualities are comparable to those of the organic solution. : :
` ; ; :
In a convenient de of preparing the water-dispersible basic polyurethane compositions, a polyester or polyether diol is reacted : in a non-reactive polar..solvent, such as acetone, me~hyl etbyl ketone, tetrahydrofuran:and the like, wi.th an excess of a diisocyanate such :as tolylene diisocyanate or, preferably an aliphatic diisocyanate which tends to give non-yellowing uretbanes such as dimer acid - 23 ~ 6~2 derived diisocyanate (DDI, commercially available from Quaker Oats Company) or another diisocyanate which i9 described herein as pro-viding no~-yellowing urethanes, and the prepolymer partially chain extended with an alkyl diethanola~ine to yield a urethane composition containing tertiary amino groups. The urethane. co~position can then be acidif.ied with a solution of aqueous weak acid (pK~ 4j such as acetic acid; the concentration of acid is not critical. An emulsion immediately forms when this composition is added to water.

The polyurethane compositions can contain from as little as 5 to 800 milliequivalents of ammonium groups per 100 grams of poly-urethane composition, preferably from about 50 to about 500 milli-.~ equivalents of a~monium groups per 100 grams.

Some useful polyols containing tertiary nitrogen atoms can be represented by the formula HO - Rlo - I - Rll - OH

where ..
Rlo and Rll are alkyl of 2 to 4 carbon atoms or a group of :-for~ula H
- R - N - R
.
where R13 and R14 are alkyl of 2 to 4 carbon atoms R12 is alkyl of 1 to 18 carbon atoms, cyclohexyl, tolyl, xylyl, naphthyl, or wlth the nitrogen atom forms piperazyl or pyridyl.

Useful polyols that contain tertiary ni~rogeh atoms include the alkoxylated aliphatic, cycloaliphatic aromatic and heterocyclic primary amines:

.. : , ................................................... .

~6~8~

N-methyl-diethanolamine N-butyl-diethanolamine N-oleyl-diethanolamine N-cyclohexyl-diethanolamine N-methyl-diisopropanolamine N-cyclohexyl-diisopropanolamine N,N-dihydroxyethylanilina N,N-dihydroxyethyl-m-toluidine N,N-dihydroxyethyl-p-toluidine N-N-dihydroxypropyl-naphthylamine N,N-tetrahydroxyethyl-aminopyridine dihydroxyethylpiperazine polyethoxyla~ed butyldiethanolamine ~ -polypropoxylated methyldiethanolamine (molecular wt. 1000) polypropoxylated methyldiethanolamine (molecular wt. 2000) polyesters with tertiary amino groups tri-2-hydroxypropyl-(1)-amine N,N-di-n~(2:3-dihydroxypropyl)-aniline N,N'-dimethylwN,N'-bis-hydroxyethylhydrazine N,N'-bIs-hydroxypropyleehylenediamine N,N'-dimethyl-N,N'bis(hydroxyethyl)-ethylenediamine stearyldiethanolamine N,N'-bis(hydroxyethyl)-piperazine The Rf-glycols can be incorporated in the water-dispersible urethane compositions in an amount sufficient to provide the desired improvement of the surface properties of the polyurethane composition.

Useful polyethe~ are well-known and widely employed in urethane technology. ~ ~

The polye~hers are generalIy prepared commercially from lower alkylene oxides e.g. ethylene~ propylene and butylene oxide and di-;",,, ;,,~,~ ",- "",,", -,";~ ,"~, ~66~4'~

or poly~unctionalalcohols. They have a molecular weight of Erom 400 to 5000. A list of commercially available polyethers, trade names, molecular weigkt range and suppliers can be found in Volume 11, Polyurethane, page 511, Encyclopedia o~ Polymer Science and Technology, John Wiley and Sons, Inc., 1969.

Hydroxy-terminated polyesters can be prepared from a polybasic acid, anhydride or aryl halide and a polyol, a~ described abo~e and/or an Rf-glycol.

Useful dicarboxylic acids are thoae deri~ed from ajsaturated aliphatic dicarboxylic acid of 2 to 18 carbon atoms or an aromatic dicarboxylic acid of 8 to 18 carbon atoms, e.g. compounds of formula B(COOH)2 ~here B is preferably alkylene of 0-161carbon atoms or arylene of 6 to 16 carbon atoms. Such acids include oxalic, malonic, succinic, glutanic, adipic, pimelic, suberic9 azelaic, sebacic, brassylic, thopsic, octadecanedioic, 1,4-cyclohexanedicarboxylic, ~ -4,4~-dicyclohexyl-1,1'-dicarboxylic, phthalic, isophthalic, tere-phthalic, methylphthalic, chlorophthalic, diphenyl-2,3'-dicarboxylic, diphenyl-4,4'-dicarboxylic, 1,4-naphthalene dicarboxylic, diphenyl-methane-2,2'-dicarboxylic, diphenylmethane-3,3'-dicarboxylic, ai- :
phenylmethane -4,4'-dicarboxylic acid and the like.

Adipic acid and phthalic anhydride are the most com~on acid and anhydride. Of the polyols, the most commonly used include ethyl-ene glycol, propylene /lycol, 1,2-, 1,3- and 1,4-butylene glycoI, i,6-hexylene glycol,' trimethylolpropane, glyerol 1,2,6-hexanetriol and diethylene glycol.
~: .
Useful hydroxyl-~erminated polyesters can al60 be derived from natural castor oil and glycerol or from caprolactones and e~hylene glycol. Such hydroxy-terminated polyesters have hydroxyl number~
ranging from 40 to 500 and very lo~ acid numbers ranging from 0 to 2.

6~

Hydroxyl -terminated polycarbonates can be obtalned by reacting an e~cess of a polyol with phosgene.

Hydroxy-terminated polybutadienes, or butadiene-styrenes and ~ butadiene-acrylonitriles are useful herein, as are hydroxyl containing - graft polymers of the polyether-polyacrylonitrile type.
; .
Any convenient isocyanate can be used to react with the Rf-glycol or Rf-containing hydroxy-terminated prepolymer. Myriads of useful isocyanates are well-known in the art. Thus, one can use aromatic isocyanates, ~iisocyanates,triisocyanates and polyisocyanates.
: ' Useful aromatic diisocyanates can be represented by the formula A(NCO)2 -:
where A is phenylene that is unsubstituted or substituted by one or two of alky 1 of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chloro, bromo and nitro naphthylene that is unsubstituted or substituted by one or two of alkyl of l to 4 carbon atoms, chloro, bromo and nitro or where A lS a group of formula a' ~a"
~ t ~ - D ~ o a a'l' wnere D is a~direct bond,~oxygen, methylene or ethylene and :
- 27 _ ~1~ 6 6 ~ ~ ~

D is a direct bond~ oxygen, methylene or ethylene : and a, a'~ a" and a"' each independently is hydrogen, alkyl of 1 to 4 carbon a~oms alkoxy of 1 to 4 carbon atoms, chloro or bromo.
.
Aromatic triisocyanates can be represented by the formula B(NC0)3 where B is the benzene or toluene group. .

Aromatic di- and triisocyanates as described abo~e include -Tolylene diisocyante (TDI) (all isomers), ~.
4,4'-diphenylmethane diisocyanate (~I) Tolidine diisocyanate Dianisidine diisocyanate m-Xylylene diisocyanate ::
p-Phenylene diisocyanate m-Phenylene diisocyanate Chloro-2,4-phenylene diisocyana~e 3,3'-Dime~hyl-4,4'-bisphenylene diisocyanate 3,3'-Dimetho~y-4,4'-bisphenylene diisocyanate 4,4'-Bis(2-methylisocyanatophenyl) methane 4,4i-bisphenylene diisocyanate 4,4'-Bis(2-methoxyisocyanatophenyl) methane nitro-phenyl-3,5-diisocyanate 4,4'-diisocyanatodiphenyl ether 3,~!-dichloro-4,4'-diisocyanatodiphenyl ether 3,3'-dichloro,4,41~-diisocyanatodiphenyl methane 4,4'-diisocyana~odibenzyl 3,3'-dimethyl-4,6'-diisocyanatodiphenyl 3~3~-d`imé~hoxy-4~4~-diisocyanaeodiphen 2,2'-dime~hyl-4,4'-diisocyanatodiphenyl 2,21-dichloro-5,5'-dimethoxy-4,4'-diisocyanatodiphenyl ~ ., .. :. . . . .

- 28 _ ~lD 6 6 8 4 2 3,3'-dichloro-4,4'-diisocyanatodiphenyl benzene-1,2,4-triisocyanate benzene-1,3,5-triisocyanate benzene-1,2,3-triisocyanate toluene 2,4,6-triisocyanate : toluene 2,3,4-triisocyanate 1,2-naph~halene diisocyanate 4-chloro-19 2-naphthalene diisocyanate 4-methyl-1,2-naphthalene diisocyanate 1,5-naphthalene diisocyanate 1,6-naphthalene diisocyanate 1,7-naphthalene diisocyanate 1,8-naphthalene diisocyanate 4-chloro-1,8-naphthalene diisocyanate -:
2,3-naphthalene diisocyanate 2,7-naphthalene diisocyanate -1,8-dinitro-2,7-naphthalene diisocyanate l-methyl~2,4-naphthalene~diisocyanate l-methyl-5,7-naphthalene diisocyanate 6-methyl-1,3-naphthalene diisocyanate 7-methyl-1,3-naphthalene diisocyanate:
poly~ethylene polyphenyl isocyanate and co-products of hexamethylene diisocyanate and tolylene diisocyanate.

UseEul aliphatic diisocyanates include those of general ~: formula A(NC0) : 2 where : :~
A is alkylene oi 2 to 16 carbo~ atoms. :

Useful aliphatic polyisocyanates include -2-ethane diisocyanate~

29 ~

1,3-propane diisocyanate 1,4-butane diisocyanate 2-chloropropane-1,3-diisocyanate pentamethylene diisocyanate propylene-1,2-diisocyanate ; 1,6-he~ane diisocyanate 1,8-octane diisocyanate l,10-decane d;isocyanate 1,12-dodecane diisocyanate 1,16-hexandecane diisocyanate and -:
other aliphatic diisocyanates such as 1,3-dyclohexane diisocyanate 1,4-cyclohexane diisocyanate cyclohexane triisocyanate 4,4'-methylene bis(cyclohexyl) isocya~ate.

Additionally, the following diisocyanates are particularly preferred because urethane compositions made therefrom tend to be non-yellowing:
~ ' 1,6~hexame~hylenediisocyanate (HDI) ~ 2,2,4- and 2,4,4-trimethylhexamethylenediisocyanate (TMDI) :~ ~ : dimeracid deri~ed diisocyanate (DDI) obtained from dimerized fatty acids, such as linoleic acid 4,4' dicyclohexylmethane diisocyanate (hydrogenated NDI) isophorone diisocyanate 3-isocyanatomethyl-3,5,5-trimethylcyclohe~ylisocyanate lysine methyl ester diisocyanate tLDIM) bis(2-isocyanatoethyl)~fumarate (FDI) bis~2-isocyanatoethyl)` car*onate.

: : Other useful isocyanates include polyisocyanates, particularly M~ triisocyanates which are readily obtained by the reaction o~ an . ~ . . ..

- 30 - ~ ~6~Z

excess o the corresponding diisocyanate ~ith water according to the following equation:
3 OCN - D - NCO ~ ~2 ~I-D-NCO
C = O
N~D-NCO
C = O ' ND-D-NCO

where D is the residue of a diisocyanate as described above;
additional polyisocyanates include polymethylene polyphenyl-isocyanate (PAPI) and tris-(isocyanatophenyl) thiophosphate (Desmodur Rf - Trademark).

Additional isocyanate components can be prepared by reacting an excess of a diisocyanate as described above wi~h a suitable hydroxyl component, such as a polyol as described abo~e or an Rf-glycol as described herein~or combination thereof, to obtain an isocyanate-terminated prepolymer.
:
In addition to the polyisocyanates, useful urethane compo- -sitions can be obtained from the aliphatic and aromatic monoiso- -cyanates. The low molecular weight urethane compositions obtai~ed by reacting an Rf-glycol with a monoisocyanate are useful to impart soil and moid-release properties to a variety of natural and synthetic polymers.

~ : :
; Some useful aro~atic monoisocyanates include -2-fluorophenyl isocyanate 3-fluorophenyl isocyanate 4-fluorophenyl isocyanatè
m-fluorosulfonylphenyl isocyanate -~
E~ -2-phenylcyclopropyl isocyanate ~ ~ :
...... . ... .

- 31 - ~ ~ ~6~Z

m-tolyl isocyanate p-tolyl isocyanate trifluoro-o-tolyl isocyanate ~9a~a-trifluoro-m-tolyl isocyanate -p-bromophenyl isocyanate 2,5-dimethylphenyl isocyanate o-ethoxyphenyl isocyanate p-ethoxyphenyl isocyanate o-methoxyphenyl isocyanate m-methoxyphenyl isocyanat,e p-methoxyphenyl isocyanate l-naphthyl isocyanate o-nitrophenyl isocyanate m-nitrophenyl isocyanate r nitrophenyl isocyanate p-phenylazophenyl isocyanate o-tolyl isocyanate.

Useful aliphatic monoisocyanates include such alkyl isocyanates of 1 to 16 carbon atoms as methyl isocyana,te ethyl isocyanate ~: n-propyl isocyanate ~ .
n-butyl isocyanate t-butyl isocyanate hexyl isocyanate octyl isocyanate: ~:
dodecyl isocyanate :
octadecyl isocyanate hexadecyl isocyanate and mixtures thereof, as well as cyclohexyl isocyanate.

Isocyanate-termînated prepolymers typically ha~ing a molecuLar weight of from 200:to about 40Q0 can be prepared by reacting an : :

- 32 ~ 668~

e~cess oE an isocyanate componellt with a polyhydroxy compotle~t. ~he isocyanate component can be a diisocyanate or polyisocyanate as previously described or can be a low molecular weight isocyanate-terminated prepolymer.
: .
The hydroxy component can be one or more of a polyol, polyester, polyether, polycarbonate and Rf-glycol, all as described previously.
., It can be seen that the properties of ultimate urethane compositions can be modified by appropriate modifications in the compositions of the prepolymers.

, In addition to the formation of the urethane compositions described above, the Rf-glycols described herein can be converted ::
to the corresponding bischloroformate by treatment with chloro~
carbonyl pyridinium chloride:
~ ;' R - R - S - CH - R - OH \ O ~ -C-Cl ~ Rf - Rl - S - C - R3 - O~ ~3 C1~3 ~ 1l : :~
Rf - Rl - S - CH R2 C
Rf - R~ - S - CH - R3 - O - C - Cl ;

;
which in turn can be reacted with an appropriate amine to yield a urethane composition: :
:
. . .

- ~ 33 - ~ ~ ~6842 o f Rl S - CH - R2 ~ - C - Cl I -~ H N - A - NH
Rf - Rl - S - CH - R3 - O - C - Cl ~ 2 ~ O
~ H
- - C - O - R2 ~ CH - CH - R3 - O - C - N - A - ~- -11 11 __ Rf Rf where A is a divale~t organic radical as previously described.
.
The reaction between the isocyanate component and the hydroxyl component can be carried out in bulk, i.e., without solvent, or in the presence of non-reactive, anhydrous, organic solvents. Solvent media in which the reaction can be carried out include ketones, such as acetone, methyl ether ketone and methylisobutyl ketone; esters such as ethyl acetate, butylacetate, 2-ethylhexyl aceta~e, hydrocarbons such as hexane, heptane, octane and higher homologs, cyclohexane, benzene, toluene, xylene or blends of aliphatic~ cyclo-aliphatic and aromatic hydrocarbons. It is also possible to employ ethers, both aliphatic~and alicyclic including di-n-propyl ether, di-butyl ether, tetrahydrofuran~and the diethers of polyalkyle~e oxides. In addition, chlorinated~solvents such as dichloroethyl ether, ethylene dichloride, perchloroethylene~and carbon tetra-chloride can be used.

Among the~eolvents listed, the wa~er miscible solvents such as~acetone and methyl ethyl ketone are most important since they~allow conversion f Rf-urethanes into ~ater soluble Rf-- 34 - ~ ~66~Z

In all cases, the solvents should be anhydrous to avoid urea formation.
.

The raaction can, if desired~ be catalyzed and those catalysts conventionally employed in the urethane art are useful herein. Useful catalysts fall principally in two groups -a) amino compounds and other bases:triethylamine and other trialkylamines triethylenediamine 1,4-diaza-2,2,2-bicyclooctane N-(lower) alkyl morpholines N,N,N',N'-tetra-methylethelenediamine N,N,N',N'-tetramethyl-1,3-butanediaminè
N,N'-substituted piperazines dialkylalkanolamines benzyltrimethylammonium chloride :
b) organometallic and inorganic compounds: -cobalt naphthenate stannous chloride stannous octoat~;
stannous oleate dimethyl tin dichloride di-n-butyltin dilaurylmercapeide tetra-n-butyl tin trimethyl-tin hydroxide di-n-butylt;ndilaurate.

Such catalysts may be used singly or in combination with each other. Beneficial synergistic catalysis may occur when combinations are used.

:, ~ : ..

- 35 ~ Z

While it i9 possible to carry out the reaction without the use of a catalyst9 it is preferable for reasons of economy and to assure a complete reaction, to utilize one or more catalysts as listed in amounts ranging from 0.001 to 1% based on the weight of the reactants. It is similarly advantageous to carry out the urethane synthesis at elevated temperature, usually between room temperature (20C) and 120C and preferably at 60 to 80C to obtain a complete reaction between 0.5 to 8 hours rea~tion timeO

The reaction can be easily followed by titration of the isocyanate group or by IR analysis.

The determination of the critical surface tension (y ) in dyes per centimeter shows that the free surface energy of a polyurethane is lowered if the novel Rf-glycols are incorporated into the urethane chain.

The critical surface tensions (y ) are de~ermined by contac~
angle measurements as described by W. Zisman7 ~
Advances in Chemistry, No. 43, ACS Publications, Washington, D.C., 1964.
-The usefulness of the polyurethane compositions is, however ;~ conveniently shown by measuring the oil, water and soil repellency ratingsof substrates such as fabrics, paper, leather, etc. which are ~reated with solutions or emulslons of the novel urethane composi-tions.

s already indicated, the urethane compositions of the inven-tion are highly effective for imparting oil and water repellent pro-perties to substrate to which they are applied and coatings of these polymers may be prepared by any of the well-known techniques. When prepared by bulk or suspension polymerization ~ec~miques, these

5 -. ~ ::

- 36 ~ 8~2 urethane composi~ions can be applied, for example, from a dilute solution in suitable a solvent such as the fluoralkanes, fluoro-chloroalkanes, fluoroalkyl substituted aromatics, alkylesters of perfluoroalkanoic acids, chlorinated alkanes or aromatic, hydrocarbon aromatics, ketones, esters and others~ Concentrations of the flwori-nated polymer in the solvent can be adjusted to provide an amount of urethane composition deposited on the substrate sufficient to provide oil and water repellency. This amounts typically to a deposit of from 0.01 to 10~, preferably from 0.1 to 1%, of urethane compo-sition, based on the weight of substrate. If the urethane composition is obtained as an aqueous latex or emulsion, the system can be di-luted with water or other appropriate diluent to similarly provide an amount fo urethane ranging from 0.01 to 10~ of the weight of sub-strate deposited thereon.

The urethane solution or latex may be applied by any of the known techniques such as by dipping, spraying, brushing, padding, roll coating or by any desired combination of such techniques. The optimum method of application will depend principally on the type of substrate being coated.

Coatings of the urethane compositions of the invention may be applied to a~y desired substrate~ porous or non-porous. They are particularly suited ~or application to porous materials such as textiles, Ieather, paper, wood, masonry, unglaz~d porcelain and the like to provide valuable oil and water repellency properties. How-ever, they may also be applied to non-porous materials such as metals, plastics, glass, painted surfaces and the like to provide similar oil and water repellency properties.

In the treatment of paper the urethane compositions may be present as an ingredient in a wax, starch, casein, elasto~ler, or wet strength resin ~orm~lation. Aq~eous emulsions oE the urethane . ' : .
- 3~-~ ..
~: :
.. . . .... .. . . . .... ..

- 37 - ~ ~66~2 compositions are especially useful in the treatment oE paper. By mixing the urethane compositions in an aqueous or oil type paint formulation, it may be applied effectively to unpainted asbestos siding, wood, metal and masonry. In the treatment of floors and tile surfaces and like substrates, the urethane compositions may be applied by their incorporaeion in an emulsion'or solution.

Because of the ability of the surfaces treated with these urethane composi~ions to withstand abrasive action, the advantages incident to the repellency to oil and water and their resista~ce to soiling imparted by coating them with the urethane compositions of this invention, preferred classes of articles to be treated are papers and textiles.

Illustrative papers are carbonizing tissue, wallpaper, asphalt laminates, liner board, cardboard and papers derived from synthetic fibers.

For application to textile materials such as fabrics woven and non-woven, fibers, films, yarns, cut staple, thread etc. or articles made from fabrics, fibers, films, yarns, etc. the urethane compo-sitions of the lnvention:are preferably prepared as aqueous latices or emulsions which are then diluted, preferably with water and applied to the textiles from pad baths which may contain other treating materials. In accordance with this technique, the fabric or the textile material is passed through the bath, passed through squeeæe rolls adjusted to leave the desired amount of latex on the fabric, dried at a temperature of about 25 to 125C and then cured in a curing o~en at a temperature in the range of from 120 to 195C for 0.2 to 20 minutes. The weight of urethane composition deposited on the fabric may range from 0.01 to 10% of the weight of fabric.
Preferably, very small amounts are used in the range of 0.1 to 1~, often from 0.1 to 0.5% to give high degrees of water and oil re-pellency. Any types of textile materials, such as cotton, wool, fiber 3~-~ ~:

, .. .. .. .... ... .. . ... .. . .. . .. . . . . . . . .. . ...

- 38 - ~ ~6~8~

glass, silk, regenerated cellulose, cellulose esters, cellulose ethers, polyesters, polyamides, polyolefins, polyacrylonitrile, polyacrylic esters, inorganic Eibers, etc. either alone or blended in any combi-nation may be successfully coated with the urethane compositions of the invention. The resulting textile material will be found to be re-pellent to water and oil, and the textile ma~erial will retain its re-sistance to such agents even after many launderings and dry cleanings.

It has further been found that besides their oil and water repellent properties the textile ~aterials also show increased dry soil repellent properties when the inventive urethane compositions are used the presence of a qua~ernary a~moniu~ salt containing a long hydrocarbon chain.
-' .

The mechanism of try soiling~ that is, soiling by particulate matter, i9 not influenced by free surface energy, but rather is a function of the surface characteristics of the finish, such as hard-ness, roughnessand, notably, the antistatic properties thereo.
For this reason, antistatic agents have been employed to reduce dry soiling in textile fabrics such as those which are intended for upholstery or carpeting. These antistatic agents are typically used at add-on levels of 3 to 10% by weight of fabric. One mechansim under-lying the operation of the antistatic agents requires the presence of ambient isture, which essentially acts as a conductor, thereby dissipating any static charge which would attræt and hold particulate matter. The hydrophilic nature of these antistatic agents and the high add-on levels required incrase wettability on the fabric by polar liquids, especially water. Thus, the properties of soil re~
sistance and wat&r repellency are antitheti al. Those textile finishes which are highly water repellent, i.e. have AATCC spray ratings of 80-100, display very poor dry soil resistance while those textile finishes that display good dry soil resistance display poor water repellency (0-60 AATCC spray ratings).
.
,~ . .
- 3~~

_ 39 _ ~l~ 6 6 8 ~ Z
These quaternary ammonium salts can be used in amounts from about 3 to 100%, based on the weight of said fluorine-contailling com-position .

The textiles characterized by oil and water repellency togetherwith improved dry soil repellence, contain fro~ 0.01 to 10%, based on the weight of textile, of a fluorochemical amd from 0.01 to 0.3~, based on the weight of textile of a quaternary ammonium salt con-taining at least one long hydrocarbon chain.

The quaternary ammonium compound can be one where the quaternizable nitrogen atom is substituted by aliphatic and/or aromatic groups or where the quaternizable nitrogen atom is a member of a heterocycle such as pyridine, quinoline, isoquinoline, imidazole, benzimidazole, morpholine, piperidine, pyrrolidine, pyridazine, pyri-midine, pyrazine, indazole, pyrazole, indole, and pyrrole.

Some of the useful kinds of quaternary ammonium compounds are de~cribed below.
.
Representative of the quaternary ammonium compounds wherein the quater~izable nitrogen atom is substituted by aromatic and/or aliphatic groups are compounds of formula -_ _ : .

a) R' X ~ :
R ~ 3 where iS branched or s~raight chain alkyl of 8 to 21 carbon ato~s;
phenylalkylene of 12 to 27 carbon atoms;
branched or straight chain alkenyl of 8 to 21; or straight or branched chain alkadienyl of 8 to 21 carbon atoms;

~ 40 ~ 3lO66B4Z
.
R'2 is brancbed or straight chain alkyl of L to 21 carbon atoms;
phenylalkylene of 8 to 27 carbon atoms;
y-hydroxyallcyl of 2 to 4 carbon ato~ns;
branched or straight chain alkenyl or alkadie~yl of 8 to 21 carbon atoms; or the group of armula ~CH2CH2o)xH .
where x is an integer rom 1 to 25;
or R'2 is alkylene of 1 to about 8 carbon atoms containing a quaterni~ed nitrogen atom whose substituents are -alkyl, phenylalkylene, y-hydroxyalkyl, alkenyl, alkadienyl or the gro~p ~CH2CH20)XH
all as previously defined;
:,' .
R'3 and R4 selected from the same group as R2 with the further -- li~itation that only one of R29 R3 and R4 can be seI~cted from the same group as Rl ~ ~ , and X is an anion.

In a more preferred embodiment R'l is as defined and R12~ R'3 and R4 are alkyl of 1 to 4 c~rbon atoms, hydroxyalkyl of 2 to 4 carbon atoms or benzyl.

Particularly preferred are those compounds where R'2 and R'3 are~methyl and R4 i~s~methyl~or benzyl. Especially preferred are the compounds where ~2, R'3 and R4~each is methyl.

- 41 - ~ID ~ ~ ~ 4 Z

Typical anions include chloride, bromide, iodide, Eluoride, phosphate, acid phosphate, sulEate, bisulfate, methyl sulfate, ethyl-sul~ate, sulfonate, carboxylate, acetate, chloroacetate, formate, oxalate, citra~e, acrylate and perchlorate. Preferably X is the anion of an acid having an ionization constant, pKa, of 5.0 or less, i.e., a dissociation such that the hydrogen ion concentration is at least 10 5.

R'l as can be seen, is a higher alkyl, alkenyl, alkadienyl or phenylalkyl component. One convenient source for the components of R; is the group of saturated and unsaturated fatty acids containing from 8 to 25 carbon atoms in the aliphatic chain. Illustrative acids include capric, lauric, myristic~ palmitic, stearic, arachidic, behenic, lignoceric or cerotic; decylenic, dodecylenic, palmitoleic, oleic, ricinoleic, petroselenic, vaccenic, lineoleic, linolenic, eleostearic, licanic, parinaric, tariric, gadoleic, arachidonic, cetoleic and erucic.

Natural sources for these acids include tallow~ cottonseed oil, coconut oil, peanut oil, palm oil, linseed oil, castor oil, safflower-seed oil, fish oil, and soya oil.
, : -The alkyl group embraced by R'2 includes, in addition to the higher alkyl components described above~ normal and branched lower al~yl co~ponents exempli~ied by methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl and octyl. -~

Illustrative y-hydroxyalkyl are hydroxyethyl, hydroxypropyl and hydro~ybutyl.

Some representatives quaternary ammonium compounds are listed below. It should be noted that the listing i9 illustrative, that these kinds o~ compou~ds independently are old and well-known, as are _ L~

'- \

- 42 - ~066842 their syntheses and that these compounds can be used singly or in admixture with other quaternary ammonium compounds.

Octadecyl-trimethyl ammonium chloride hexadecyl-trimethyl ammonium chloride cetyltrimethylammonium bromide te~radecyl-trimethyl ammonium chloride dodecyl-trimethyl ammonium chloride dodecyl-trimethyl ammonium bromide ~: decyl-trimethyl ammonium chloride : octyl-trimethyl ammonium chloridé
octyl-trimethyl ammonium bromide (10-phenyl) octadecyl-trimethyl ammonium chloride ~. octadecenyl-trimethyl ammonium chloride ; octadecadienyl-~rimethyl ammonium chloride .
dioctadecyl-dimethyl ammonium chloride di-hexadecyl-dimethyl ammonium chloride di-(10-phenyl) oJctadeyl-dimethyl ammonium chloride hexadecyl-trimethyl ammonium bromide octadecyl di~2Thydroxyethyl)-methyl ammonium chloride -octad~y~dimethy~-benzyl a~monium chloride .
hexadecyl-dimethyl-benzyl ammonium chlorida octadecyl~he~adecyl-dimethyl ammonium chloride : .
eicosyl-trimethyl ammonium bromide dioctyldimethyl ammonium chloride didecyldlmethyl ammonium chloride : :
decyltriethyl ammonium chloride hexadecylmethyI-di-(hydroxyethyl) ammonium chloride :.-hydrogenated tallow-tri~ethyl ammonium chloride ~.
soya-trimethyl~ammonium chloride coco-trimethyl ammonium chloride octadecyl-di(polyethylenedioxite 7)-methyl ammonium chloride :
N-(9-phenyl-octadecyl)-N,N-dimethyl-N',N',N'-trimethyl propane diammonium dichloride - 43 ~

stearyl-benzyl-dimethyl ammonium chloride octylsulfonamidopropyl-trime~hyl ammonium chloride . stearylcarbonamidoethyl-trimethyl ammonium sulfate :~ b) Among tbe useful aromatic heterocyclic quaternary ammonium compounds are those of formula X
where R'l X and R'l are described above and where is pyridine, quinoline, isoquinoline, pyridazine or pyrimidine; ~ .:
: a is an integer from 0-3 and :; R' is selected Erom hydrogeng alkyl of 1 to 4 carbon : atoms, hydroxyalkyl of 1 to 4 carbon atoms, halogen : ~ (Cl, Br, I, F) alkoxy of 1 to 4 carbon atoms, carboxyl, carbalkoxy of 2 to 4 carbon atoms, acetyl, ben~yl, sulfo, carbamyl and cyano. :~
: ~ :
: When a is greater than 1, the substituents can be the sc~me or different.

Representative pyridine starting materials include pyridine;
2-methylpyridine; 3-methylpyridine; 4-methylpyridine; 2-ethyl-pyridine; 4-n-butylpyridine; 3,5-dimethylpyridine; 3,4-dimethyl- :
pyridine; 2-benzylpyridine; 3-benzylpyrid;ne; 3-bromopyridine; 4-chloropyrid me; 3,5-dibromopyridine; 3-ethyl-4-methylpyridine; 4-. . : .
L/ 3 ::

_ ~4 ~ 6~4~
isopropylpyridine; 4-metho~ypyridine; 2,4,6-trimethylpyridine;
3-pyridinecarboxylic acid; 3,5-pyridinedicarboxylic acid; 3-pyridine-sulfonic acid; 3-pyridinecarboxamide (nicotinamide); 2-amino-6-methyl-pyridine.

Useful quaternary compounds are exemplified by hexadecyl-pyridinium chloride hexadecyl-pyridinium bromide.

Representative quinoline and isoquinoline starting materials include quinoline; 3-chloroquinoline; 2-methylquinoline; 4-methyl-quinoline; 8-methylquinoline; 2,6-dimethylquinoline; isoquinoline;
etc. to obtain such quaternized compounds as hexadecylquinolinium chloride and hexadecylisoquinolinium chloride.
. .
c) Other useful heterocyclic quaternary ammonium compounds can have the formula - -~ ~ ~ R
~+

J R~
where R~3 a, R, R'l, R'3 and X are as previously defined and ~;; ; ~ N ~

is imidazole, benzimidazole, morpholine, piperidine, pyrrolidine, pyrazine, indazole, pyrazole, indole, and pyrrole.

~: :
`

. . ~.. : ~ .. .... .. .. .. .. . .. ....

- 45 - ~ ~66~Z

Representative compounds include l-methyl-1-(2-hydroxyethyl)-2-heptadecyl imidazolinium chloride 1 methyl-1(2-hydroxyethyl)-2-heptadecyl imidazolinium methylsulfate N-hexadecyl-N-ethyl morpholinium ethosulfate.
, `~ The quaternary compounds can be prepared by alkylating the corresponding tertiary amine in known manner. The quaternary ammonium salt is typically employed in an amount of from 3 to abou~ lO0~ based on the weight of fluorine-containing composition~ described below.
Most conveniently, the salt is added to a solution, suspension or emulsion of fluorine-containing composition. The preferred range is from about 10% to about 33% of the weight of fluorochemical. This amount provides a dry textile carrying from 0.01 to 10~ bàsed on the weight of textile, of fluorochemical and from 0.01 - 0.3%, based on the weight of textile, of the quaternary ammonium salt. The pre-ferred range is from 0.03% to about 0.1% of qu'aternary ammonium salt based on the weight of textile and from 0.05 to about 5% of fluorochemical, based on the weight of textile.

It will be of ten advantageous to use the urethane compositions ! :~: of the invention in combination with ccnventional finishes, such as mildew preventatives, moth resisting agents, crease resistant resins, lubricants, softeners, fat liquors, sizes, flame retardants, antistatic agents, dye fixatives and water repellents.
~: :

:~,: :

- 46 - ~066842 Example 1:

2,3-Bis(1,1,2,2-Tetrahydroperfluorodecyl~hio)-butane-1,4-diol . . .
C8Fl 7c~l2cH2scHcH2oH
C8F17CH2CH2scHcH20 .: .
2-Butyn-1,4-diol (l.lg; 0.013 ~ole) and 1,1,2,2- tetrahydro-perfluorodecanethiol ~13.64~; 0.028 mole) were stirred together in 16 ml 2-butanone with 0.4 g azobisisobutryonitrile ~ABN) catalyst.
The solution was heated to 83-85 for four hours, then a further 0.4g of catalyst was added and heating and stirring were continued for a total of 24 hours. After cooling, the solvent was removed by eva-poration and the product was recrystallized from benzene to give 8.28g of the desired product (61% conversio~). Further purification was effected by distillation of the material (b.p. 180-204 at 0.6 mm Hg) and final recrystallization from benzene. The pure product melted at 110-112. The infrared spectrum showed OH stretching frequency at 3370 cm~l; CH stretching frequency at 2938 and 2878 cm 1 and CF stretching/'frequency from 1330 to 1100 cm - . , .
The structure was confirmed by nmr examination, which showed signals at:
2.0 - 3.4 ppm, -CH2CH2S- and OH (lOH~;
3.8 ppm, OCH2 (4H); and 4~3 ppm, SCH(2H)-Analysis ~for C24H16F342 2 Calculated: C, 27.55~; H, 1.54; F~ 61.73 Found: C, 27.54; H, 1.67; F, 61.46 : ~: t ~: :

., - 47 ~ 6~8~'~

Example la:

2,3-Bis(1,1,2,2-Tetrahydroperfluorodecylthio)butyl-1~4-Dimethacrylate C8Fl7cH2cH2scHcH2ococ(cH3) CH2 8 17 2 2 H H2 COC(CH3) CH2 A 50 ml flask was charged with 2,3-Bis(1,1,2,2-tetrahydro-perfluorodecylthio) butane-1,4-diol (10.46 g; 0.01 mole), pyridine (1.58 g; 0.02 mole) and a mi~ture of lS ml heptane ~nd 10 ml methyl-ethyl ketone. The solid diol was dissolved with warming to 70 and continuous stirring. Methacrylyl chloride (2.00 g; 0.02 mole) was added over a 30 minute period, under nitrogen. A white solid gra-dually precipitated from the liquor. To ensure complete reaction the mixture was stirred at 70 for 8 hours. All solids were removed by filtration and the solvents were stripped under reduced pressure.
Puriication of the crude dimethacrylate on neutral alumin~ gave 7.2g product (61.1~ of theory) as a white, waxy solid.

.
The structure was confirmed by spectroscopic examination.
Infrared bands were observed at 1735 c~ 1 (C-O stretching frequency~
and 1637 cm 1 (C=C stretching frequency). Nmr showed peaks at 1.9~ppm (6H) CH3; 2.0-3.3 pp~ (lOH) C8F17CH2CH2SCH; 4.35 ppm (4H)OCH2;
5.58 ppm (2H) H trans to C=O; 6.1 ppm (2E) H cis to CaO. ~mr and GLC
examination also showed the presence of a small amount of unreacted starting diol,which was difficult to remove. For this reason no true elemental analyses could be obtained.

On standing the monomer spon~aneously polymerized to a brittle solid.

, ~ ,, . . . . .. , .: ., ........ . ~ , . .. ..

- 48 - ~ ~6~
` .

Example lb:

2,3-:Bis(1,1?2,2-Tetrahydroperfluoroalkylthio?butyl-1,4-Dimethacrylate R~CH2CH2SCHCH20COC(CH3)=CH2 RfCH~cH2scHcH2ococ(c~l3)=cH2 Rf=Mixture of C6F13; C8F17; ClOF21 .
2,3-bis(1,1,2,2-tetrahydroper1uoroalkylthio)butane-1,4-diol (40 g; 0.038 mole) was converted to its dimethacrylate by treatment with methacrylyl chloride (8,5 g; 0.082 mole) and pyridine (6.5 g;
0.082 mole) in heptane/methyl ethyl ketone solvent at 70q for 8 hours.
Isolation and purification of tha product gave 29 g mixed dimethacryl-ate, as an off-white waxy solid. The structure was confirmed by in-frared and nmr spectroscopy. Infrared showed stretching frequencies at 1735 cm (C20) and 1638 cm (C=C). ~mr signals were at l.9 ppm (6H) CH3; 2.0-3.34 pp~ (lOH) GE2; 4.35 PP~ (4H) OCH2;
5.59 ppm (2H) H trans to C=0; 6.12 ppm (2H) H cis to C=0.

Example 2:

2,3-Bis(1,1,2,2-Te _ hydroperfluoroalkylthio)-butane-1,4-diol R~CH2CH2SIC 2 f 2 2 2 a) Sol~ent Free Process In a 500 ml Morton flask, 400g (0.8 mole) 1,l,2,2-tetrahydro-perfluoralkanethiol (similar to that described in Example 3, but having an average molecular weight of 500) was mixed with 327g ~96~
_ ~9 _ (0.38 mole) 2-butyn-1,4-diol. With moderate stirring the flask was heated to 75 under nitrogen by means of an ex~ernal oil bath. Azo-bisisobutyronitrile catalyst (AB~) was added in 5 equal portions of 1.32 g each, at 25 minute intervals (total catalys~ = 6.6 g; 0.04 mole or 5 mole % based on thiol). After the second catalyst addition, an exotharmic reaction was noted, which took the reaction temperature to 78 for a period of approximately 1 hour. The course of the reaction was followed by periodically removing samples and analysing hem by gas-liquid chromatography (GLC). This showed that af-ter

6-1/2 hours no further reaction was occurring. The composition of the crude reaction product was (area %) thiol (RfC~2CH2S~) 6.2~
mono addition product (RfCH2CH2SCCH20H) 1.9; diaddition product HCC~20H

(RfCE2CH2SC~CH20E) 86.4; unknowns 505.
I
(Rf CH2CE12SCHCH20H) -The crude product was purified by passage through a falling film molecular distillation apparatus at 110 and 8 mm Hg. giving 352 g. (85.0% conversion) product consisting of 1.2% thiol, 1.5%
monoaddition product, 93.0~ diaddition product and 4.3% unknowns.
: .
Recovery of unreacted thiol was 34g, bringing the overall yield (conversion and recovery) to 93.5%.
.
b) Solvent Process In a 2 liter Morton flask, 1,1,2,2-tetrahydroperfluoro-alkanethiol (as defined in Example 3) (483 g; l.0 mole) and 2-butyn-1,4-dlol (43.05 g; 0.5 mole) were mixed in 500 ml heptane.
The system was deoxy~enated with nitrogen bubbling below the liquid surface and was then heated to 75 with a blade stirrer rotating a high spe~d. A~obisisobutyronitrile catalyst (ABN) was added in en .
. -. ., :
/q - _ 50 _ ~ ~66~Z

portions of 1.64 g each over A 5 hour period. The reac~ion was con-tinued for a total of 20 hours. During this time the upper part of the flask not covered by the heating mantle was insulated with glass wool to prevent the deposition of the forming product on the walls.
The reaction mixture was cooLed, with stirring, to allow the product to crystalli7.e. Filtration and drying at 40 and 0.5 mm Hg permitted the recovery of 441.7 g product (83.7% conversion). From the filtrate and the material removed during the pumping operation 61.2 g un-reacted thiol were obtained. The overall yield was 96.4%. The product melted over the range 73 - 94~. Gas chromatographic examination showed it to be the dialkyl diol with no trace of the monoaddition product.

Examples 3-7:

Further examples of the free radical addition of 1,172,2-tetrahydroperfloroalkanethiol to 2-butyn-1,4-diol areshown below.
Except where indicated, Rf is a mixture of perfluoroalkyl chain~
C6FI3, C8F17 ~nd CloF71.

' ' ' ~':

~: .

; :

. - ~

- 51 - 1~668~

oo ~ ~
~,, , ., . . . .
P~ C~l ~ CJ~
. .
_ . .
C . . .
. i~ ~o ~
,~ ~o o o C ~ b4 C~
C
,~ ~
. ~,,, ~ o ~ C
o o ,~ ~ ~ V
~ C~ , . .
~ o ~ ~ ~ V . .

C~ ~, ~ .,, C~ V bO 00 ~D ~0 U~
b4 i ~ _I
a~
o I~ ~ ~ C ~
~ ~ ~ X oo , ,, _ ~a ~o~ oo ~ ~ V ~ , .
Z ~~o ~ oo ~ .~ ~ .
_ n~. ~ ~ :
: ~ V ~O ~t Q~ ~ ~ .c ~ O C O ~ ~ ~ ~ .
. ~ ~ :
-1 .u~ 3 u~ p, ~ ~
~: o 1~ u O ~1 . .
,: u~ ~ :C ~ X :r: ta ,~ ~ _ ~ ~ :: :~ ~ e a o :-~ X o ~ ~, ~ ~ ~q O
~1': . o . ~ ~ ~ .~ ~ O W
W, .-: ~ ~~o ~ 00 ~o P~
o .. . U~ U~ ~ V
~ o~ 00 ~ ~ :~ O
_ : ~ o o - ~: Oa O ~ O. C~ ¢ ~ :
~: ooooo ~
~? .

~: ~ 00 0~ ~ ~ 00 o ~ . .

L
~: ~ ~ ~ ~ : ., . ~ ~ ~ ' ~,' , . ..

- 52 - ~ ~668~Z

Example 8:

2,3-Bis(1,1,2,2-Tetrahydroperfluorodecylthio)-l)utane-1,4-diol ., C8F1 7CH2CH2SCaCH20H

The example shows that the addition may be carried out thermally, without the need for added catalyst.

1,1,2,2-Tetrahydroperfluorodecanethiol (4.8g; 0.01 mole) and 2-butyn-1,4-diol (0.43g; 0.05 mole) were sealed in an ampoule, under nitrogen, with no solvent. The reagents were stirred at 158 for 20 hours during which period a hard, light brown solid formed.
Gas chromatographic examination showed this to be 2,3-bis(1,1,2,2-tetrahydroperfluorodecylthio)-butane-1,4-diol. The mono addition product was not formed. The product was purified by crystallization from benzene, and then melted at 105 - 109. The infrared and nmr -data were identical to that obtained for the product of Example 1.

' Example 9:
--.

2,3-Bis(4-Heptafluoroisopropoxy-1,1,2,2-tetrahydroperfluorobutylthio)-butane-1~4-diol (c~3)2cFocF2cF2cH2cx2scHcH2oH

(cF3)zcFocF2cF2cH2cH~cHcH2oH
4-Heptafluoroisopropo~y-1,1,2,2-tetrahydroperfluorobutane-thiol (80g; 0.229 mole) was~stirred at 74 with 2-butyn-1~4-cliol (9.39g; 0.109 mole) under nitrogen. Azobisisobutyronitrile catalyst 1.88g; 0.0114 mole) was added in 5 equal portions at intsrvals of 5 ~ -_ 53 ~ 8~

25 minutes. Af~er 10 hours GLC indicated that no Eurther reaction was occurring. The crude product was washed with benzene, filterecl and dried to give 69.5g product (81.9~ of theory). A small sample was further recrystalliæed and had m.p. 84-88.

The infrared spectrum showed strong O-H stretching frequency at 3300 cm 1 and characteristic C-F bands at 1100 - 1300 cm 1.

Nmr showed: 2.0 - 2.6 ppm, CFCH2 and OH (6H); 2.85 ppm, SCH2(4H);
3.1 ppm, SCH(2H); and 3.9 ppm7 OC~2(4H).
~` .
` Equivalent wt: Calc. 389; found 388.

AnalySis for C18H16F224 2 Calculated: C, 27.77, H, 2.07; F, 53.69 Found: C, 28.03; H, 2.03; F, 53.32.
.
. .
'~ Example 10:
' 1 2,3-Bis(Heptafluoroisopropyl-1,1,2,2-tetrahydroperfluoroalkanethio)- .
butane-1,4-diol ~: :
; (CF3)2CFO(CF2CF2)mCH2CH2Scl~cH2 (CF3)2cFo(cF2cF2)mcH2c82scHcH2 m = 3 or 4 ~;-HeptaIluoroisopropoxy-1,1,2,2-tetrahydroperfluoro-; alkane-hiol [(cF3j~2cFo(cF2cF2) CH2CH2SH] (consisting of 73% m = 3 homolog and 27% m = 4~homolog~ (80g; 0.14 mole) was added ~o 2-butyn-1,4-diol (5~.72g; 0.067 mole) using ABN catalyst (1.15g; 0.007 mole) in the ma~ner described in the previous example. In this case the crude~product was puri~ied by passage through a molecular distilla-~ ~ .

_ 54 - '~ ~ 6 6 ~ ~ 2 tion apparatus. This gave 69.7g product and 12.2g recovered thiol.
Conversion is thus 83.92 and yield is 99.2% based on starting thiol.
The waxy product had a melting point o~ approximately 37C. Its nmr and infrared spectra were very similar to those of the preceding exa~ple. GLC e~amination showed that the product was a mixture of three products, formed from the two original thiols. In area % there were: m = 3,3 43.3%; m = 3,4 40.9%; m - 4,4 15.80%.

Analysis:
Calculated: on the bais of wto % = area %
C, 26.36; H, 1.29; F, 62.07 Found: C, 27.3~; H, 1.39; F, 61.19.

Examples 11 to 13:

Addition of available thiols to commercial acetylenic alcohols and esters is illustrated by Examples 11 to 13. In each case a free radical catalyzed addition of 2 moles of thiol to 1 mole acetylenic alcohol is involved. The experimental procedure is as described in Example 2a.

~ .

~ ~ - 5~1-~ ,. , .. . . .. . ' _ 55 ~ 8~L2 _ . ~

~x~
ô~ ô~
~, o ~ ~ oc~, o~
~ ~, V~
~ d` ~ C~l ~ X ~
, C~ ~ I~ I~
o ~ oo .
~ ~,, V, ~
~ '~"' o ~
- ., -o~ ~ o~ ~ :.
O a ~ ~
0 ~ ~ V~ ~ ~ -~ 0~ ~ ~
~ _ '.- :.' : ~ : ..

~:~ ~
. ~ ~ ~ ~ i ~ ~ ~
O ~ ~ ~ ~, .~ ~ ~ ~1 ~
0 ~ ~ ~ ~ ~ CO ~ ~ ...... ..

~: ~ = ~ ~ ~

~ i~66~2 : Example 14:

2,3-Bis(1,1,2,2-Tetrahydroperfluorodecylthio)butane-1,4-di(hydroxy ~` ethyl ether) _ C8F17CH2CH2SCWCH20(CH2Ca20)n C8Fl7cH2cH2scHc~l2o(cH2c~l2o)n n a average 1 .~ .
In a glass ampoule, 1,1,2,2-tetrahydroperfluorodecanethiol (15.4g; O.Q33 mole) and 2-butyn-1,4-hydroxyethyl ether* (2.61g;
0.015 mole) were shaken and heated at 75 with 492 mg ABN for 18 hours in 20 ml heptane. A waxy product was ob~ained which after removal of excess thiol, melted in the range 26 - 48. Infrared examination con-~rmed the assigned structure, showing 0-H stretching frequency at 3405 cm Nmr showed signals at 2.2 - 3.2 ppm SCH2CH2Rf and 3.2 -- 4-2 ppm -CHO(CH2CH20)nH with the correct integrals.
. , .
Elemental analysis:
, :
, Calculated for C28E24F344S2 (average n = 1) - C 29.64; H 2.13; F 56.93 Found: C 30.04; H 2.25; F 55.84 * A commercial product H(OCH2CH2)nOCH2C-CCH20(CH2CH20)nH~
with n - 1 average, but actually being a mixture of at least five distinct compounds.

:' :: ::
: : ~ : :: :

:~: : : : : :

57 ~f;3668~2 Example 15:

2,3-Bis(1,1,2,2-Tetrahydroperfluorodecyltbio)butyl-1,4-diacetate C8F17cH2cH2scHcH20co~H3 In a similar manner as Example 14, 1,1,2,2-tetrahydroper-fluorodecanethiol (15.84g; 0.033 mole) 2-butyn-1,4-diacetate (2.55g;
0.015 mole) and 492 mg azobisisobutyronierile were heated àt 75 for 19 hours to give 12.3g (6?~` product boiling at 185 at 0.1 mm Hg.
Infrared analysis (C=0 stretching fre~uency at 1750 cm 1 and the absence of all 0-H frequency bands) and nmr examination confi~ed the structure.
Nmr showed signals at 2.3 - 3.2 ppm (8H) SCH2CH2; 3.45 ppm (2H) SCH;
and 4.38 ppm (4H) OCH2. The methyl protolls resonated at 2.05 ppm.
,, . ~
Elemental Analysis:

Calculated for C28H20F3404S2 Found: C, 29383 H, 1.78 F, 56.59 ~: :

Example 16:

2-tl,1,2,2-Tetrahydroperfluorodecylthio)-2-butene-1,4-dlol -~

H2oH

Z,2-Tetrahydroperfluorodecanethiol (24g; 0.05 mole) wa~added slo~ly to a mixture of 2-butyn-1,4-diol (6.5g, 0.076 mole) ;in~heptane,~contaiDing~a20~mg ABN catalyst.

- 58 - ~ ~66~2 This procedure gave a product enriched in the butenediol desired but also containing some of the diadduct (butanediol). The mono-adduct butenediol was obtained in a pure state by sublimation at 150 and 0.7 mm Hg.
~;
~I.P. 87 - 89. ~mr showed pe~sat 2.2 - 3.2 ppm (4H) CH2CH2S;
3.8 ppm (2H) OH, 4.22 ppm (2H) S-C-CH20; 6.24 pp~ (lH) = CH. The yield was 26%.

Elemental Analysis Calculated for C14HllF172S C~ 29-69 H~ 1-96 F~ 57-03 Found: C, 29.49 H, 1.89 F, 56,71 ,~ .
Examples 17 - 29: The following e~amples illustrate the wide variety of solvents which may be used in the reaction. All reactions were carried out with 1,1,2,2-tetrahydroperfluorodecanethiol (5.28g;
0.011 mole), 2-butyn-1,4-diol (0.43g; 0.005 mole) and 164 mg azobisisobutyronitrile. A reac~ion time of 18 hours at 76 was uni-form for each example. Product analysis was made by gas chromato-graphy~ Since an excess of thiol was used, the results are given be-low in two sections. The first shows the thiol present in.relation ~ -to the mono- and di-adducts and is thus an indication of the suitabili-ty of the sol~ent. The second section shows the relative amounts of mono-adduct to dl-adduct, without regard to the thiol present. In each case the mono-adduct is C8F17CH2CH2SCC~2H and the di adduct is C8F17CH2CH25CHCH2H
gF17CH2C~12SCHCH20H.

The results show that an inert, non~polar reaction mediu~9 typically n-heptane, leads to maximum conversion of thiol and :
greatest production o~ di-adduct.

g ~

, : , ' . , , . ` ,' ' ' .. .. : ,' : . : . ~ : .. ' : : ': : ' :

_ 59 _ ~1136t~8~Z

1 ~ r~

~ ~ OO, ~
~ ~ Cl~ I tU
IC~I Cp~ oo U~ ~.D U~
c . ~ , O cn 1~ ~ O Cl:~
o co Oo ~ ~ .
5~ ~ t w ',',.
: ~ _ . , 1,~ ~
~ _~ ~0 ~ `D ~D cn ~ ~ ~ ~ o~ ~ O co 1~ C~l C) ;
t~ ~ ~ I~ c~ ~ o ~-~ co ~3 : ~ .~ a~ u~ ~ .
c~ ~ ' ,. . ' v . ~
~ ~ oo ~ c~ o ~J r) o c~ ~ ' ' .
: O r~ ~ ~ ~ ~ ~ ~ ~D cr~ r~ ~ ' .
~4 , O ~ ~ ~ o ~ ` ~
, ~ .,~
_ ~ -- a~ 0 ' ' : , ;C ~ ~ ~D .
: : : ~ 3 : : ~ ~ w : ' ~ ~ ~ ~ . O h ' pt o ~1 ~ r~
Ei: 5~ c~ ~ o o _I O O c~l : ; 0 ~ ~ CJ ~ cd ~ ~ ~ ,, E3 : _1: ~ 0 ~ _I W
: ~ , o ~ ~ ~ ~ : ~ ~ ~ C
: ~ a : ~ ~0 ~ ~ :~ ~ o : ~ ~: O; ~ ~ V I ~w: ~
I: : u~ : ~::: : ~ : ~ E~
: '.":
"",~ ~ _ :~ ~

~66'B~2 E_amples 30 to 36: Various free radical catalysts~ in addition to ultraviolet irradiation, may be used to initiate ~he addition re-action. Below shows the effect of several differentchemical initia-tors. Their ef~ectiveness is judged by the amount of thiol consumed.
In eachreaction 1,1,2,2-tetrahydroperfluorodecanethiol (4.8g;
0.01 mole) and 2-butyn-1,4-diol were heated wit:h the desig~ated catalyst (10 mole ~ based on thiol). Heptane was used as a solvent except as indicated.

_ ~ Reaction . _ ~
Example Catalyst Temp.~C Ti~e Hrs. Consumed . .. ~ . _ benzoyl peroxide gO 18 45 31 lauroyl peroxide 85 18 42 32 azo bisisobutyronitrile 75 18 78 33 2-~-butyl azoisobutyro-100* 17 75 nitrile 34 l-l-butyl a~o-l-cyano- 117* 17 76 cyclohexane -2,5-di~ethyl-2~5-di 130** 20 28 (t-butylperoxy) hexa~e ~
36 di-t-butyl peroxide 140** 20 ~3 * ~ethyl isobutylketone solvent ** o-xylene solvent ': .
All peroxides gave poor conversions of thiol to di-adduct and also gave rise to considerable amounts of unidentified by-products.
Thus the actual conversion of thiol to di-addùct în these cases is ~ .
~uch lower than the actual thiol consumption.
, ~ .
: . :
:
~: .

b .
~ .

- 61 - ~ 8~2 ~.

Examples 37 to 45: Other examples of the radical catalyzed addition ::`
of Rf-thiol to commercial acetylenic alcohols and esters, using reaction conditions as shwon in Example 2a are listed below.

Examples 37 to 45 illustrate additiona'L combinations of Rf-thiols with acetylenic diols and esters. The reaction conditions are those of Ex~mple 2a.

: ' .

t~

. ' . .

, .

:: ::

~668~Z

_ . .. _ _. _ _ .

o o ~ :~
o o C~
~ ~ o o o o 5~ ,~ o~ o~
~ C`I

C~
~ ~ e;~
C) C~ C~ C~
~ ~ X~ ~
C~ C~ ~ o o u~ ~ u~
x~ r ~ x ~ . -C~ ~ , ~
_~ C~ 4 ,~ ~ ~ ~ ;;, ~ a~ oo oO oo P~ C~C~ ~ C~C~ C C~ C~ C~ ~-1` c~ c~ 1` ..

lY o C~ C~ o o cr~ c~ ~ "~ ~-~, ~ 111 O ~ O
¢ ~ c5 ~ :' + + + +

X~ ~ X
s~ r, :: U~ ~ ~ ~ C~
~:: ~ C~ ' C~

O ~40 ~C~ ~' a~ ~
~ ~ : C?~ .
~3 : ~
.
:: , . .
G ~ -. . . , . . . ~ - ` . . . ~ " ~ .,. , - ... .. . . .. .. .

-~ 63 ~ ~ 66~

~ r _ _ _ _ _ ~ , x~ ~ x O ô ~ r tl 5 c~ O O
5~ P ~ ~ s ~~ ~~ c) c ) c~~ ~ 0~ 0~ 0~ 0~ Oc~l O
~C) c) ~ O O c~ c) c~
O O O O
t~
, ~ m ~ X:~:
U~ C ~ ~ 3~ q , c~ J ~ m ~ m ~ ,, ~ m~C) ~ c c~ c~ c C) C) 1~ C) ~ ~ P~ o, c 8 ~o ~z; z;~ rf~ æ ;~z z æ
. ~ o ~ ~ ~ ~ ~ ~3 ~ ~ ~ ~ ~
~ ~ r ~r ~ P o~ r x P~ c) ~ ~ C~ r~ ~ ~
C~ I` '` I` I` I` I` X r~ ~ I~ r~ ., ~ .
~1 ~1 ~1 ~ ~CO ~00 ~oO ~co ~co ~a o ~ ~ ~ ~
~ c) c~ c~ c) c) ~ c~ c) ~ ~ . .
c~ c~ ~ ~ ..
~ ~ '~ o ,, J c~ .''''.
o c) o o c ~ 111 ~ ` ~ 111 c~ ~ c x ~ c) ~ ~ . .
O U~ Co lCI I C) Co :':
.C ~ CO ~C~ ~ o ': .' : ~ O ~ ~ O ~ .-,' + + ~ + + .
~ U~
r~ ~
x 5 ~ ~ ~ ..
~ c~ : ~
~ r~ u c o~ z~ z~
r~ c)l ~ a "., . ,, ,~ ; .
,~ ~ ~ ~ ~ ~

O C~ ~ c,~ :' .
c~
. ~ _ ~ ___ ~ x ~ _I c~l ~ ~ u~
~ o~ ~ ~ .

- 6~ 66~2 E~ample 45a: This e~ample illustrates the conversion of a per-fluoroalkylalkylene iodide to the corresponding thiol by reaction with thiourea.

In a 1 liter flask is place 100 g (0.138 mole) of CllF23CH2CH2I, 12.6 (0.166 mole) of thiourea and 100 ml of anhydrous ethanol and the mixture is refluxed for 5 hours. Then about 50 ml of the ethanol is stripped off under vacuum and 400 ml H20 and 11.04 g (0.138 mole), of 50% aqueous NaOH are added and the reaction mixture is boiled., The mercaptan, CIlF23CH2CH2SH, is collected in a Dean-Stark trap as a lower layer in good yield.

~:
Example 45b: This example illustrates two alternate synthetic methods for preparing the thiol Rf - Rl - SH

A. Reaction of Rf - CH = CH2 with H2S.
`
The olefin CgPlgCH = CH2 is reacted with H2S at ~53C at 200 - PSIG H2S, the mole ratio of H2S to olefin being about 30:1 in a water jacketed quartz tube irradiated with the ultraviolet light furnished by two 36" germicidal lamps under static conditions. The major product is:
; ; C9~l7cH2cH2sH
B. Reaction o~f RfCH2CH2I with thiourea followed by hydrolysis.

In a 5 liter round``bottom flask equipped with a water cooled condenser, stirrer and heating mantle is placed 624 g (1.0 mole) of (CF3)2CF(CF2)6CH2CH`2I, 114 g~thiourea (1.5 mole) and 3 liters of absolu-te ethanol. The reaction mi~ture is heated at reflux for 26 hours. Ethanol is then~removed ~hile addin~ wa-~er to maintain ` . . .
::
~.

- 65 - ~ ~66~

constant volume. 200 ml of lM WaOH is then added and the solu~ion co distilled with water into a phase separator. The aqueous phase i8 returned to the reaction vessel. Further distillation gives the pure mercaptan (CF3)2CF(cF2)6cH2cH2 Example 46: The diol of Example 1 (7.85 grams; 0.0075 mole) and Tonco 70(Trademark- a commerical mono-isocyanate containing 70% octadecyl iso-cyanate and 30% hexadecyl isocyanate 4.31 grams; 0.05 mole) ~ere dissolved in 20 ml urethane grade methyl ethyl ketone in a sealed re-action vessel. As a catalyst, 456 mg of a 1% solution ofdibutyl-tindilaurate (7.5 x 10 6 moles catalyst) in MEK was added and the re-actor was heated at 75, with agitation, for 18 hours, when infrared examination showed all -NCO functionality to be absent (no stretching vibration at 2275 cm ). 11.3 grams of urethane was obtained as an amber wax by evaporation of the solvent. The product melted at 73 to 88~-The infrared spectrum showed'N-H str. at 3335 cm 1 and C=O
str. at 1694 cm 1.
:: .
Elemental Analysis: Calculated: C, 45706; H, 5.45, N, 1.73, F, 39.86 Found: C, 45,00, H, 5,41, N, 1.74, F, 39,69 :

Example 47: When the diol of Example 1 (7.85 grams; 0.0075 mole) and Desmodur RF [Trademark- a commercial thiophosphoryl tris (4-phenylisocyanate~ (2.09 grams; 0.005 moles) are reacted according to the conditions of ~xample 46 there are obtained 8.0 grams o~
urethane product as a hard granular material.

Low molecular weight urethane compositions such as are described inIEx~mples 46 and 47 are useful as coatings on vinyl surfaces to render the same soil repellent. The urethane composition . . . ` ,.` ., ., . ` . ~ . ~ . . .. .... ,. ;.. , .. ,, , . ' . .. `, ,.` .. ;,. . '. ., . . ,. - .

66 ~ ;68~L~
:
composition can be applied from MEK solution to vinyl sheeting and the treated material resists soiling according to a standard test, in ` contrast to an untreated sample.

E~amples 48 to 52: 2,3-bis (1,1,2,2-tetrahydroperfluorodecylthio)-butane-1,4-diol (the diol of Example 1) was converted by reaction with equimolar amounts of a diisocyanate to a high molecular weight urethane composition characterized by the presence of a segment of formula:
O O
.~ Il 11 . .
0 - CH2 - CH - CH - C~12 - 0 - C - NH - A - NH - C -S S
. I I
ICH2 ~CH2 where A is the residue obtained from the indicated diisocyanate.
- .
;~ The Rf glycol and the diisocyanate were dissolved in about ~ 20 ml urethane grade methyl ethyl ketone in a sealed reaction vessel.
i The indicated amount of catalyst was added and the reactor heated for17 hours at 73~C with agitation. The results are summarized below.
` ~; :' :

~,~

: ~:

~ ` . .

'` ., .: , . ' ` ', " `' ' ' `, ~ ' ' ' ' ` ', ' . ' '" ' ' ` ' ' ` ~ , ,, . , : ; . ~., " ' . ' ' . ' , ' ' '` . ` ` , : '' ' - 67 - ~06~34;~

, . ~ . . . .,.. .. .
~ ..
\ ~ CO O u~ ~D
~*e ~ oo U~ o *~ ~ ~ ~1 ~1 ~iq ~ co ~O ,, ~ u~ r~ I` `J ~1 ~I r~ o ~ r~ u~
oo ~ ~ I~ u~ ~ ~ ~ o~ ~ ~D 00 1 ~d o ~ u~ 1 ~ O
U~ ~ ~ ~ U~ ~ U~
~ _ __ __ ~1 o a~ ~ o 1~ ~ ~
U~ U~ ,, ~ ,, ~ ,--, ,-, C~i ~,. ~ ~
~ _I ~ ~ ~ u~
.-1 C~ ~ Z 14 C:~ X 14 C~ CC h C~ S h c~ 5: h ~4 _ _ _ _ ~ O, O ~ C`l 00 ~ ~o O O O O
~-1 0 1-- ~ I ~ ,~ ..

3 ol) ~ In lo u~ lo ~1 10 10 ~ 10 X
_I _I ~ ~ ~ ~ tq ~: ' ~d X ~ ~ 0,~ - --C . _ _ . _ _ _ O ~ ~OQ '",.
K
5.~
o~ 0 I ~ U
oo O oO O c~ t~
~ ~ ~ ~ ~ ~O `D ~ -1 J O
: ~_ , a~ oo O ~ O ~ u :: ' ,ol O 0 ~0 0 0 O ~ ~ ~ O
~ 0 0 0 0 0 ~ ~ O~1 ~: ~ _ . _ _ __ ,,,, . ~ 1 U
~- ~ O _J '~
.~ oo ,i oo ~1 o~ C~
: 3 _ ._ __. _ K t~

U :
~ ~ ~ U
~ ~ ,E~ ~ o o : ~q : : ~
~ ~ ~ O ,~ 1~1 ~ 3 ' ~~ O ~ ~ O O ~
:
: ~ ~ O ,~
. . , . , ~ __ ~, ~ _ _ , ..
: ::, _ - 68 - ~ ~6~

Example 53: A hydroxy-terminated R~~containing prepolymer was prepared as follows:

2,3-8is(1,1,2,2-tetrahydroperfluorodecylthio)butane-1,4-diol tthe diol of Example 1) (20 g; 0.0191 mole ) was mixed with lysine diisocyanate methyl es~er t2.7 g; 0.0127 mole) in 20 g. methylethyl ketone. Dibutyltindilaurate was added (23 mg; 3.82 x 10 5 mole) to the resulting solution and the reaction vessel was heated to 75 with agitation until all isocyanate had reacted, as shwon by the dis-appearance of the N=C=O band in the infrared. Che solution was di-vided into two equal parts. One was used for Example 54. The other was poured into cold heptane to precipitate the urethane product.
After drying, this portion weighed 21.0 g. Infrared showed peaks at 3480 cm (O-H str.); 3340 cm (N-H str.) and 1715 cm (C=O str.;
ester and urethane).

Elçmental Analysis: Calculated for CgoH72F102N4014S6-C, 30.33; H, 2.04; N, 1.57; F,54.38 Found: C, 30.61; ~, 2.00; N, 1.67; F,53.96 Example 54: The hydroxy-terminated Re-containing prepolymer was converted into a urethane composition by reaction with additional diisocyanate and the reaction product capped by reaction with a mono-alcohol.
: :
~ ~ .
The prepolymer of Example 53 was treated at 75 with further amounts of lysine diisocyanate (1.35g; 0.0064 mole) to cap the free OH groups and the urethane was terminated by the addition of 2,3-bis~l,l,2,2-tetrahydroperfluorodecylthio) propan-l-ol (6.5 g;
0.0064 mole) Reaction was judged to be complete when no isocyanate peaks were visible in the infrared. The product was precipitated by pouring the MEK solution slowly into chilled heptane. After drying the final urethane weighed 28.9g, and had a rubbery consistency.

.
~ ' : ::

- 69 ~

No OH stretching frequencies were visible in the infrared, but N-H stretching frequency was present at 3335 cm and C=O (ester and urethane) was a broad band centered at 1715 cm Elemental AnalySis for cl54Hl24Fl7o 8 24 10 Calculated: C, 30.72; ~19 2.08; N, 1.86; F, 53.64 Found: C, 30.75; H, 2.10; N, 1.94; F, 52.95 ~ ' .
Example 55: This example illustrates the formation of diisocyanate-terminated Rf-containing intermediate and the conversion thereof to a high and low (relativej molecular weight urethane compositions.

A. High molecular weight 2,3-Bis(1,1,2,2-tetrahydroperfluorodecylthio)butane-194-diol (the diol of Example 1) (57.33g; 0.055 mole) was dissolved in I50g methylethyl ketone. Lysine diisocyanate methyl ester (5.83g;
0.0275 mole) ~as added, followed by 3.46 g of a 1% solutio~ of di-butyl tin dilaurate as catalyst. The solu~ion was heated under reflu~ and stirred in a nitrogen a~mosphe~e for 2-1/2 hours. Then dimer acid derived diisocyanate (DDI, available from The Quaker Oats Company) (33.0g; 0.055 mole) was added and heating and stirring were continued for a further 3 hours. To complete the urethane formation the isocyanate capped intermediate was divided into two equal parts. The first was treated with lysine diisocyanate methyl ester (2.77g; 0.013 mole) and N-methyl diethanolamine (3.11g9 0.027~mole), to glve a materiàl which was purified by e~aporation of the solvent followed by~freeze drying from benzene. An infrared spectrum of ~he material showed N~H str. at 3336 cm 1 and a broad ; carbonyl band (C-j str.) with a main peak at 1690 cm 1, due to the ester and urethane linkages. The material was only sparingly soluble in methanol. ~ `

- 70 ~ 6~Z

Elemental AnalysiS for C152~226F68N1020 4 Calculated: C, 46.4; H, 5.8, F, 32.8 Found: C, 46.5; H, 5.6; F, 33.8 Critical surface tension for wetting, y - 11032 dynes/cm.

B. Low molecular weight The second half of the isocyanate capped prepolymer was treated with lysine diisocyanate methyl ester (2.77g; 0.013 mole) and N-methyldiethanolamine (3.67g, 0.031 mole). The excess ter~ination diol acts as a chain terminator and gives a lower molecular weight poly-urethane. By freeze drying, a quantitative yield of polyurethane was obtained. The infrared spectrum and elemental analyses were similar to those o~ part A. The principal difference was that the low mole-cular weight urethane was very soluble in methanol, and could only be recovered in good yield by freeze drying from ben~ene.
' ' Critical surface tension or wetting, y = 12.37 dynes/cm.
'.' ,,.

.
E _m~ 56: A hydroxy-terminated Rf-containing prepolymer was pre-pared as follows:

Methyl ethyl ketone (600 g) was charged to a 2 1. flask fitted with a stirrer,~thermometer, nitrogen inlet and a condenser pro-tected with a drying tube. 2,3-Bis-(1,1,2,2-tetrahydroper~luoroalkyl-thio)butane-1,4-diol~ (600g;~ 0.571 mole)* was added toge~her with a 1 mixture~of 2?2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylenediisocyanate (80.16 g; 0.~81 mole). All re-a~ents were rinsed in with an additional 50 g ME~. The solution was heated to boiling and S0 g solvent was removed by distillation to effect azeotropic drying of all materials. Then dibutyltindilaurate :::: : : : . .

=-~

- 71 - _~lf~fff~6~

(0.692g; 1.14 x lO 3 mole; 2 mole % based on diol) was added as a catalyst and the solution was heated under reflux for six hours, when the reaction was judged to be complete by the absence of the N=C-O
lnfrared band at 2270 cm . The solution was cooled to room tempera-ture (25) and diluted with ~EK to a total of 2042 g (33-V3%
solids). A portion oE the above material was taken to dryness. A
; quantitative recovery of a resinous material was obtained. Elemental analysis showed 52.8%F (theory: 53.4~F). Infrared bands at 3460 cm ~ (O-H str.), 334fCf cm (N-H str.) and 1705 cm (C=) str.) confirmed ; the structure of the hydroxy-terminated urethane prepolymer.
:
* The diol has the formula RfCH2CH2SCHCH20H
., RfCH2CH2SCHCH2H
where Rf is a mixture of perfluoroalkyl chains consisting of C6F13, C8F17 and CloF2~. The diol is described in Example 2.
''.: ' Eæample 57: The hydroxy-terminated prepolymer of Example 56 (53.7g solution, 17.9g solids) was treated further at 75C with dimer acid derived diisocyanate (6.0g, 0.01 mole) (DDI, Quaker Oats Gompany) for two hours, then the urethane chain was completed by the addition of trimethylhexamethylene diisocyanate (2,2,4 and 2,4,4 isomer mixture) (1.05 g; 0.005 mole) and N-methyldiethanolamine (1.19g; 0.01 ~ole). Reaction was complete in three hours, as shown by the disappearance of the N=C-ff'f band (2270 cm 1) in the infrared spsctru~. A sample taken to dryness gave a quantitative yield of an off-white powder containing 35.8%F (theory 36.6%F). For appli-cation to textile fabrics the polyurethane was applled either from solvent (MEK solution) or as an aqueous emulsion. The latter was made by first quaternizing the tertiary nitrogen atoms with glacial acetic acid and then pouring the MEK solution into a sufficient volume of water to give a clear emulsion.

: .

~ 72 -Example 58: The prepolymer of Example 56 (53.7 g solution; 17.9g solids) was treated as in Example 57 with dimer acid derived iso-cyanate (6.0g; 0.01 mole) (DDI, Quaker Oats Company) for 2 hours at 75 followed by further reaction with N-methyldiethanola~ine (3.57g;
0.03 mole) and dimer acid derived isocyanate (15.0g; 0.025 mole) (DDI). Reaction was judged to be complete in 3 hours. An aliquot of the polyurethane solution was taken to dryness to yield a quantitative amount of off-white powder, containing 23.0~F (theory 22.4%). Application to fabrics was made either as a solvent based material or as a self-emulsifiable quaternized polyurethane as described in Example 57.

.
Example 59: When the prepolymer of Example 56 (53.7g solution; ~' .
17.9 g solids)~is treated was dimer acid derived isocyana~e (DDI) (6.0 g; 0.01 mole~ for 2 hours at 75; there is obtained an iso- , cyanate terminated prepolymer. This is extended with 2S2-bis~hydroxy methyl)-propionic acid (1.34g; 0.01 mole) and trimethylhexamethylene-diisocyanate"'(l.O5 g; 0.005 mole). This acidic function is neutralized by the addition of potassium hydroxide and the produc-t is self-emulsifiable when poured into water.

ExampIe 60: The utility of the urethane compositions of the pre-ceding examples is illustrated below. The compositions were applied ,~ -to fabrics at a loading of 0.082F based on the weight of fabric (OWF) and tested for oil and water repellency.
- :
The AATGC water spray test rating was determined according to Standard Test Method 22-1971~of the American Association of Textile Chemists and Colorists. Ratings are given from O (minimum) to 100 (maximum).
. ; ~ ..
~:;

8~Z
The AATCC Oil Rating was dete-.^mined according to Standard Test Method 118-1972 of the American Association of Textile Chemists and Colorists. Ratings are given fro~ O (minimum) to 8 (maximum~.
A commonly accepted lower value on soil repellent fabrics in the U.S.
is an oil repellency of 4.

All mentioned ~TCC Tests are listed in the Technical Manual of the American Association of Textile Che~ists and Colorists, Volume 48, Edition 1972.

Dry soil resistance was determined according to the ~olLowing procedure:

Finished and unfinished test fabrics are rotated together with standard dry soil in an Accelerator:
no abrasive lining is used in the Accelerator for this text. Excess soil is removed under controlled conditions: the difference in appParance of the two samples is then evaluated instrumentally on a Gardner Color Difference Meter, and reported as change in whiteness (RD value).

; Two 4" ~ 4" fabric samples~one finished and one unfinished, are required for each test. White fabric is recommended, as this emphasiæes the observed differences in soiling; but dyed fabrics may also be tested if the styles in question are of particular interest.

Preparation - Each fabric sample is treated to prevent un-raveling by sealing its edges with a solu~ion of 10~ Elvacite 2041 Trademark) in trichloroethylene. This is applied with an eyedropper and allowed to dry; then the sa~ples are conditioned overnight at 75~ 5C and 65% RH.

- ~3^
~:: :
: i, ~

... .. . , ... . . ~ - . ~ - - ` ~ - , . , _ 7~ 66~4~

Portions of dry soil, each 0.20g, are weighed into disposable aluminum dishes, and stored overnight to a dessicator over Drierite or similar drying compound. The first pair of siamples are removed from the conditioning chamber. These samples are Eolded in half, face side out, and one is placed around each blade of the Accelerator propeller.
The accelerator is closed and one portion (0.2t) g ) soil is introduced into the Accelerator through the small top port hole. The Accelerator is then run for 30 seconds at 3000 rpm. Contimlous manual adjusitment is needed during this 30-second soiling period to quickly achieve and maintain 3000 rpm. The test specimens are next re~oved from the Accelerator and placed in the Soil-Removal Unit.
:
The Soil-Removal Unit consists of a No. 5 Standard Buchner Funnel (186 mm. ID, 2-L/2" deep, such as those supplied by the Fisner Scientific Co.), firmly supported and fitted with an acrylic cover. The acrylic cover has twenty-five 3/16" air vent holes and a 1/4" hole at 45 to the plane of the cover, through which air is ~ -injected to blow the fabrics free of excess soil.

The acrylic cover is put in place and held down with one hand.
The V4" copper tubing air line is inserted in the 45 opening pro-vided; the tubing must not protrude more than 1/8" into the ch~mber.
Air is then injected through the copper tubing at 40~3,psi or one minute, causing rapid rotation of the fabrics and removal of excess soil~ The samples are stapled side-by-side onto 9-1/2" x 9-1/2"
squares o~ white blotting paper. T~o tests (four specimens) may be placed on each square. The specimens and squares are stored in 10" x 15" polyethylene bags, to await evaluation, and the soiling procedure is continued with the ne~t pair of fabric samples.

The Gardner Colorimeter is switched on and alLowed to stabilize for at least 20 min. The largest-size glass cover plate is installed on the sensor and the instrument is adjusted and cali-~:
brated to read on RD, A, B scales. The first piece of blotting paper, ::

:~ :

- 75 ~ 68~Z

with samples attached, is removed from its polyethylene bag. It is positioned so that a treated specimen is on the sensor of the colori-meter, and backed with a white enamel plate; a~d a whitenesss reading (RD scale) is ~ade of the specimen, backed by the blotter, backed by the pl~te. The whiteness of the corr~esponding untreated specimen is then obtained in a similar manner. Test results are reported as change in whiteness after dry soiling (delta RD~ caused by finishing the fabric. This value is obtained by subtracting the RD value for the untreated specimen from that of the corresponding treated specimen; it is positive when the finish improves dry soiling properties, and negative when the treated fabric becomes more soiled than the llntreated.

Sandard Dry Soil Used:

Ingredient Supplierl 38 Peat Moss Michigan Peat, Inc., Capac. Mich.
17 ~ Cement Portland Cement 17 Kaolin clay, P~erless R.T.Vanderbilt Co.,Park.Ave.
New York City 17 Silica Floated Powder - about 240 Mesh Fisher Scientific Co., Fairlawn, 1.75 Molacco Furnace Black Colombian Carbon Co., Madison Ave.
New York City 0.50 Red Iron Oxide Chas.Pfi~er and Co., New York City 8.75 Mineral Oil Standard Oil Co. of New Jersey, ~u]ol Trademark~ Elizabeth, New Jersey The peat moss is dried 12 hours at 105C in a forced draft convection oven~ weighed, and then blended with other ingredients in a ball mill (without ceramic balls) 2 hours. The blend is dried on a large pan 8 hours at 50C in a forced draft convection oven, and ball : - ~5-:
.

-... . ~ i, , ., , . ~ ., .. ,. , .,,, .. ,, ~. . ..... ...... ... ...

milled with ceramic ball for 24 hours. The soil is passed through a 40-mesh sieve, mi~ed in a ball mill without balls for 4 hours and then stored in a closed jar.

The novel urethane compositions were applied to polyester fabric, or polyester-cotton twill (65/35~ in such a way that 0.08%
fluorine was deposited onto the fabric. The cotton/polyester fabric is a 65% polyester-35% cotton blend. The polyester is one formed from ethylene glycol and terephthalic acid, sold for example under the Dacron trademark.

Polymers dissolved in a non-aqueous medium were mostly applied to fabric by a padding process and were evaluated after air drying and after curing in a hot air oven at ~150C for 3 minutes.

Polymers prepared in water or a water-solvent mixture or a solvent which is water-miscible were applied to polyester-cotton -twill by padding from an aqueous pad bath containing a permanent press resin, catalyst and surfactant, followed by drying and curing.

.-, .. .

.. . .

;:

: ~ 77 ~ 1~6 :, Evaluation of Polyurethanes as Oil and Water Repellents Applied at a Level of 0.08% OWF

. . ____ -- . ..... __ . _ Urethane Oil Water Fabric*
of E~ample Repellency Repellency . _._ -- ,.... _ . .. ~. .. _ .
46 O - 1 O Cotton/PE

51 6 80 .
52 1 8Q ll 53 5 O Cotton/PE
54 4 - 5 70 ll 55A 3 70 ..
55B 3 70+ ,.
57 ` 6 80 58 6 80+ ..
~ ~_ _ * Cotton/PE = 35% cotton, 65% polyester PE - 100~ polyester.

' , .

:

:: ~

,. :
~: ' ' ' ' ' - 78 - ~6~

Example 61: Incorporation of small amounts of Rf-glycol into poly-urethane elastomer compositions imparts excellent release properties to molds made from the elastomer. The Rf-glycol itself contains 60%F, but incorporation of only enough Rf-glycol to give the final formulation of 0.6%F is sufficient to produce the desired mold release properties.

2,3-Bis(1,1~2,2-tetrahydroperfluoroalkylthio~butane-1,4-diol (47g; 0.046 mole) the diol of Example 1, and tolylene-2,4-diisocyanate (322g; 1.85 mole) were mixed and allowed to react at 80 for 30 minu-tes. This gave a solution of fluorinated diisocyanate prepolymer in e~cess TDI. To this solution was added Polymeg 1000* ~521g) and Pluracol 2010** (573g), keeping the temperature below 50 with exter-nal cooling. Then the reaction was completed by heating at 82 for 2 hours to give an isocyanate capped polymer containing approxi-mately 2% and its free surface energy, Yc was 12 dynes/cm.

This material was blended with a polymer made without the addition Qf Rf-diol, such that the final fluorine content was 0.6%. Moldsmade from this blend exhibited excellent release pro-perties. Molds made from non-fluorine containing polymers caused considerable sticking of molded parts.

* Quaker Oats Company tradema~k for Polytetramethylene ether glycol ** BASF-Wyandotte trademark for Polypropylene glycol . .

~ .

.

. .
: ,, : ~: ~. ' , - 79 - ~6~Z

Example 62. Polyurethane varnishes are well-known commercial items.
Generally, they provide clear coatings with e~cellent mechanical and solvent resistant propertles. By incorporating a small amount of Rf-glycol (sufficient to give as little as 0.5%F :in the final film) the general polyuretbane properties are not impaired and the incor-porated fluorine allows better wetting of the surfaces to be coated by the varnish. The final9 hard fluorine containing film has a critial surface energy y of 12 dynes/cm, which means that it cannot be wetted by most common liquids and that it is therefore more soil resistant than ordinary polyurethane coatings.

2,3-Bis(1,1,2,2-tetrahydroperfluoroalkylthio)bu~ane-1,4 diol (0.1 mole) the diol of Example 2 is reacted with 3.2 mole toluene-2,4-diisocyanate to give fluorinated isocyanate propolymer. This is then mixed with tris-(hydroxymethyl) propane ~1 mole) and warmed to complete reaction.

A commercial hydroxyl terminated polyester(Desmophen 800-Trade~
mark)(l7.3 parts by volume)is dissolved in a standard polyurethane solvent (glycolmonomethylether acetate, butyl acetate, ethyl acetate and toluene) and to the solution is added 41.5 parts by volume of the isocyanate capped polymer described above, and well mixed. The solution is then ready for brushing or spraying on the surface to be coa~ed, hardens to a clea~ varnish after a few hours exposure at ambient conditions.
.

Fiber reactivity of the polyurethanes can be achieved through a -NCO terminated polymer. Application of such a material from a non-reactive solvent (e.g., trichloroethane) to a cellulosic fiber, followed by a high temperature cure reslllts in a urethane bond formation between the -OH groups of the fiber and the -NCO groups of the polymer. Alternatively~ cross-linking may be achieved between the polymer chains by reaction of the terminal -NCO groups with al-- ~ - 1 OeG684Z
ready formed urethane linkages, to give allphanate structures.
O O
e.g. RNCO~ R'NHCOR" ~ R-N-C-O-R"
isocyanate urethane CONHR' allophanate ' ,, Another alternative is or a conventional hydroxyl ter~inated polymer, as previously exemplified, to be co-applied, from solvent, with a fiber-reactive resin, such as a polymethylolmelamine, which will react, on curing, with the -OH groups of both the fiber and the polyurethane.

Exa~ple 63 Methyl ethyl ketone (600 g) is charged to a 2 1. flask fitted with a stirrer, thermometer, nitrogen inlet and a condenser protected with a drying tube. 2,3-bis (1,1,2,2-tetrahydroperfluoro-alkylth~o~butane 1,4-diol (600g; 0.571 mole,) the diol of Example 2, is added ~ogether with a 1:1 mixture of 2,2,4ftrimethylhexamethylene diisocyanate a~d 2,4,4-trimethylhexamethylenediisocyanate (80.16g;
0.381 mole). All reagents are rinsed in with an additonal 50 g MEK.
The solution is~heated to boiling and sn g solvènt are removed by distillation to e~fect azeotropic drying o all materials. Then di-butyltindilaurate~;~(O.692 g; 1.14 ~ 10 3 mole; 2 mole % based on dioll is added~as a catalyst and the solution heated under reflux for six hours.~At`the end of this time the reac~ion is jutged to be~complete by the absence of the N=C=O infrared band at 2270 cm 1.
A further aoo~ml of MEK àre~added and the hydroxyl terminated pre-polymer treated further~with dimer acid derived diisocyanate (228.5g;
0.381 mol~) (DDI~for~two hours. The urethane chain i5 completed by~the;~addlti of further~dimer acid derived diisocyanate ~457.6g;
0,762 mole~ (DDI~and~l,4-butanediol (68.5g; 0.762 mole).`

- 81 - ~ 42 The presence of -NCO bands in the final. product i~ shown by infrared absorption (2270 cm ). Addition of 1450 ml MEK gave a pro-duct containing 33-1/2% solids. This product i.s applied to fabrics by application from solvent by diluting the concentrate with 1,1,1-trichloroethane such that the. treating bath contains approximately 0.2%F. Fabrics so treated typically exhibit an oil repellency of 6 and a water spray rating of 80.

Exa_ple 64: A series of emulsions of perfluorinated polyurethanes was prepared from prepolymers of Example 56 according to the proce-dure of Example 57 by preparing polyurethanes having the indicated molar amounts of each of the four components:

MOLES OF COMPONENT
_ Component Run: A B C D E F G H
. . ... _ . _ .,.,, .
Rf-diol 3 3 3 3 3 3 3 3 trimethylhexamethylene- 2 2 2 2 2 3 4 5 diisocyanate *dimer-acid diisocyanate 6 2 3 5 10 1 0 0 -methyl diethanolamine 5 1 1 4 9 1 1 2 The emulsions as completed had the followin~ composition:
.
Rf-polyurethane 22.50%
stabilizer (1) 0.6i acetic acid 2.89 Methyl ethyl ketone (MEK)24.00 quaternary ammonium cpd (2) 0.06 water to make100%

' - g /

~ .
, :: . . . . -, . . . . :

~ - ~2 - ~ ~66~Z

(1) the stabilizer had the formula .
(CH2cH20) 7H
18 37 \ CH3 Cl (CH CH 0) H
(2) Dicocodimethyl ammonium chloride sold as a 75% solution in iso-propanol as Arquad 2c-75(Trademark)by Armak Chemical Corporation.

* a diisocyanate derived from dimerized oleic acid and sold by General Mills Company.

White cotton-polyester poplin fabric (35% cotton, 65% polyester) was treated with a padbath containing the urethane emulsion of Run A
to provide 0.06~F on the fabric and 0.03%F of the dicocodimethyl ammonium chloride and compared with the identical formulation devoid of the quaternary ammonium compound. The results are as follows:
.

% F on fabric 0.06 0.06 -% Quat. ammonium salt on fabric - 0.03 AATCC oil repellency 5 5 AATCC water repellency 70~ 70~
Dry soil resistance 6.2 14.3 : RUDS :B through H were formualted as abo~e and evaluated with (I) and without (-) the quaternary am~onium sal~. The results are summarized below. As can be seen, the dry soil resistance in each case shows a substantial increase without substantially affecting the soil or water repellency. s , .-.. , .. .. ~ .. . . .

- 83 - 1 ~6G842 . .
Quaternary AATCC
AmmoniumOil Water RUN CompoundRepellency Dry Soil Resistance _ 6 70 6.9 + 5 70 13.5 C _ 6 80 8.3 ~ 6 80 14.9 D _ 6 70 7.9 + 6 80 16.9 E _ 6 80 6.7 + 6 80 14.2 F _ 6 70 7.3 + 5 70 15.9 G _ 5 70 7.1 + 4 50 14.3 H _ 5 50 6.9 + 5 50 13.5 . . _ , _ _ __ ,-'' ' Ex mple 65: A series of emulsions of perfluorina~ed polyurethanes was prepared from prepolymers of Example 56 according to tbe p~rocedure of Example 57 by preparing polyurethanes having the indicated molar amounts of each of the four components:
~, .
.
. MOLES OF COMPONENT
_ _ Component Run: A B C D E F G H I
Rf-diol 3 3 3 3 4 3 3 3 3 trimethylhexamethylene 3 3 3 3 4 4 4 4 5 ~ diisocyana~e ' ; ; ~ dimer-acid diisocyanate 2 3 4 5 1 2 3 4 10 N-methyl diethanolamine 2 3 ~4 5 2 3 4 5 12 :
_ _ _ 1 _ :

- 84 ~ 684Z

The emulsions as completed had the following composition:

Rf-polyurethane 25%
acetic acid 3 water 49 f The emulsion was added to the padbath formulation.
a) without a quaternary a~monium salt (-) b) with 0.06% hexadecyl trimethylammoniunl bromide t~) .
and evaluated on cotton-polyester poplin (35Z cotton, :
65% polyestsr). The results are summarized below, it being noted that no bath stabilizer was employed.
Quaternary AATCC :
AmmoniumOil Water :
RUN CompoundRepellency Dry Soil Resistance ~ _ .
A _ 6 80 8.4 :
~ 6 70 13.9 :
B _ 6 80 ~.4 : : ~ 4 60 15. ~ .
C _ 5 80 8.6 : ~ 4 60 13.2 :
: D _ 6 80 6.0 :
5 70 12.8 :
E 5 70 6.2 ~ : ~ 4~60 14.1 : F ~ 5 70 7.
: ~ : ~ 4 60 ~ 12.8 : G 6:10 7.1 5 70 12.0 ~ a ~ _ ~ ~ 6 70 6.4 + : ~ 5 70 11.9 I~ _ : 6 80 8~9 :~ ~ + 5 70 9.7 _ --: ~ : ~ _~ ~-.. : . ~ . .. .. , .. . .. ... , :

- 85 - ~ ~6~42 xamples 66-79: A polyurethane emulsion was prepared accord;ng ~o the procedure of Example 57 using the following moLar amounts ~o pre-pare the Rf-polyurethane:

Component Moles : . .__ _ _ __._ R~-diol 3 trimethylhexamethylenediisocyanate 9 dimer-acid diisocyanate 2 N-methyl diethanolamine 5 bis-2-hydroxyethyldimerate* 3 * The di(hydroxyethyl) ester of dimerized oleic acid sold by Emery Industries.

The emulsion as completed had the following composition:

Rf-polyurethane 25%
acetic acid 3 water 49 This emulsion was added to the padbath for~ulation together with 0.06% of the indicated quatenlary am~onlu~ compound. No padbath stabilizer was used, except that examples 69 and 78 contained 0.02%
of the stabilizer of example 64. Cotton-polyester (35/65) was treated and evaluated. The results are summarized below.

~ . : , . . . : .,, - : - .. . ..

- 86 - ~ ~6~84Z

Example Name o~ Quaternary MTCC Dry Soil Number Ammonium Compound Oil/Water Resi 9 tance _ _ _ _ _ Repellency _ _ _ _ ~ 66 hydrogenated tallo~-tri- 6/70 17.8 ; methylammonium chloride 67 (10-phenyl)-octadecyl-tri- 5/70 15 methylammonium chloride 68 soya-trimethylammonium 5/70 16.6 chloride 69 di(-9-phenyl)octadecyl-di- 6/80 14.0 methylammonium chloride octadecyl-di(-2-hydroxy- 6/70 15.4 ethyl)-methyla~monium chloride 71 octadecyl-di(polyethylene- 5/70 12 oxide-7)-methylammonium chloride i 72 2-heptadecyl-1-(2-hydroxy- 5/70 15.8 ethyl)-l-methyl imidazolinium methylsulfate 73 hexadecyl-pyridinium chloride 6/70 16.0 74 hexadecyl-trimethylammonium 5/70 15.9 bromide N-(9-phenyl-octadecyl)-N-N-, li- 5/50 16.0 methyl-N'N'N'-trimethyl pro-pane 1,3-diammonium dichloride 76 octadecyl-trimethylammonium 4/70 16.5 chloride ~
77 C8~17S02NHCH2CH2cH2N(cH3)3 5/70 14.0 78 stearyl-benzyl-dimethyl- 5/50 14.8 ammonium chloride 79 N-hexadecyl-N-ethyl-morpho- 5/70 14.5 lium ethosulfate - ~ ~ _ : : _ - 87 ~ 6~

Example 80: The Rf-polyuret~lane emulsion of Example 66 was used to prepare padbaths as follows:
~ .
A - padbath ~ R~-polyurethane B - padbath + R -polyurethane + 0.06% di-cocodimethyl-ammonium ch~oride + 0.02% stabilizer (see Example 66) C - padbath ~ R~-urethane ~ 0 6% di-cocodimeth~lammonium chloride + 0.02% seabilizer D - padbath ~ 0.06% di-coco-dimethylammonium chloride + 0.02% stabilizer.
.
The emulsions were padded (50% net pickup) on cotton-polyes~er ~35/65) and evaluated.

The results are summarized below.

.
The data show that, in general, the lower addon level~(Run B) gives better results than the higher level (Run C).

Padbath AATCC Repellency Dry Soil Resistance -Oil Water -_ ._ ___ _ A 5 70+ 9 B 4 70 13.4 C 3 70 8.4 D _ _ ~

Example 81. These exampl4s illustrate the proposition that all surfac~ants do not perform similarly, that the various known sur-factants are ~ot equivalent and cannot be freely interchanged.

. ~ ~

,: . . .. -, . . , . . :. : .,. ,- . ~., , .. , . ~ ~ : . . : . : -- 88 - ~ ~66~L~

A series of emulsions of perfluorinated polyurethanes was prepared from the prepolymers of Example 56 according to the pro-cedure o Example 57 by preparing polyurethanes having the indi-cated molar amounts of each of the indicated components:

. _ _ Mt)LES
:~ Component RUN: A B C
Rf-diol 3 3 3 trimethylhexamethylene-diiso- 3 3 2 cyanate N-methyl diethanolamine 3 1.8 4 butane-1,4-diol - 1.2 -` ' , ~ The emulsions as completed had the following composition:

, Rf-polyurethane 22.50%
Stabilizer(l) 0.61 ~cetic acid 2.89 MEK24.00 emulsifier 0.06 water to make 100%

: (1) see Example 64.

.
: ~ .
~: :
.

g~ : -- 8~ -. . . AATCC _ _ _ Repellency Dry Soil RUN Emulsifier 0;1 Water Resistance ~ .
A None 5 70+ 6.6 nonylphenoxypolyoxyethylene 5 50 6.7 alcohol (9.5 moles ethylene oxide) ,. .. _ ._ B None 5 80 4.7 nonylphenoxypolyoxyethylene alcohol (9.5 moles ethylene oxide) 1 0 3.9 octadecyl-di(polyoxyethylene~ 3 70~ 4.6 ~ :
amine (15 moles ethylene oxide) . .
_ . . . . _ .
C None 6 70 7.9 alkyl-aryl-polyoxyethylene 4.5 70 7.3 alcohol*
hexydecyltrimethyl ammonium 5 70+ 14.7 _ bromide . _ __. -; : * Sold under the trademark Triton-X 155 by Rohm & ~aas Co.
.
: It is clear that the various known emulsifiers do not provideequivalent results and that best results are obtained when a quaternary am~onium salt containing a long hydrocarbon chain is used.

.:

::

, :: : : : :
:

. .
-- -- - - . - --. .. ~ ., , ., . , : . .

Claims (28)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the manufacture of a polyurethane containing at least one unit of the formula which comprises reacting at a temperature of 20 to 120°C in the presence of a non-reactive anhydrous organic solvent or without any solvent a) an organic isocyanate or an isocyanate polymer and b) at least one of i) an Rf-glycol of formula ii) a hydroxyl-terminated polymer containing at least one residue of formula where Rf is perfluoroalkyl of 1 to 18 carbon 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 car-bon atoms, alkyleneoxyalkylene of 2 to 12 carbon atoms, or alkyleneiminoalkylene of 1 to 12 carbon atoms where the nitrogen atom contains as a third substituent hydrogen or alkyl of 1 to 6 carbon atoms;

R2 and R3 independently are straight or branched chain alkylene of 1 to 12 carbon atoms, said alkylene substi-tuted by 1 or 2 of phenyl or cyclohexyl; or a group of formula CmH2m(OCkH2k)r where m is an integer from 1 to 12, k is an integer from 2 to 6 and r is an integer from 1 to 40.

2. A process according to claim 1 in which Rf is per-fluoroalkyl of 6 to 12 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms;
R1 is branched or straight chain alkylene of 2 to 8 carbon atoms, alkylenethioalkylene of 2 to 8 carbon atoms, alkylene-oxyalkylene of 2 to 8 carbon atoms or alkyleneiminoalkylene of 2 to 8 carbon atoms and where the nitrogen atoms contains hydrogen or methyl as a third substituent; R2 and R3 are each independently straight or branched chain alkylene of 1 to 4 carbon atoms or a group of formula CmH2m(OCkH2k)r where m is an integer from 1 to 4, k is an integer from 2 to 4, r is an integer from 1 to 20.

3. A process according to claim 1 in which Rf is per-fluoroalkyl of 6 to 12 carbon atoms, R1 is alkylene of 2 to 4 carbon atoms, and R2 and R3 are each alkylene of 1 or 2 carbon atoms.

4. A process according to claim 1 in which the organic isocyanate is an aromatic mono-isocyanate or an alkyl mono-isocyanate of 1 to 16 carbon atoms in the alkyl moiety.

5. A process according to claim 1 in which the organic isocyanate is an alkylene diisocyanate of 2 to 16 carbon atoms, in the alkylene moiety, or an aromatic diisocyanate of 6 to 30 carbon atoms in the aromatic moiety.

6. A process according to claim 1 in which the organic isocyanate is a monoisocyanate, diisocyanate, triisocyanate or polyisocyanate.

7. A process according to claim 4 in which the aromatic diisocyanate has the formula A(NCO)2 where A is phenylene that is unsubstituted or substituted by one or two of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chloro, bromo or nitro, naphthylene that is unsubstituted or substituted by one or two of alkyl of 1 to 4 carbon atoms, chloro, bromo and nitro, or where A is a group of formula where D is a direct bond, oxygen, methylene or ethylene and a, a', a'' and a''' each independently is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chloro or bromo.

8. A process according to claim 1 which comprises reacting a) an isocyanate-terminated polymer having at least one group of formula b) at least one of i) an Rf-glycol of formula ii) a hydroxyl-terminated polymer containing at least one group of formula and iii) a polyol where Rf, R1, R2 and R3 are as defined in claim 1.

9. A process according to claim 8 in which the polyol is a polyhydroxy polyether or polyester having a molecular weight of 200 to 4000.

10. A process according to claim 8 which comprises reacting a) an isocyanate-terminated polymer having a molecular weight of 200 to 4000, and b) at least one of i) an Rf-glycol of formula or ii) a hydroxy-terminated polymer containing at least one Rf-group of formula where Rf, R1, R2 and R3 are as defined in claim 8.

11. A process according to claim 10 in which Rf is perfluoroalkyl of 6 to 12 carbon atoms or said perfluoro-alkyl substituted by perfluoroalkoxy or 2 to 6 carbon atoms, R1 is branched or straight chain alkylene of 2 to 8 carbon atoms, alkylenethioalkylene of 2 to 8 carbon atoms, alkylene-oxyalkylene of 2 to 8 carbon atoms or alkyleneiminoalkylene of 2 to 8 carbon atoms and where the nitrogen atom contains hydrogen or methyl as a third substituent; R2 and R3 each independently straight or branched chain alkylene of 1 to 4 carbon atoms or a group of formula CmH2m(OCkH2k)r where m is an integer from 1 to 4, k is an integer from 2 to 4 and r is an integer from 1 to 20.

12, A process according to claim 11 in which Rf is per-fluoroalkyl of 6 to 12 carbon atoms, R1 is alkylene or 2 to 4 carbon atoms and R2 and R3 are both alkylene of 1 or 2 carbon atoms.

13. A urethane composition containing at least one unit of formula where Rf is perfluoroalkyl of 1 to 18 carbon atoms or said perfluoro-alkyl 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, alkylene-oxyalkylene of 2 to 12 carbon atoms, or alkyleneiminoalkylene of 2 to 12 carbon atoms where the nitrogen atom contains as a third substituent, hydrogen or alkyl of 1 to 6 carbon atoms, R2 and R3 each independently is straight or branched chain alkylene of 1 to 12 carbon atoms; straight or branched chain alkylene of 1 to 12 carbon atoms substituted by one or two of phenyl or cyclohexyl; or a group of the formula CmH2m(OCkH2k)r where m is an integer from 1 to 12, k is an integer from 2 to 6 and r is an integer from 1 to 40.

14. A urethane composition according to claim 13 in which Rf is perfluoroalkyl of 6 to 12 carbon atoms or said per-fluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, R1 is branched or straight chain alkylene of 2 to 8 carbon atoms, alkylenethioalkylene of 2 to 8 carbon atoms, alkyleneoxyalkylene of 2 to 8 carbon atoms or alkyleneimino-alkylene of 2 to 8 carbon atoms and where the nitrogen atom contains hydrogen or methyl as a third substituent; R2 and R3 are each independently straight or branched chain alkylene of 1 to 4 carbon atoms or a group of formula:
CmH2m(OCkH2k)r where m is an integer from 1 to 4, k is an integer from 2 to 4, and r is an integer from 1 to 20.

15. A urethane composition according to claim 14 in which Rf is perfluoroalkyl of 6 to 12 carbon atoms, R1 is alkylene of 2 to 4 carbon atoms, R2 and R3 are both alkylene of 1 or 2 carbon atoms.

16. A urethane composition according to claim 14 which additionally contains from 5 to 800 milliequivalents of ammonium groups per 100 grams of urethane composition.

17. A composition according to claim 13 comprising a urethane and from about 3 to about 100 %, based on the weight of the urethane, of a quaternary ammonium salt containing at least one long hydrocarbon chain.

18. A composition according to claim 17 in which the quaternary ammonium salt has the formula a) where R? is branched or straight chain alkyl of 8 to 21 carbon atoms; phenylalkylene of 12 to 27 carbon atoms;
branched or straight chain alkenyl of 8 to 21; or straight or branched chain alkadienyl of 8 to 21 carbon atoms; R?
is branched or straight chain alkyl of 1 to 21 carbon atoms; phenylalkylene of 8 to 27 carbon atoms; r-hydroxy-alkyl of 2 to 4 carbon atoms; branched or straight chain alkenyl or alkadienyl of 8 to 21 carbon atoms; or the group of formula (CH2CH2O)xX
where x is an integer from 1 to 25; or R? is alkylene of 1 to about 8 carbon atoms containing a quaternized nitrogen atom whose substituents are alkyl, phenylalkylene, .gamma.-hydroxy-alkyl, alkenyl, alkadienyl or the group (CH2CH2O)xH
all as previously defined; R? and R4 are selected from the same group as R? with the further limitation that only one of R?, R? and R4 can be selected from the same groups as R?;
and X? is an anion b) where R? and X? are as defined above a is an integer from O to 3, R is selected from hydrogen, alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, halogen alkoxy of 1 to 4 carbon atoms, carboxyl, carbalkoxy of 2 to 4 car-bon atoms, acetyl, benzyl, sulfo, carbamyl and cyano and \

is pyridine, quinoline, isoquinoline, pyridazine or pyrimid-ine or c) where a, X?, R, R? and R? are as previously defined and is imidazole, benzimidazole, morpholine, piperidine, pyrro-lidine, pyrazine, indazole, pyrazole, indole and pyrrole.

19. A composition according to Claim 18 in which the quaternary ammonium salt has the formula where R? is branched or straight chain alkyl of 8 to 21 carbon atoms; phenylalkylene of 12 to 27 carbon atoms;
branched or straight chain alkenyl of 8 to 21; or straight or branched chain alkadienyl of 8 to 21 carbon atoms; R?, R? and R4 are each independently alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 2 to 4 carbon atoms or benzyl and X? is an anion.

20. A composition according to claim 18 in which the quaternary ammonium salt has the formula where R1 and X? are as defined in claim 18, R? and R? are methyl and R4 is methyl or benzyl.

21. A composition according to claim 20 in which R4 is methyl.

22. A composition according to claim 17 wherein the medium is aqueous.

23. A method for rendering a substrate repellent to water and oil which comprises applying thereto a solution, emulsion or dispersion of an effective amount of a urethane composi-tion according to claim 13.

24. A method according to claim 23 which comprises apply ing from 0.01 to 10 % of the weight of substrate of the urethane composition.

25. A method according to claim 23 which comprises in-corporating in said solution, emulsion or dispersion from about 3 % to about 100 %, based on the weight or said urethane of a quaternary ammonium salt containing at least one long hydrocarbon chain.

26. The method according to claim 25 in which the quater-nary ammonium salt has the formula where R? is branched or straight chain alkyl of 8 to 21 carbon atoms; phenylalkylene of 12 to 27 carbon atoms;
branched or straight chain alkenyl of 8 to 21; or straight or branched chain alkadienyl of 8 to 21 carbon atoms; R?
is branched or straight chain alkyl of 1 to 21 carbon atoms; phenylalkylene of 8 to 27 carbon atoms; y-hydroxy-alkyl of 2 to 4 carbon atoms; branched or straight chain alkenyl or alkadienyl of 8 to 21 carbon atoms; or the group of formula (CH2CH2O)xH
where x is an integer from 1 to 25; or R? is alkylene of 1 to about 8 carbon atoms containing a quaternized nitrogen atom whose substituents are alkyl, phenylalkylene, y-hydroxy-alkyl, alkenyl, alkadienyl or the group (CH2CH2O)xH

all as previously defined; R? and R4 are selected from the same group as R? with the further limitation that only one of R?, R? and R4 can be selected from the same group as R?, and X? is an anion b) where R1 and X? are as defined above/a is an integer from 0 to 3, R is selected from hydrogen, alkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, halogen alkoxy of 1 to 4 carbon atoms, carboxyl, carbalkoxy of 2 to 4 car-bon atoms, acetyl, benzyl, sulfo, carbamyl and cyano and is pyridine, quinoline, isoquinoline, pyridazine or pyrimid-ine or c) where a, X?, R, R? and R? are as previously defined and is imidazole, benzimidazole, morpholine, piperidine, pyrro-lidine, pyrazine, indazole, pyrazole, indole and pyrrole.

27. A textile substrate characterized by oil- and water repellency carrying from 0.01 to 10 % by weight of a urethane composition according to claim 13.

28. A textile according to claim 27 characterized by oil and water repellency together with improved dry-soil epellence said textile carrying from 0.01 to 10 % based on the weight of textile of a urethane composition and from 0.01 to 0.3 %
based on the weight of textile, of a quaternary ammonium salt containing at least one long hydrocarbon chain.