CA1102344A - Fluorocarbon modification of fibers - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Fluorocarbon additives are provided which may be introduced into fibrous articles to provide improved anti-soiling, anti-stain, water repellency and/or oil repellency properties which resist abrasion and laundering. The additives may be intro-duced into the fibrous article by incorporation into the melt prior to extrusion of the fiber, or alternatively absorbed into a previously formed fibrous article by contacting the article with a liquid medium containing the additive, optionally followed by annealing the treated article to further improve the article's surface properties.

Description

3~

BACKGROUND OF T~E INVENTION
, ~ "
~IELD OF THE INVENTION
This invention relates to process and composition for the treatment of fibers, and more particularly to process and composition for imparting anti-soil properties to artificial fibers.
DESCRIPTION OF THE PRIOR ART
In the past, man-made fibers, such as nylon and poly-ethylene terephthalate, have found widespread use in home and industry as carpets, drapery material, upholstery and clothing ~owever, deficiencies in these fibers include a lack of water~
and oil-repellency, as well as poor soil release properties. To extend the usefulness of the material, it has been sought to ;-~
impart to these fibers properties tha~ will enable them to resist soiling and to release such ~oil as is applied to the fabric, thereby decreasing the need for cleaning, while at the same~time increasing the effectiveness of such cleaning operations as are in fact performed on the fabricated article. - ?
20~ Past efforts at 1mparting such soil resistant and soil release properties have concentrated on applying polymeric materials, such as polymers of acrylic and methacrylic esters containlng perfluoroalkyl groups, to the fabricated article, usually as emul-~- sions of the additive. However, such treatments have not proven entirely successful due to the uneven fiber coatin~s which are applied and due to the relatively poor adhesion of the fluorocarbon polymers to the substrate fiber. As a result, only low abrasion levels are needed to remove or substantially diminish the effective-ness of the polymeric anti-soilant fluorocarbon finish and thereby expose the urlderlying fiber to soiling. Such abrading away of the ;
~ .

34~L

fluorocarbon coating occurs, as for example, in wear and laundering of clothing material which has been treated by such polyMeric finishes.
Moreover, the easily abraded surEace gives rise to a need to apply the polymeric finishes to the fabricated article since sub-stantial quantities of the finish applied to fiber filaments would be abraded away, and hence lost, upon subsequent procesing of a treated fiber to form the desired fabric. In addition, fabricated textile products generally cannot be dyed after they have been coated with acrylic polymers containing perfluoroalkyl groups since the polymer coating acts as a barrier to effectively prevent the penetration of dye into the fibers. Thus, polymeric finishes must generally be applied as a separate step after dyeing, removing the possibilities of a simplified process scheme in which the finish is applied prior to dyeing.
SUMMARY OF THE PRESENT INVFNTIO~
In accordance with the present invention, there are provided novel fluorocarbon additives for imparting oil- and stain-resistance surface properties to a wide variety of fibers and articles fabricated therefrom. ~s used herein, the term "fibrous article" is in~ended to refer to monofilament fibers, ~iber bundles and articles fabricated therefrom (e.gO, textile fabrics), woven and nonwoven. These fiber additives may provide oil repellency, water repellency or both to a fibrous article, with various degrees of laundry stability and abrasion resistance, allowing the production of fibrous articles having a wide range of surface properties.
These fluorocarbon chemicals can be applied to fibrous articles by several methodsO First, the selected additive may be intimately blended with resin and the blend then extruded to form a fiber having the selected additive incorporated therein. Subse-quent heat treatment of the extruded fiber may be employed to ~23~

further lower -the surface tension of khe fiber. In accordance with a second embodiment of the process of the present invention, a fibrous article to be treated may be contacted with an organic solvent having the desired fluorocarbon additive dissolved therein, followed by subsequent annealing of the article 50 contacted.
Alternatively, the fibrous article may be contacted with an aqueous medium containing the selected fluorocarbon additive, again followed by annealing of the treated article. The aqueous fluorocarbon additive medium may comprise either an aqueous emulsion or disper-sion of the selected additive. In accordance with a third embo-diment of the process of the present invention, a fibrous article is contacted with a liquid medium containing an additive of the present ., .
invention which possesses at least one hydroxy group together with a difunctional or trifunctional epoxide or isocyanate compound and suitable amine catalyst, and annealed for reaction of the additive and epoxide which have been absorbed into the fiber.
It has been found by observation of fiber cross-sections under high magni~ication that the monomeric fluorocarbon additives of the present invention enter into the fiber surface and become an integral part of the fiber, in contrast to the non-compatible polymeric fluorocarbon chemicals of the prior art. Thus, while fibers obtained following treatment with the monomeric additives of the present invention may possess a concentration gradient of the additive, with the highest concentration of additive at the surface of the fiber, these fibers are more nearly homogeneous in compo-sition. Thus, a fiber is produced which tends to retain its oil and stain resistant properties longer than fibers provided with a prior art polymeric fluorocarbon coatlng since the additive, once incorporated into the fiber surface, resists being abraded away with wear or laundering.
In addition, it has been surprisingly discovered that .
~ " .

the fluorocarbon additives of the present invention do not prevent the fibrous articles Erom being dyed subsequent to the introduction of the additives into the fiber. Indeed, these additives have been found capable oE being absorbed by a fibrous article from a dye bath, thereby resulting in a substantial reduction in processing and equipment costs which arise ~rom the use of separate dyeiny and oil/stain-proofing steps. Further, it has been observed that the additives of the present invention wil] not appreciably transfer from the treated fibrous article to an untreated fabric or fiber, thereby enabling laundering or further processing of fibrous arti-cles treated in accordance with the process of the present invention.
Thus, the additives of the present invention may be in-corporated into a fiber, yielding a modified fiber f~om which a desired fabricated article (e.g., a carpet) may be made as by ~se of such standard fiber processing steps as crimping, twisting, tufting, kni~ting, weaving, etc. without destroying the modified surface properties of the fiber.
The additives of the present invention have also been found to impart improved anti-static properties to fibrous articles due to decreased build-up of static charges, and have also been found to increase the stability of dyed fibers to ozone e~posure.
DETAILED DESCRIPTION OF THE INVENTION
We have identified the following classes of compounds as being suitable additives in the practice of this invention:

( ) Qn ~ ~

wherein n is an integer of frGm zero to 4; L is D2R2, hydrogen, `
or -(CH2~f (CHOH)f (CH2)f OH, wherein fl and f3 are the same or different and are integers of from 1 to 4 and wherein f2 is either zero or l; Q is a member selected from the group consisting of ~2~

methyl, chlorine, bromine, fluorine and iodine; Dl and D2 are divalent radicals independently selected from the group consi.sting of alkyl of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -~C~2) CH(OH)(C~2)p O-, -C6H4(cH2~p -'-~6H4O(cH2)P ~~ -CçH4-, -C6H4O- and -CHCH2-, wherein Pl and P2 are integers and are inde-pendently selected from the group consisting of 1 to 4; and Rl, Rl' and R2 are independently selected from the group consisting of ( mF2m~l), (CmF2m_l) and -(CF2)mOX, wherein m is an integer of 2 to 20 and X is selected from the group consisting of peefluorinated :
alkyl of 1 to 6 carbon atoms;

2 1 1 ~B) Qn ~ . .

_ . _ t wherein n, Q, Dl and Rl are as defined above; Z is alkylene of 1 to 4 carbon atoms, and t is an integer and :is 2, 3 or 4; Y, when t is 2, is selected from the group consisting of~
(i) >O, (ii) >C(c~2H)2 (iii) >CH2 (iv) >CH(CH3) (v) >C(CH3)2 ' '~ ~
(vi) >C-CH3 `
OH
~vii) >CHOH, ~-(viii) -CH2(OCH2C~2)rCH2-, and (ix) -(CH~OCH2)r . _5_ ~,~', .

~2~4~L

.;
wherein r lc. an integer of 1 to 10; Y, when t is 3,is -CH or -COH;
and Y is -C- when t is 4; provided that Z is not -CH2- when Y is oxygen;
Qn Qn 2 q 1 1 L~C02 ' Z '2C~
( C ) RlDl-02C~
wherein q is 1 or 2, z' is alkylene of 2 to 4 carbon atoms, n, Q, ::
Dl and Rl are as previously defined;

(D) 1 ~ T - ~ A2 - Qn Qn wherein Al and A~ are independently selected from the group f R -OR t::-ODlRlr -DlR1 and C2Dl 1 Dl and Rl are as previously defined, and T is a member selected ~
from the group consisting of: ~ ;
(-i~) n ~ n' -C~
0~ _ n ' ' O
' (ii) O CO--~)C ~
Q' :
CH2- 0CH2~
(iii) -OCH ~ , and (iv) -CH2O ~
Q n' Q n' wherein Q' is a member selected from the group consisting of CH3 and halogen and n' is an integer of from 0 ~o 4;

.:

'¢~ ' ~ 2~39s~ ~

(E) ON ~ 2 2 ~ D3R3 wherein B is a member selected from the group consisting of:

( i ) -C02DlRl, (ii) -CON < 1 1 , and (iii) -CON(Z"~
10 where D3 and D4 are divalent radicals independently selected from ~ ::
the group consisting of alkyl of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)p CH(~OH)(CH2)p20 , C6H~O(C 2)pl ~ 6 4 1 2 1 : ~:
-C6H40- and -CHCH2; R3 and R4 are independently selected from the gro~p consisting of ~(CmF2m+l)~ ~(CmF2m 1) and ~(CF2)mx' ~" is alkyl of 1 to 4 carbon atoms, and:wherein Pl~ P2t m~ Dl, D2, Rl, R1', R2 and X are as previously~defined, with the proviso that when : -D2R~ and -D3R3 are different, then at least one of D2 and D3 must ~ ~ .
contain at Least 3 methylene group : _ y- ;

(F) (RlD1)2NC ~
O ~

wherein Rl and Dl are as defined preY iously and Y' is selected from the group consisting o.f oxygen and alkylene of 1 to 6 carbon atoms;
E E
(G) I O ¦

E ~ E
wherein two E groups are El, and two E groups are E2, in which El is -CON(DlRl)2 or -C02DlRi and E2 is -C02(CH2)x (CHOH)x CH2Q"
wherein xl is an integer of 1 to 5, x2 is an integer of 0 to 4, Q"
is -OH, hydrogen or halogen and Dl and Rl are as previously defined, _, with the proviso that when Q" is -OH, xl and x~ are each l;

(H) CO2DlRl C2R2 [~C2R2 ' ~ C02DlR

C02DlRl C02DlRl wherein R2' is selected from the gr~up consisting of -(CH2~X CH -~ H2, y g n~ (CH2)xl(cHoH)x2cH2Q and -(CH2)(CHOH)CH2OCH2CH(OH)CH2OH, wherein x2 is an inteqer of 0 or 1 and wherein Dl, Rl, xl and Q~
are as defined above;
[I) n / Z iNHCR2 MlcZ 3CN<
n n O O ~Z2NHCRl , O :
; wherein Zl~ Z2 and Z3 are the same or different and arealkylene of ~rom ; 1 ~o 4 carbon atoms; and Ml is selected from the group consisting of .
: f~ .
2 2 and O(CH2)x (CHOH)x CHzQn', wherein Z is alkyl of 1 to 4 carbon atoms; Qll ~ is -0~, halogen, or hydrog n and wherein xl and x2, Z, R1 and R2 are as defined above, with the proviso that if Q"' is hydrogen, then xl and x2 are each 1;

(Jj OM . M O
n .3 ,4 "
RlCNZl n n n n ~Z6N ~ C ~ R3 ~>~CZ 3CNZ 4NCZ 5CN~
2n 1 2 M6 M7 7 ~ n 4 ~ -~

wherein M2, M3, M4, M5, M6 and M7 are independently selected from ~:
the group consisting Qf hydrogen and Z, in which Z is alkyl of 1 to ::.

4 carbon atoms; Zl~ Z2~ Z3~ Z4~ Z5~ Z6 and Z7 are the same or different and are alkylene of from 1 to 4 carbon atoms,-and Rl, R2, R3 and R4 ~23~
are the same or different and are as defined above; and (K) o 1~
~ CSM' R2CNHZ2 yn ~:
O ' '' , ~
wherein M' is selected from the group consisting of -(CH2)X CH-/CH
O
and -(CH2)~ (CHOH)X CH2Q", and Y" is oxygen or sùlfur, wherein xl, Rl, R2t ~1~ Z2 and " are as defined above and X3 is 0 or 1.
- The terms "alkyl" and nalkoxy" employed in the definition of the divalent radicais Dl, D2, D3~ D4~ Z~ Z Zl~ 2~ 3~ 4 5 Z6 and Z7 and in the de~inition of the monovalent radical Z" are meant to include branched and straight-chained divalent radicals.
The additives of Class G can be the isomer of the~
- Class G formula, in which the El groups are ~
in a meta-position with respect to each other, and thus~in which the E2 groups are in a meta-position with respect to each other.
Alternatively, mixtur~s of the para isomer Wlth the corresponding nmeta-isomer" (in which the EI groups are in a meta-position with respect to each other) may be employed. Preferably, 50:50 molar mixture of the para- and meta-isomers of Class G additives are empIoyed in accordance with the process of the present invention.
Likewise, the para -CO2DlRl Class~H addltives (in which the -CO2DlRl groups are in a para-position with respect to each ;~
other) and the meta -CO2DlRl Class H additives (wherein the -CO2DlRl groups are in a meta-position with respect to each other) may be employed singl~ or in combination, e.g. as a 50:50 molar mixture of the para- and meta-CO2DlRl Class H additives.

~, .
-8a-, :.

In addition to having the foregoing chemical structure, the additive must also possess certain physical properties. The additive which is to be incorporated into a fiber by extrusion of a ~ixture of resin and additive, must be substantially thermally stable at the temperature at which the filament is extruded.
This temperature normally is wi-thin the range of 200 to 350C, and is preferably from 240 to 280C. In addition, when the additive is to be incorporated into a fibrous article by absorbtion from aqueous or organic solvent media, the additive must be substan tially thermally stable at the temperature used in the subsequent heat treatment step, which generally will range from 90 to 230C.
An additive is thermally stable if it survives the extrusion and/or heat treatment process without forming undesirable decomposition products and without decomposing to such an extent as to lose an appreciable amount of the effectiveness in imparting soil and stain repellency to the filament. In addition to being thermally stable, the additive must also be non-fugitive, i.e. not appreclably ;
volatile, at the selected extrusion and/or heat treatment temperature, otherwise it would escape from the filament. A further requirement is that the additive must have a low surface energy in order to impart a low surface energy to the filament. To be suitable, the additive must have a surface energy of less than the surface energy of the untreated fiber, and preferably of less than 18 dynes/cm., and most preferably less than 15 dynes/cm. ~ -;

, .
,~ .

~ 2~4~

Examples of fluorocarbon additives falling within the above classes are as follows:
Class A
O2CH2CH2CF2C~2~CF(CF312 --C02C~2CH2CF2CF20cF(cF3)2 (2) Br2 ~ CO2c~2cH2cF2cF2OcF(cF3)2 CO2cH2cH2cF2cF2OcF(cF3) CO2CH2~ CF CF2CF2OCF(CF )2 :.
~ ~ 2 2 . 3 ~:
10~ CO2CH2CH2CF2cF2cF3 .

:' ~C02CH2CH2(CF2)6CF3 CO2CH2cH2(cP2~6cF3 -~ -CO CH
~ 3 :' C02CH2CH2CF2CF20CF(CF3)2 :~
,, C02CH2CHCH20H
(6) ~ OH
CO2cH2c~2cF2cF2OcF(cF3)2 `
:, '' ~ ' ~ 2CH2CH2CF2CF2OCF(CF3)2 (7) C14 ~ : :
Co2cH2cH2cF2~F2ocF(cF3)2 ~ ~ 2CH2cH2cF2cF2ocF(CF3)2 ; (8) (CH3)4 ~
C2CH2CH2CF2CF2CF(CF3)2 (9) CO2CH2cH2cF2cF2OcF(cF3)2 ~$~4 'C2cH2cH2cF2cF2cF(cF3)2 (10) ~ ' Co2cH2cH2cF2cF2ocF(cF3)2 Class B

CO2CH2CH2CF2CF20CF(CF3)2 ``C02CH2CH2~ '0' (12) ~ C2CH2CH2CF2CF2CF~CF3)2 .
CO2CH2 - . - CHOH

CO2CH2CH2cF2cF20cF(cF3)2 ¦ CO2CH2 ~ C(CH20H) ....
(cF2)6ocp(cFl)2 CO2CH2 ~ 4 (15) [ ~ O CH ]
2~
_ _ .
(16) ~ 02CH2CH2CF2CF20cF(cF3)2 ~ :
: Cl CO2CH2 _ (17) ~ ~ CO2CH2cH2cF2cF20cF(cF3)2 Cl Cl C02C 2 2 -~
~ 2tCH2)3(CF2)40CF(CF3)(C2Fs) : (18) ~
CO2(CH2)3 ................. __. - CHOH
~ 2 ~19 ) I ~2 2 2 2 2 ( 3 J--¦

CH2 ~ . :

t 20 3 r ~ C2CE~2CH2CF2CF2CF ( CF3 )~
CO ~ C H i!CH 2 (21)~(~CO C3 !C32(CF2)6O ( 3 2 ] , CO~CH2CH2cF 2C~2CF t CF3 ) 2 ~ :

t 2~ ~ ~ `- :
2~H2 --CHOH

~2CH2CH2CF2CF2OCF ( CF3 ), .
(23) ~ :-.. . C2C 2 --C ( CH 2~) 2 ~ ~;

C02CH2C~2CF2CF20CF ( CF3 J 2 t CF3 ) 2FCOCF2CF~CH2CH203 20 ( 24 ~
CO2 2 2 CH2CH2CH2CH2 - CH2CH2O2c co2tCH2)3tcF2)4cF3 CF3(cF2)4(~H2)3 ~25) ~
C2~H2 . ---- -- CH20CH2 ~ CH2C02 "

t26) r~Co2CH2CH2~CF2)40CF(CF3)2 1 L co2(cH2)3 I CH

L CO2C~2C~2(CF2) gCF3 ~ C O H

~1~234~

(27a) CO2CH2CH2CF2CF20CF(CF3)2 102CH2CH2 - C -¦ C~2 ~27b)~ CO2CH2CH2CF2CF2 C02CH2CH CH(CH3) (27C) [ ~ 2 2 Z 2~ 1 ;

CO2(CH2) 4 ~ ~ 3 Z

~ -- ,. ,: ,, , :

(27d) ~ CO2CH2CH2 (cF2) 5 ~ CO 2CH 2CH 2CH 2 -- \CH
:~ _ 2 ; ~
-12 a -.:

' ' '' ' , , -C5~2C~2cB2cy2cF2ocy~ 3) 2 28) [~3 . co2~ca2)3~--. _ ~ 2 129 ) ~--SO2C~2 ~ CY2 ) 3C 3 C~2_ 2 130) lCF3)2~ cF2)2~a~2o2c~ a~ ~ 202e~ C~2)2~2)2OC~CF3);2

3,0 j31) y~ 2C~aO2~>C~ 2 Cla~ D
a32) f~ll2c~2~P2 2 ~ 3 2 ~CI!332~`COCF2~C~
O ~ 3~ S
' - q32~ O2C~ C~2~21 F2~ 3)2 ~CF3) ~FCO~F2 2 2 2 2 ~
O_ -O_ C

~; 2 2 2~P2~2~F ( ~3 3 2 ~ C~3 ) ~CO~F2CF2C~2 , .... C--{~~ . O
~CEl;!cl32(cP~2)8o~ F(cF3i2 IGP'332PC~5CF2)8~2 ;2~3 g:--O ~~--O
~D ~
~3~a) ~ a)3~F~)2CF(CP3)2 ~CZ~3)2~ cF~)2 ~2-- ~ X~ - C02 ~~t 2)3~Pa)20CF~C~3~2 ~C~3)2FtO(t F~)alCH2)3 ~0 ~3~) 1 0 ~
--O'--C ~ C--0 ,~

~,3 .

,,~

~Z~4~

~ 2)3(1F2~20C~(C~3)2 ~e~3)2~F3~cF2)2(c02)3o ~o ~c -~
C~3 C 3 36 ~ ~CIa2 ~ 3 ( CF2 ) ;~ CF3 ~ 2 1 I:E'3 ) 2~CO l C 1'2 )2~ CB2 C5~3 a~
0~ 0 137) O(~ )3 ~F2)2o~F332 ~ P3~2~tO~F2);~CE~2)30 ~X-. ' .
t3~3 ~X 3 Z (OEr3) 2FCO (CF2) 2 ~C~2~ 2i~2 ~

13~) (CF3)2CFO(c~2)~ a)3o ~ OIC ~5co2 ~ -0(C3z)31CF2)z~' F(cF3~

S40) 1CF3)2cpo(cF2)2~ca2)3~-oc~2~ ~ ;20 ~C02)3~CFI)2~r(5F3~2 ~40~) ~CP3~aCPO(cF2)2~cE~2~2o~o2c~ol~o~ 2)3(~p2)2oc S~S12 H2?3~cE~2~ cF~)2 ~CF3)2 PC(eP2)2~ 2 3 ~ ~

O------CH~>CH

~ .

_, .

~OC3 ~4:~3)2CFOCF;~CF2~C82~3 ~ .2 ~ C1320(1::02)3CFaCF20tP(~F3)2 t41~ fE~2C~2C132CP25 @2~ F(CF3)2 ~CY3)2YcocF2~ ~2~ ~2C 2 ~0 CU~
8 æ
~ .
~4~) ~W [~2~3) 2 2 ~2~B2~2CF2~ P3 1 2 C~2CF2CP20cP ( C~3 ) 2 ~132CH2cF2cF20cp ~ C~3 ) 2 2C02~ ~2~P2CF20~Ft~ F3)2

4 ~ ( C1~2 ) 3CF2C~20~F ( cF3 ) 2 l 2 .. ..
C~2 ) 3CE!2CF2ocp ~ ~ Ç'3 ) 21 2 ~C~2C112~:F2CF3 C112C~ acF2~x P~CF3 j2 2cE~2cF2~ F3 C~12--CP2CF3 (45a~ ttH2C~3)2 ~:02~}12C~2 ~c:F2C~2) 40C~ (~F3) 2 _~B8 P
(~6) ï ~ , . - .
~ 3 ) 2FCCF2~2~2C~ZC~ CO~--,"~ ~ .
, ~7) fl~tCi'~)5C~C~2C~2~ O

) fg~ 3)2~cocF2cpal F;2~ 2c~2 IClas~ C
C02DIRl ~C2 a~2~a~2)~ S~t2C~2Q
IDlR~ C1~2)" (C~O~), Cl32Q~
~9 ) ~ r~
SO 3 ~ ~:E12CB~O}~CEl2Cl .
.
. 5~ El(O~)C1120 Sl ~~2~a t C~2 ) 40CP ( CF3 ) 2 CB2CE120~
:52 ~ a~ lo~ ) C~2~r "_ 53~ q -CR2CEI10~)C~
S~ --CEl2cB21~F;~5cF3 55) s ~ 112t:~0EI)Ca20}1 2a 56~ 2c~2~c~2)6~3 S~) --CÇI2~ ~2~F2)~ 3 --t:B2g~ 3 - S~ ~;2C~ F2)8CF3 -CE2~B~0~ 2ar 59~ ~ac~2~c~2)9eF3 ~}1a~:8~ 2~1 ~iO) -~C~)3~CF2)9CF3 61) ~ 3)G~2l~ F2)7c~3 R
62)-~c02)4crl~3)cF~ cr3)2 ~;2e~2Cl ~3) --~2c~c~2c~2cFc~ F~cF3)2 -C~2~ ) 2 . t 93 C~CP3) 2 ~;3~ C~2CH IOH~ CH~C~20- (CF2 ) 7CF3 --CH2C~ ~OR) C~3 30 ~b) El - -CON IDlRl ) 2 ~a ~ ~2)x~l S~~)x2 --1¢-.

... . . . .

, ",~.,.

` ~
34~

DlRl -CH2 ) X ( CHH ) X2CH2Q
64 -cH2cH2cH2cF2cF2ocF(cE3)2 2 2 65 -(CH2)4(CF2)7CF3 -CH~CH20H
-CH2CH2CH2CF2cF20cF(cF3)2 -C~2CH(OH)cH20H
( 2)5 3 -CH2CH(OH)CH2Cl 6~ -(CF2)5CFCF2CF3 -CH2CH(OH)CH2Br Class H
l 1 2 lO 69 -cH2cH2cF2cF2ocF(cF3)2 -CH2CH20H
" -CH2CH(OH)CH2Cl 71 " -CH2CH(OH)CH20H : ~ :
72 -CH2CH2(CF2)40cF(cF3)2 73 -C~12CH2(CF2)5CF3 "
74 " -CH2C~(OH)CH2Br -CH2CH2(CF2)7CF3 -CH2c~(OH)cH
76 -(CH2)4CH(OH)CH20 :
77 " -cH2cHcH2o~2çHcH2o~
OH OH ~:
20 78 -CH2CH(CH3)CH2(CF2)3CF3 -CH2CH2c~ ~ H2 O

Class I :-O O O, ~ ~ ' 79 H3COC(CH2)3CN[CH2CH2NHc(cF2)30cF(cF3)2]2 :
. O O O
- "
80 H3CNHC(CH2)3CN[CH2CH2NHC(CF2)3 ( 3 2 2 O O O . ' 81 ClCH2CH(OH)CH20C(CH2)3CN[CH2CH2NHC(CF2)30CF(CF3)2]2 O O O
': ~ ,- .
30 82 ClCH2CHOHCH20C(CH2)3CN[CH2CH2NHC(CF2)6CF3]2 .

~;Z3~4 (82a) /0 CH2-CHCH20C ( CH2 ) 3CN ~CH2CH2NHC ( CF2 ) 2CF3 ]2 O O

' ~".

'. '' '; ~' :

-17a-~2~3~4 o o o ,. .. .. .
83 BrCH2CH(OH) (CE~2)30CCH2CH2CN[CH2NHC(CF2)6CF3] 2 O O ~ ,,' " " "
84 HOCE~2CH (OH ) CH20CCH2CN [ ( CH2 ) 4NE~CCF2CF3~ 2 O O O
,- - .~ .
85 H3CCH(OH)CH2CH20CCH2CH2CN[CH2CH2NHC(CF2)4CF37 2 Class J
:
O O O O O
10 86 [(cF3)2cFo(cF2)3cNHcH2cH2] 2NC(CH2)3CNH(CH2)6NHC(CH2)3CN~
- [ CH2CH2NHC ( CF2 ) 30CF ( CF3 ) 2] 2 O
Clas s K
, /\ ~ ~' 87 ) [(CF3 j2CFO(CF2)3CNHCH2CH2]2NCS2CH2CH CH2 ~ ~
:~ O O - ~:
88 ) [CF3(CF2)6CNHCH2CE12]2NC52CH2 2 ' ' . . ': ,.' ':

:
: ' ' ., :
:
, 30 ~' ~
,i -18-,' ' .

PREPARATION OF ADDITIVES
The phthalic ester additives of Class A are prepared by first forming a mono-(DlRl) phthalic ester, which corresponds to the compoun~ of Class A wherein L is hydrogen. This intermediate may be prepared by reacting phthalic anhydride with the corresponding reactant having the formula (I) l lH (I) wherein Rl and Dl have the meanings previously given for the additives of Class A. The reaction may be carried out in an inert solvent,-such~as benzene, with or without a base catalyst such as pyridine, at temperatures ranging from room temperature to the reflux temperature of the reaction mixture ~oweYer, reaction temperatures greater than 110C. may lead to substantial disproport~ionation of the desired intermediate into phthalic anhydride and bis-(DlRl) phthalate esters.
- The reactants (I) are well known materials and may be prepared by conventional methods. where9 for example, the reactant is a primary alcohol, it may be readily prepared by reacting the corresponding primary lodide, having the formula (II) RlD I (II) wherein Rl and Dl are as defined previously, with oleum for oxidation of the iodide and subsequent hydrolysis of the resulting intermediate to form the desired primary alcohol. The hydrolysis step may be effected in an aqueous solution at temperatures of from about 80to 100C., and the desired primary alcohols may be recovered as by extracting the aqueous phase with ethyl ether. Alternatively, primary alcohols of formula (I) may be obtained in accordance with the method disclosed in co-pending application o~ F. Mares and B. C.Oxenrideri entitled "Process for Preparing Par~ially Halogenated Alcohols~, Serial No. 256,124 filed June 30, 1976. The latter process may also be used for obtaining secondary ",,, ~ . -19-',,~ "

1~2~

alcohols of formula (I).
The required primary iodides may themselves be prepared by known procedures. For example, wherein Dl is alkyl, e.g., ethyl, and ~1 is -(CmF2m+l) (m is as prevlously defined) the desired primary iodide may be obtained by way of a telomeriza-tion (radical addition) reaction of the commercially available perfluoroalkyl iodides with the corresponding alkene, e.g. ethylene, at temperatures of from about 80to 100C. employing a peroxide, e.g., benzoylperoxide, as a radical reaction initiator. Preparation of omega-perfluoroisoalkoxyfluoroalkyl iodides is more fully described in U.S. Patent 3,514,487 (issued in 1970 to Annello et ~ -al.~.
The phthalic ester additives of Class A wherein L is ~2R2 and wherein DlRl is the same as D2R2, i.e. the bis(DlR
phthalic esters, may be prepared either by reacting phthalic anhydride with the corresponding reactant (I) in an inert solvent ~ ;
such as benzene, with or without the presence of a catalyst ~
such as pyridine, at temperatures-of greater than 0C. In addition, the bis-(DlRl) phthalic esters of Class ~ may be obtained by reacting the corresponding mono-(DlRl) phthalicester intermediate wi~h thionyl chloride to produce a compound of the formula (IV) ~2DlRl (IV) COC 1 : ' which may then be reacted with the corresponding alcohol (I) to the desired bis-(DlRl) phthalic ester.
The phthalic ester additives of Class A wherein L is D2R2 and wherein D2R2 is different from DlRl, i.e. the bis (DlRl~ D2R2) phthalic esters, may be prepared by reacting the desired mono-(DlRl) phthalic ester intermediate with thionyl chloride as above to produce a compound haviny the formula (IV) which may then be reacted with the desired alcohol compound having the formula (V) 13l~2~

2 20H (V)whereby the desired additive is obtained.
The terephthalic ester additives of Class A wherein L is D2R2 and wherein D2R2 is the same as DlRl/ i.e. the bis-(DlRl)-terephthalic esters, may be prepared by reacting the commercially available terephthaloyl chloride with the corresponding reactant (I) in an inert solvent at temperatures of about 25 C. thereby yielding the desired bis-(DlRl) terephthalic ester. Alternatively, a conventional esterification of terephthalic acid with reactant (I) may be employed to form the desired bis-(DlRl) terephthalic esters.
The terephthalic ester additives of Class A wherein L is D2R2 and wherein D2R2 is different from DlRl, l.e. the~bis~

(DlRl,D2R2)- terephthalic esters, may be obtained by hydrolyzing the corresponding bis-(DlRl) terephthalic ester with potassium hydroxide in an inert solvent RlDl-alcohol (I) mixture to produce a mono-potassium salt having the formula (VI) C02K COCl (VI) ~ (VIa) ~ ~ ;

C2DlRl 2 lRl which may then be reacted with thionyl chloride to form a mono-ester ~hloride(vIa~ follo~ed by reaction with the desired R2D20H
reactant (V) to produce the bis-(DlRl,D2R2) terephthalic ester.
Alternatively, the bis-(DlRl,D2R2) ester may be produced by esterifying terephthaloyl chloride with benzyl alcohol and hydro-lyzing the resulting dibenzyl terephthalate with potassium hydroxide in the presence of benzyl a:Lcohol to produce an insoluble mono-~ potassium salt having the formula (VII) ,' C02K

~ (VII) .~

~1~2~

This mono-potassium salt may then be reacted with thionyl chloride to form the corresponding acid chloride, which may be subsequently reacted with the desired RlDlOH reactant (I) to produce a mono-DlRl, benzyl ester having the formula (VIII) 2 lRl (VIII) C2C 2 ~
, . , This ester may be hydrogenated over palladium catalyst to liberate toluene and form a mono-(DlRl) terephthalic ester intermediate, corresponding to Class A compound wherein L is hydrogen, having the formula (IX) C02DlRl (IX) CO H
This ester may be reacted with thionyl chloride, followed by addition of a R2D2OH reactant (V) to form the desired bis-(DlRl,D2R2) terephthalic ester.
The above procedure for producing a bis-(DlRl,D2R2) terephthalic ester in which a mono-(DlR]) terephthalate ester is formed as an intermediate, is based on the insolubility of the mono-potassium salt (VI) in the selected RlDl reactant (I~, and can only be applied to the lower molecular weight reactants in which potassium hydroxide is soluble.

In the case of the higher R D OH reactant in which potassium hydroxide is not soluble, dibenzyl terephthalate may be prepared by well known processes and then hydrolyzed in benzyl alcohol by potassium hydroxide to form potassium benzyl terephthalate, which may then be converted to the ester chloride by reaction with thionyl chloride. The ester-chloride may then be esterified by reaction with the corresponding RlDl-alcohol to form benzyl, DlRl-terephthalate. The latter compound may then be hydrogenated over a 34Lg conventional hydrogenation catalyst, such as palladium-on-alumina catalyst, in an inert solvent (e.g. dioxane) yielding the mono-(DlRl) terephthalate ester intermediate (X).
The phthalic and terephthalic esters of Class A wherein (CH2)fl(CHOH)f2(CH2)f3OH, i.e. the bis (DlRl, alkyl diol) phthalic and terephthalic esters, may be produced by conventional methods. Thus, where L is -CH2CH2OH, the phthalic or terephthalic ester may be formed by reacting the corresponding mono-(DlRl) phthalic or terephthalic ester intermediate with ethylene oxide to produce the desired additive. Similarly, a mono-(DlRl) phthalic or terephthalic e~ter intermediate may be reacted ~ith glycidol to produce the Class A additive wherein L is -CH~CH(OH)CH2O~.
The monoester required for the halogenated derivatives of the foregoing additives of Class A may be prepared according to the method illustrated in the hereinbelow Examples 14, 15 and 16.

The additives of Class B may be obtained by standard techniques employing the corresponding mono-(DlRl) phthalic ester chloride (IV) or terephthalic ester chloride (VIa). The desired mono--(DlRl)- phthalic or phthalic ester chloride may be reacted with the corresponding reactant illustrated in Tables Ia and Ib below.

~Z;344 .

S~ble ~a ~reparation of Class B Additives:Phthal~te E~ter Additives , . . . . .
re~ Adaitive ~tnr~ing M~ter~als ~or~ul ~ster-Chloride React~n~
.
~ ~ 2 1~ 2DlRl ~Z~2 : 2~ - - o ~nCl ~ ~ 2 1 1 ~ Z)2c~cH20~)2 ; L. 2~ ~ 6tC~oc)2 2 1 1 1 t~OZ)2C~OH

' 1 '' ~~
, . ~ 2 . . ., .~ 2D1Rl . ~Z~c~2c~2)r~
.. 2 2 ~2(QC~2C~2)rC~2-~10Z ~C~2)rZ00 L 2~C~ ) ' ~ ~ 2~ OZ~CB20cB2)rZo0 L 2Z - - J 2 - ~C~aC~2)r~
, ' ' ' ' ' ' , . . ' , ~ .

-24.
.: ' -", ~2;~4~

q~able I~ (cc~nt. ) r~r~tion of Class B Additives.Phthal~te Ester Additives l~sl~ed Addit$-~e ~tarting M~teri~l~
. ~or~ula Euter-Chloride Reactant (~[ 2 1~1 ~ 2DlR1 1 810Z~C
. ~ 2 ' r~2D1~ C0 ~ ZO~ ~ 3 L C02~t-~

~ ~F021~1R~ )8 ) 3 LC~2~O~ - -~able lb : Ithalate Est~r Additives ~tarting Materi~l or~ula l~-ter-Chlori~ie R~ct;-nt .~2Dl~l . ~21J1Rl ~302)20, , . ~--__o -. , - . 2 ~2Dlkl t 90Z) 2C ~ C~;!~ ) 2 ~2~--~ 02~)2 DlRI - ( ~ao~s ~ 2C~OH

~0a3--e~o~

.

~1 ; .

23~L

able lb (csnt. ~

IBtarting Haterlal ~o~ ula l~ter-Chloride 2e~ctant ¦' ~2D~ D~IOZ ~ 2c~2 ) ,, l ~CB2(0C~2c~2~rc~2 ~2Dl 1 1 liO~ 2~ r~~
L 2~C~2)r_ ~)201Rl , . , ~Oz~cla 20CE12)r~:0~
. . ~, . ..
, . . ~ 2~ ( ~20C~2 ) r . . 2 h -, ~2DlRl . , , ~ ~210~ C
~2Z--_ 2 ~2DlR1 1 C~ ( ~0~ ) 3 X~--~
'. 3 r ¦- ~2 ~ ( ZS)E~ ) 3 L ~3~CO~ ' .

,' ' " ' .'' ' ' ".
, --26-- .

: . ' .

~ . "

For phthalic acid esters of Class B, the reaction of the mono-tDlRl) phthalic ester intermediate with thionyl chloride to form a mono-(DlRl) phthalate ester chloride (IV) can be avoided if trifluoroacetic anhydride is employed for esterification of the mono~(DlRl) phthalic ester intermediate. In this reaction, the mono (DlRl) phthalic ester intermediate is reacted with tri-fluoroacetic anhydride in the presence of the desired reactant, e.g.
C(CH2OH)4, shown in Tables Ia and Ib, preferably in an inert solvent such as, for example, benzene, dioxane, ethers and chlorinated hydro-carbons, at temperatures of from about 0 to 50C.
The ring~halogenated derivatives of the above Class Badditives, i.e. Class B additives wherein n is an integer of 1 to 4 and Q is halogen as defined previously, may be prepared*by reacting the corresponding halogenated phthalic anhydride having the formula (X) Q~ ~ / (X) with a RlDlOH reactant tI) in a slight excess of pyridine at a temperature o~ about 3DC. to yield a pyridinium salt which ma~ then be treated with thionyl chloride in an inert solvent at from about ~20C to ~30C./ to form an ester-chloride which may be reacted with desired reactant of Table Ia. A similar procedure is employed when halogenated terephthalic ester additives are desired.
The additives of Class C wherein q is 1 may be prepared by reacting chlorides having the formula (XI) co2CH2C6H4 ,~
Qn OCl (XI) wherein n and Q are as previously defined and which may be ob-tained by conventional methods, with an alpha-omega diol having *See the heréinbelow Examples 17-22.

the formula (XII) (OH)2 (XII) wherein Z'is previously defined, to produce compounds of the formula (XIII) ~ ~ :

~2CH2C6H4 Qn ~ C2z' 2 (XIII) which may then be hydrogenated~: over palladium-on-alumina catalyst to form the corresponding acid having the formula (XIV) C2H : ~:
~n ~ CO2Z' _ ~ (XIV) The acid may then be reacted with thionyl chloride to obtain the corresponding acid chloride, which may be ~eacted~-^ with RlDlOH
alcohol (I) to produce the desired Class C additives, having the -~-formula (XV) _ ~02DlRl : Q ~ C02Z' _ ~XV) The additives of Class C wherein q is 2 may be produc*d : in the manner similar to that employed in producing the additives of formula (XV). ~hat is, chlorides having the f~ormula (XI) may ;
be reacted with a dlol having the:;formula (XVI) ,~2ZbH

(XVI) Qn CO2ZOH
wherein Z is as defined previously, to produce compounds having the formula (XVII) ~ 2 2 6 5 ICO2CH2C6H5 (XVII) Q ~ 2Z C2 ~ 02-ZC02 ~ Qn : -, .. ~ . . . ,, , , . ~ . .
. . . .
, 2349~

which may then be hydrogenated (e.g. over palladium-on-alumina cata-lyst) to produce the corresponding di-acids in which the -CH2C6H5 groups of (XVII) are substituted by hydrogen. The di-acids may then be reacted with thionyl chloride to Eorm the corresponding acid chloride, followed by esterification of the chloride with the desired RlDlOH al.cohol of formula (I) to produce the desired Class C additives having the formula (XVIII) CO2DlR1 ~ 2 1 1 (XVIII) ~ ~ CO -ZCO ~ Q
Qn CO2Z'CO~'~ ~ 2 2 n Qn The additives of Class D wherein T is:

- OCH2~ ~ CH2-may be preparedby reacting a phenol of the formula (XIX) ~H

:~ 1 ~ (XIX) wherein Al is previously defined, wlth a bis(chloromethyl?- :
benzene such as either 1,4-chloromethylbenzene or 1,2-chloromethyl-~ benzene, to produce an additive of Class B having the formula (XX) :,~
~ r~~
~0 ).-ocH2~j)~ " ~ Al ( XX ) ~ --- CH2~~
The above reaction is preferably performed in an inert solvent such as acetone~ and under reflux conditions. A reaction pro-moter such as potassium iodide and or potassium carbonate may be added to speed the reaction and increase the conversions ob-tained.
The additives of Class D wherein T is OCH --CH2 ~
. 30 may be prepared by reacting the corresponding dihydroxy phenol with a compound of the formula (XXa) 4~
,~2Cl ~ 1 (XXa)wherein Al is as previously defined. The latter compound (XXa) may be conveniently prepared by reacting a compound of the formula (XXb) l (XXb) with formaldehyde and hydrogen chloride in the presence of aluminum trichloride.
The additives of Class D wherein T is -C~
o l_ may be obtained by reaceing a chloride of the formula ~XI) , Z39~9L

~1 ,~ , ~XX~ ) a~
~it11 a ~(hydro~y) benzene, ~uch ~B olther 1,11-bl~5hyd~oxy)-b~aser~e or l,2-bi~hy~roxy) l~nzene to product ~n ~l~di'clve of Cl~ss D laav~ng the ~o~sul4 ~ ~o (~_~C ~ ~II ) - . , O O
ID ~ ~ai1ar s~bloll, the ~itive~ sf ~ 156 1 10 ~shereln ~ 1~

.' O O
~y ~e p~o~uc~d by re~ctlng "che corse2~pond~n~ phenol ~XIX) ~ith tb.e ~ors~p~ndlng ~ lther toræphth~ or phthall~ acid, to produoe n additi~e of ~IA~S D h~vlog 'che ~or--ul~ XIII) She b~lo~enated u~el ~ethyl~te~ ~e~ivatives o~ the fo~egolng :~ 20 cl~s~ ditlve~ ~ay b~ produeed by i~tandara oethods.
~huæ~ ~or ~mple, the ~alog~n~lted del~iv~lti~s o~ t~e l~tt~Y ~itlves o~ ~oYzllulA (25XISI ) ~y. b~ o~tained by ~eoctlng tho co~r~p4adin~ halogenated ~o~npoun~ Ying tbe ~or~ul~ V) , CO~l Q ~ IV) , COCl ~her~ln Q an~ rl are a~ ev~ously ~3e~ned, ~ith ~ odiu~ ~alt of the ~orre~pon~lng ph~rlol ~XIX) ln ai~x~ne at 50C. Sor a period of two 30 hour~, thes~by p~ucir,lg a h~logenatod cla~s D ~dditiv~ having -~2~4~

the formula (XXV) ~--oc {~co{~ ( xxv) O O
The ortho- and para-substituted phenols of formula (XIX) wherein Al i5 -Rl may be produced by reacting the corresponding primary iodide RlI with phenol or phenyl acetate at elevated temperatures, e.g. about 250C, to produce a mixture of the de-sired ortho- and para-substituted phenols.
The ortho-substituted phenols of formula (XIX) wherein Al is DlRl, in which Dl is alkyl of at least three carbon atomsl may be produced by reacting the corresponding olefin substituted alcohol of the formula (XXVI) OH
~` (CH2)~dcH CH2 (XXVI) -wherein d is an integer of 1 to 3, with a primary iodide;, having -~
the formula RlI, in the presence of azo-bis(butylrOn1trile)~at reflux temperatures to produce an iodinated-alkyl substituted alcohol of the formula (XXVII) ~H I ~-~ (CH2)d CHCH2Rl (XXVII) which may then be treated by potassium hydroxide in the presence of methanol solvent at 25C. and hydrogenation of the resulting olefin- `
substituted alcohol over a conventional catalyst (e.g. palladium-on-alumina) to produce the desired ortho-substitated alcohol. Alter~
natively, the foregoing iodinated-alkyl substituted alcohol (XXVII) may be reduced in a mixture of zinc, ethanol and dry hydrochloric acid to obtain the desired ortho-substituted alcohol of formula (XIX).
The para-substituted alcohols of formula (XIX) wherein Al is DlRl, in which Dl is alkyl of at least three carbon atoms ~' ' .

.. . .
' , 23~9L

may be produced by reacting a para-olefin substituted phenol of the formula (XXIX) OH
~XXIX) ( CH2 ) dCH=CH2 wherein d is as defined above, with an iodide of the formula RlI
in the presence of ABN at reflux temperatures to produce a secondary iodide intermediate which may then be reduced either (1) by reaction with potassium hydroxide in the presence of methanol at 25C. and ;~ hydrogenation of the resulting olefin-substituted phenol, or (2) by reaction with zinc and ethanol in the presence of dry hydrochloric acid, to produce the desired para-substituted alcohol.
The ortho- and para-substitute;d phenols of formula (XIX) wherein Al is -DlRl in which Dl is alkyl of 2 carbon atoms may be produced by reacting a~primary iodlde~ o the formula RlCH2CEl2I
with phenol in a conventional Friedels-Craft reaction in the presence AlC13 to form a mixture of the desired phenols. Likewise, a mixtur~e of ortho- and para-substituted phenol (XIX) wherein Al is -DlRl in which Dl is a mekhylene i~- radical may be produced by~reacting RlCH2I with phenol in such a Frledel-Crafts reaction.
The ortho-substituted phenols of formula (XIX) wherein A
is -ODlRl in which Dl is of at least three carbon atoms may be produced by refluxing a mixture of 1,2-bis(hydroxy) benzene and an olefin chloride of the formula CH2=CH-(CH2)dCl, wherein d is as defined previously, in an inert solvent in the presence of potassium iodide and potassium carbonate, to yield a compound of the formula ; (XXVIII) QH
~ O ( CH2 ) CH-CH2 . .
~ d (XXVIII) which may then be reacted with an iodide of the formula RlI in the :

~1~23~4 presence of azo-bis(isobutyronitrile) (ABN) ak reflux temperatures.
Reaction of the resulting product with potassium hydroxide in a solvent such as methanol at 25C., and hydrogenation over a pal-ladium-on-alumina catalyst/ yields the desired ortho-alcohol.

In a similar manner, the para-alcohols of formula (XIX) wherein Al is -ODlRl, in which Dl is alkyl of at least three carbon atoms, may be produced by reacting a compound of the formula )dCH CH2 -;
~ lo ~oJ
wherein d is as defined previously, with a RlI primary iodide in the presence of ABN at 80C., eliminating HI from the resulting lodide with potassium hydroxide in methanol at 25C./ and hydrogenaking the phenoxy olefin so produced over a catalyst (palladium-on-alumina), to produce aPhenYl alkyl ether of the formula (XXXII) CH2)dCH2cH2 ~ (XXXII) This phenyl alkyl ether may then be converted to a compound of the formula (XXXIII) O ( CH2 ) dCH2CH2Rl (XXXIII) by a ~riedel-Crafts acylation in which the phenoxy alkyl ether com-pound is reacted with acetic acid anhydride and aluminum chloride in the presence of an inert solvent (such as CS~) and at reflux tem-peratures. The formula (XXXIII) compound may then be oxidized, for example, with meta-chloroperbenzoic acid, in the presence of CHC13, and at reflux temperatures to produce a para-substituted benzene having the formula (XXIV) :

~ `~
3~

O ( CH2 ) dCH2CH2Rl ~~ , (XXXIV) OCO~IC3 This para-substituted benzene may then be subjected to hydrolysis by reaction with potassium hydroxide in methanol at 25C. to achieve the final desired alcohol.
The ortho- and para-substituted phenols of formula (XIX) wherein Al is -ODlRl in which Dl is -CH2- may be produced by reacting a potassium salt having the formula (XXXIVa) ~ OH (XXXIVa~

with an iodide of the formula RlCH~I. Phenols in which Al is ~
-ODlRl in which Dl is -CH2CH2- may be formed by:reacting the ~ :
corresponding dihydroxy benzene with C~ -CH2 and chlorination of the resulting -OCH2CH2OH substituted phenol with HCl in the presence of ZnCl a~ catalyst. The chloride may then be reacted with a compound of the formula RlLi (which may be formed as from the corresponding : 20 RlI iodide) to yield the desired ortho- and para-substituted phenol ~-(XIX). ~ :
: Ortho- and para-substituted phenols (XIX) wherein Al is -ORl may be formed by reacting iodobenzene with a cesium compound having the formula RlOCs to produce a compound which may be reacted with CH3COCl to yield a mixture of ortho-and para-substi-tuted intermediates, i.e. ~.
OR~ ORl - ~ COCH3 (XXVa) and .~ ~ (XXVb) The ortho-and para- intermediates may be separated by conventional ~2~

methods and oxidized with meta-chloroperbenzoic acid, followed by a conventional hydrolysis of the resulting product to form the desired ortho- or para-substituted phenol (XIX) in which A is ORl- :~
The ortho- and para-substituted phenols of formula XIX
wherein Al is -CO2DlRl may be produced by conventional methods from the corresponding hydroxy benzoic aclds and RlDlO
alcohols in the presence of trifluoroacetic anhydride.

The phthalic ester additives of class E wherein B is -CO2DlRl may be prepared by reacting an acid chloride of the formula (IV) with a secondary amine of the formula (XXXVI) ; NH = ~2R2 (XXXVI) wherein D2, D3, R2 and R3 have the meanings previously assigned.
Such secondary amines, wherein D2R2 lS the same as D3R3 and~wherein D2 is 1 or 3 or more carbon atoms, may be prepared by reacting a primary iodide of the formula R2D2I with sodium cyanide in the ~-~
presence of dimethylsulfoxide to produce the corresponding nitrile which may then be hydrogenated, e.g. at a pressure of 40 psia,over a platinum oxide catalyst in the presence of acetone to produce a mixture of primary, secondary and tertiary amines having the 2 2 2' (R2D2)2NH and (R2D2)3N, respectively. Isolation of the desired secondary amine may be effected by standard tech-niques. Likewise, preparation of a secondary amine of the formula (XXXVI) wherein D2R2 and D3R3 are different and wherein D2 and ` D3 are each 1 or 3 or more carbon atoms may proceed by reacting the above primary amine R2D2NE12 with an appropriate R3D3I iodide to form an intermediate iodide which may be then treated with sodium hydroxide or sodium carbonate to form the desired free aminetXXXVI) .

~Z~44 S~e phthalic ~ter ~itl~ o~ C:i8Ei~ her~ 18 -ODN ~ay ~ I?~o~u~o~ ~y ro~cltlon o~ o~tor c~lo~lde tlV~) \~4a~ ~lt~ econd~ry ~lne of the ~or~ SXXXVI~.
~rbe te~phtb~lle e~t~r a:~itSYe~ o clas E ~hereln B
O2D~ ay be psoduce~ ln a s~ilar ~anno~ ~s the above phthalic ~t~r ~dAti~ by ~Isub~titutlng ~ ~hlo~ae o~ tbe 0s3~ul~
ClOC ~ COCl or ~ci~ 6hlor~e (IV) .
91!h~ a~ldltl~e~ of cl~ Y ~y be p~oaucea. ~y rewtlng a o~poun~ of the for~ul~ 6X~VII) XVII) ~hereln Y' ~ a3 pr~vlou~ly deflned~ Ylth ~C~3C03~20 ~nd AlC13, in Frleael-Cr~t~ acylation reaotlon o~ ing the re~ulting co~pound .
tho ormula ~IXXVIII ) 3 ~ ~C~3 ~XXX~lII ) ~b brs~lne ln a t2n pe~o~nt.~quo~ E~ta~iu~ hydroxide solution 20 to proauce t~o correspon~lng ~ acid, ~hiolh lo~y be re~ctea w~th th~onyl c~lo~de ~t ~lux t~por~t~res to produce the correspond~n ~lichlorlde of the ~or~ula~ ~IX) Cl~"' ~>--COCl ~ XIX) ~Ich ~y then be r~act~a ~rlt~ the ~equired ~eoond~ry a~sine~ of the forlaul~ SR;~D11217~ ln trlethyla~Dlne ~nd ~cetone 21nd re~luxed to ~o~uce 'che d~sirea Cl~w F ddltl~re.
Sh~ ~daitlY~ of Cla~s G whereln E~ C02DlRl ~ay be proauce~ by ~ eactior~ of ~ RlD100 compound ~I) ~ith pyromellit~c 30 ~ci~ anhydride t~> pro~uce a ~i~ture ~ add~tlve lnter~edi~te co~re~ponding tD those olE C1~8B G ~he~eln El 18 -C02DlRl and E2 is .1~....

2~

-CO2H, followed by (2) reacting the foregoing intermediate with the corresponding epoxy compounds, e.g. CH2-CHCH2Q'I, in the presence of a tertiary amine (such as, for examplel pyridine, heterocyclic aromatic bases, and cyclic tertiary amines) as catalyst. Like-wise, Class G additives wherein El, is -CON(DlRl)2 may be produced by reacting the suitable secondary amine, HN(DlRl)2, with pyro-mellitic anhydride.
The additives of class H may be prepared BY first forming intermediate isomeric half-esters corresponding to the formula of Class H additives wherein R~' is hydrogen. These half esters may ~
be formed by heating trimellitic anhydride together with thionyl ~-chloride or phosphorous pentachloride at temperatures greater than 50C. to produce a compound`of the formula (XL) n ;
C ~ O
` ~ C=O (XL) ~
; ' , ;~
20 ~ followed by reaction of these chlorides with a compound having the formula RlDlOH to produce the deslred half-esters.
The additives of Class H wherein R2' is -(CH2?x ~H CH2 wh~rein xl is 1, may be produced by reacting the appropriate half-ester intermediates with a halohydrin (e.g. chlorohydrin) in the presence of KOH. The Class H additives wherein xl >1 may be formed by treating the corresponding half-ester intermediate with thionyl-chloride, followed by reaction of the resulting chlorides with an omega-alkenol of the formula CH2=CH(CH2)nlOH, in which nl is an integer of 2 to 5. The products may be oxidized as with meta-~38-, ;~ .

~orop2rb~nzole ~ctd to yield the ~e~ired i~o~erie Cl~sh ~2 13 tc~;2)xlc~2 in ~h~ch ~1 i8 2 ~0 5 ~he adl~itlv~s o~ Cl~ 8 ~th~ n R2' i8 ~ 2)~ tC~}J)x ~2Q~
~ ~lsh ~2 1~ 1 aR~y be produe-d byr re~etion o~ the corresponding Clasl~ ~ d~tl~re ln ~hich R2' 1~ ~(C~2)~lC~ 2 Mith th~ or~er ~diti~ hieh Qa 1~ OB or ~rlth o hydrogen hal~de 1 oY ~r1 to yi~ n aaditl~re in ~hich 5~ is h~loglsn.
ti~ ~h~eb x2 ~ ro ~ay ~e ~or~ea !3y a:eact~ng the 10 alppsop~st~ ka~.f-le~ter lnt~r30sdi~t~ ~ith ~ethylelle o~c~deO
~e dd~tlv~s of Cl~ heYeln ~2' 18 ~ ail2~tOE~ 20sll2c~(o~)s:~aoll~ ~ay ~ proauoed ~y ret~ctir~g ~che ¢~rr~pondi~g hal-e~t~ ter~edlAte ~rith th~ Cl~s~ ~ ~dditive, ~er~ln ~ ~2Q(~)~28, ~th glyo~aol, catn~yze~ b ~c~rt~y a~ ~s e.
2~e ~ldlti~es of Cl~ y be prep~red by ~on~rentional ~thod~ ~r~lR kno~ ~ e preGursors, Ih#ving the for~ula IXLI) O
' IIOCZl~ 321~CR2 . . ¦XLI ) .
& l a2~ ~2~ Rl ~nd ~2 h~ve the ~e~nings a~siqned ~el~lously. ~ee, ~.9.~ tbe ~ono~midQ~ oS 1~.~. Patent 3,0~6,153.
~, 'Cial3~8 ~ ~aaitl~e~ ~er~ln ~l ls -3Z ~ay ~e ~orr~sd by ester-.
atlon of the E~eodes t c~rboJcyl gr~up o~ the ~ide 3pre~ur~or (XLI ) Ity rea~t1On witb ~ ~uâtable ~O~ ~leohol ~nd trlfluQroa~etic ~nhydride.
as ~. aDditlve~ ~herein ~ Ni~ ~Day be obt~ined by Eeaction of tb~ ~recur~or ~XLI) ~h ~ ~uit~hle ~socy3nate to ~or~ an iinterlDedia~e : ~ob ~oy ~e h~ate~ to ~olve C02, 3~1elâing the desired ~dditive.
E'or C1088, I ~ddltives ~herein Ml 1~ -O(CH2)~l(CNOH)x2CH2Q
- Iher~ln . x2~ the precur~or ~cid ~XLI ) ~ay be reacted ~rith ~n olef in~c -3~

., ,~
.,, ".~,, ., ' ~

~32~

alcohol in trifluoracetic anhydride, followed by epoxidiziny the resulting olefinic ester to yield an epoxy ester which may then be (1) hydrolyzed with water to give the desired additive in which Q" is hydroxyl, or (2) reacted with a hydrogen halide (e.g.
HCl or HBr) to give the above Class I additive in which Q" is halogen. For Q" = hydrogen, the precursor acid (XLI) may be reacted with propylene oxide.
The foregoing Class I additives in which x2 is zero and xl is 1 may be formed by reacting the precursor acid (XLI) with ethylene oxide and treatment of the resulting hydroxyl with hydrogen halide for Q" = halogen. Class I additives wherein x2 is zero and xl is 2 to 5 may be formed by hydrogenating the epoxide ester pro-duced as above with water in the presence of a hydrogenation catalyst.
For Q7' = hydrogen the above acid chloride may be reacted with an alcohol, and for Q" = bromine or chlorine, the acid chloride may be reacted with the corresponding omega-halogenated alcohol. For Q" =
chlorine, the Q" = hydrogen additive so produced may be reacted with HCl.
The additives of Class J may be formed by reacting a precursor acid (XLI) with a suitable diisocyanate and heating the resulting intermediate to drive off CO2 and yield the desired diamide Class J additives. These additives may be reacted with a suitable alkylating agent, e.g. Z2SO4, wherein Z is alkyl of 1 to 4 carbon atoms, to yield additives wherein at least one N-H hydrogen (i.e. M2, M3, M4, M5, M6 and M7) is substituted by Z.
Class K additives may be produced by reacting the corresponding secondary amide of the formula (XLII) o RlCNHZ
NH , (XLII) R2CNHZ2 ~
o 2;~4~

~hi~h ~y be pro~uced by conventlon~ ae'chods, ~ith a eo~pound o~
t~e for~ul~ CXS ~l.e., either CS2 or COS) in the presence of UaOH
t0 ~lola ~ ~o~ nlt of a thioc~rbon~te or ôithioc~r~onate ~hich ~ay l~hon It~e r~a~t~ w~th ~ halog~n4te~ ol~in of the for~ula ~lO~c~2)X c~-ca;2 lin ~hl~h "~lalo~ r~pre~ent~ ~I b~logen ~uch ~ chlor-~e or br~ne) ~olloYe~ by ~p~ssi~lz~Lng the resultlng ao~pound w~th ~er- aca~0 ~uch as p~r~erl~oic ~cia, to yiela Cl~s~ ~ sdditi~e~ ln ~- ~C~aalSlc~ 7~2- 9~h~re x~ t~e ~bove tbloc~r-. bon~te ~md althlocarbonate ~lts ~ay l~e reactefl ~lth correE~pondlng balo bydrin. S~o~e n~ditl~e~ y then b~ c~ily converted l~t~ a~itlves ~erein ~ C~2)~ C~lO~)C~2Q~ by reactlon w~th ~ter or Q~-O~ or ~lth hydroge~ ~llde t~.g. ~Cl) ~r Q~ha~ogen.
Sn tbe oregoing proce3ses ~or prepar~ng tbe ~dditives of t~ pre~ent ln~entlon, it ~hould be understood th~t ~o~erci~lly .o~ bls perfluoroiodide3, ~uch as ~r~ mark~ted under the tr~dename 8G ~5 hy ~hl~kol, Inc., ~y be e~ploy,~d to pro~uce add~tlve~ of the - pre~t invont~on wberein the ~luorocarbon yroups are o 31~ed chain-l~ngth~. Sbus, ~or ~æ~ple, the eo~mer~ially ~Y~ ble ~C*645 GO~-~rlslng an hppro~i~ate telomer ~xtur~ of CF3(CF2)n~I ~here~n n~ ~S~30~, 7l50~) and 9t20%~ y be ~e~ to produce a portially 1uor~-~at~a 31cohol (I) h~vlng the for~goin~ CF3tCF2)n~ - group ln tbe above-r~tlo~ of ~h~in-length6, Yhich ln t~ ay be pro~essed into ~ny o~ tbe ~boYe ~ditive cl~s~e~ ~herein ~1 co~prises the~e perfluoro-carbon cba~n~ o~ v~rying l~nqths.
~EPARATION OF ~BERS
ffhen lt 1~ ae~lr~d that the ~elected ~dditlve.o the ~resent invention be lncorporsted ~nto the Dppropriate resln prior t4 e~tru~ion of th~ resin to form the fiber, the fil~ent~ of this ~0 lnvention ~ay be pr~pared by ~orming An inti~te blend of the ~ddltlve ~nd the re~ln, ~nd then extrua~ng the blend into fll~ments ln accordDnce ~1~h wethod~ known to the ~rt. A ~ethod of or~1ng . ''' *~. ' ' .

Z3~4 the blend is not critical. The blend can be formed by treating the resin in powder form with a solution of the additive and then flash evaporating the solvent. Also, pellets of resin can be treated with a solution of the additive followed by evaporation of the solvent.
The pellets with additive incorporated thereon may be then extruded to form a fiber or first extruded and again pelletized. Another method of forming the blend comprises dry blending the additive with the resin in powder form and then working the mixture on a rubber mill or similar device. The additive is preferably, however t added direct-ly to the resin melt in the extruder.
While the ~uantity of additive incorporated into the resin prior to extrusion thereof may vary widely depending on~the degree of surface tension lowering desired, the particular additive and resin selected for use, the extrusiQn temperature and other factors, addi-tives of the present invention are gen~erally employed in the resin in an amount of up to about 3 percent by weight, preferably from about :
0.01 to 2.5 percent by weight, and most preferably from about~0.1 to 1 percent by weight of the resin.
The incorporation of these additives into the resin does not interfere with the formation of the filament or fibers drawn therefrom and the compatible additives do not disturb the normal microscopic homo-geneity of the polymer phase. This is surprising in view of the criti-cal rheological conditions involved in the extrusion of filaments.
In some instances, the surface energy of the filament can be lowered even fwrther by annealing the filament after it has been extru-ded and drawn. Annealing increases the mobility of the additive and allows additional additive to migrate to the surface of the filament.
Annealing is preferably carried out at the highest practical tempera-ture, which is normally above the glass transition temperature of the fiber and below the lower of (1) the fiber degradation tempera-ture and (2) the additive degradation temperature. Annealing is performed for an optimum period which can be readily determinedfor each particular fiber by simple experimentation. For fibers prepared from nylon-6, the preferred period is from about 5 to 240 minutes. For such periods, the additives of the present in-vention are generaly thermally stable at temperatures of up to 230C, although the degradation temperature of a given additive can be readily determined by routine experimentation, as by thermogravimetric analysis. Annealing can be performed in an inert atmosphere, such as nitrogen, to prevent oxidative degradation of the fiber, but can also be performed in air, as in a circulating air oven. Alternatively, the surface energy of the fiber may be lowered by other conventional treatments, such as by treating the fiber with steam, for example, at a temperature of from about 100~
to 220C., boiling the fiber in water or boiling the fiber in an aqueous solution containing up to 1 weight percent of a swelling ---agent for the fiber, such as any of the carrier solvents typically employed in dyeing the fiber, e.g. methyl salicylate for poly-ethylene terephthalate fibers.
The extruded fiber may be dyed or further processed as for example by tufting, weaving, texturizing, crimping, etc.
to produce a fabricated article having the desired low energy sur-face properties. Dyeing of the fiber or of an article fabricated therefrom has been found not to be adversely affected by the pre-sence of the addi~ive in the fiberJ and level dyeing is observed.
Use of a conventional swelling agent and/or dye bath temperatures -greater than about 75C are preferable to enhance the rate of ab-sorption of the dye by the fibrous article.
The embodiment of this invention wherein the additive is added to the resin prior to extrusion thereof, is generally applicable to filaments prepared from any fiber-forming thermo-plastic resin, such as polypropylene, polyethylene, polybutylene, polyamide, polyeste~, polyacrylonitrile and blends thereof.Particularly good results are obtained with polyamide and polyester resins (including blends thereof). When nylon-6 or nylon-66 is the resin, especially preferred results are obtained using the additives of Classes G, ~, I, J and K. When polyethylene terephthalate is the resin, the preferred additives of the present invention are B, G and H, with additives of Class G being especially preferred.
In accordance with a second embodiment of the process of the present invention, the selected additive may be applied to a fibrous article under conditions sufficient to allow the additive to be absorbed into the fiber. Subsequently, the fibrous article can be heat treated as by annealing, contacting with steam or boiling in a suitable solven~, to develop the fiber surface and to achieve the desired surface energy. The amount of additive to be incorporated into the fibrous article by this method is not critical and may vary widely depending upon the additives selected, the desired lowering of surface energy sought, the fiber, and other factors.
Generally, however, additive is absorptively incorporated into a fibr~us article in an amount o~ up to about 2.5 percent by weight, preferably from about 0.01 to 2 percent by weight, and most prefer-ably from about Ool to 1 percent by weight of the article. Thus, the quantity of additive that is contained in the liquid medium will generally be sufficient to provide a fibrous article having the additive incorporated therein in the above amounts, e.g. up to about 2.5 percent by weight of the fibrous article.
The additive may be absorbed into the fiber before or after the application of a spin finish to the fiber and before or after crimping or texturizing of the fiber. Spin finishes ~7hich may be employed are conventional and should be selected to prevent inclusion of a component of the spin finish which -4~-~z~

substantially reacts with the fiber or the additive. The spin finish may be employed in any amount conventionally used to produce the intended processing characteristics of the extruded fiber. The additives may also be ahsorbed into a fiber from which the spin finish has been removed, as by employing a con-ventional scouring process (e. g., washing with a soap solution).
~owever, unscoured fiber may also be treated in accordance with the process of the present invention.
Absorption of the selected additive into the fibrous article may be achieved by several methods. Thus, the article may be contacted with an aqueous emulsion or dispersion of the additive or with an organic solvent having the additive dissol~ed therein. The amount of additlve incorporated into the ~;

liquid medium for contact of the flbrous article may vary widely depending upon the additive, fiber, the fiber properties desired, and other factors. Generally, however, the additive is incorpor-ated into the liquid medium in an amount of from about 0.1 to 50 by weight, and most preferably from about 0.5 to 10% by weight.
The temperature of the liquid medium used to treat the article is also not critical and may vary from 0 to 50C. However, higher and lower temperatures may be employed with advantageous results.
The liquid medium containing the selected additive and the fibrous article may be contacted by any standard method employed in the industry to contact a liquid and fiber fllaments or articles fabri-cated therefrom. Thus, the article may be sprayed with the selected liquid medium or immersed therein. In the preferred practice, the fiber is first formed into a fabricated article such as an article of clothing which is then contacted with the liquid medium containing the selected additive.
When an aqueous emulsion or dispersion is selected for use, the aqueous medium is prepared by employing a suitable emulsi-fying or dispersion ayent. The choice of these agents is conven-tional and may be easily determined by routine experimentation.
Thus, for example, when an aqueous dispersion of a Class B additive wherein DlRl is 4-perfluoroisopropoxy-3,3,4,4-tetrafluoro-butyl, t is 4, y i5 ~C- and n is zero, is desired to be prepared, Marasperse N may be used as the dispersing agent; and when an emulsion of a Class I additive is desired, N-hexadecyltrimethyl-ammonium bromide and Igepal may be employed as the emulsifying agent.
The liquid medium may, in addition to the additive and selected emulsion or dispersion agent, also contain such carrier solvents as are typicaliy employed in the industry to aid;dyeing of the fib-rous article which is being treated. Such carrier solvents typically enhance the ability of the additive to penetrate the fiber, thereby increasing the efficiency with which the fiber absorbs the additive.
Thus, where a polyethylene terephthalate fiber, or article fabrica-ted therefrom, is desired to be treated with an additive of the pre-sent invention, the commercial solvents sold under the trademarks * * * *
Carolid, Charlab RP-3, Tanarol and Latyl and methyl salicylate may be employed as carrier solvents in the liquid medium to accelerate the rate of absorption by the fiber of the additive contained in this medium. Carrier solvents are employed in conventional amounts.
When it is desired to employ an organic solution of the additive, the organic solvent selected will, of course, depend upon the solubilities of the solvent for the additive. Suitable organic solvents, which may be easily determined by routine experi-mentation, include: ethers ~e.g. dioxane); ketones (e.g. acetone);
alcohols (e.g~ isopropanol); chlorinated hydrocarbons (e.g. chloro-form); aromatics (e.g. benzene~; and substituted aromatics (e.g.
chlorinated benzene). It is required, however, that the organic sol-vents selected for use no~ also be a solvent for the fibrous articlewhich is being treated to prevent substantial degradation of the *Trade Mark -46-' ,,~;i ~ ~Z3~9L

fiber when the additive solution is brought into contact therewith.Again, the amount of additive incorporated into the liquid medium wherein organic solvent is employed is not critical and may vary widely depending upon the additive and solvent selected, the fiber treated, the fiber properties desired and other factors. But the organic solution will generally contain from about 0.1 to 10 weight percent additive, and most preferably from about 0.5 to 10 weight percent additive. The temperature of the organic solution and khe time which is required for contacting of the fiber with this organic solution of additive is not critical, but is generally from about 0 to 50C. and contacting for a time of from about 1 second to 3 hours. However, higher and lower temperatures and shorter and longer times of contacting may be employed. Here again, as with the aqueous medium containing the additive, an organic additive solution may be brought into contact with the fiber in accordance with any of the standard procedures employed in the art to contact liquid medium and fiber filaments or articles fabricated theref~om. ~owever, immersin~ of articles fabricated from the fiber into the selected organic additive solution is the preferred method. The organic additive solution may also contain a swelling agent or other carrier solvent which accelerates the xate of absorption by the fiber of the additive~
It will be appreciated that the additives of the present invention may be applied to a fibrous article by spraying the additive thereon as from an aerosol formulation comprising (1) a liquid medium containing the additive and (2) a suitable aerosol propellant. The precise aerosol formulation selected is, of course, in no way critical to the present invention, and the liquid medium may also contain such surface active agents as are necessary to disperse or dissolve the selected additive in the liquid medium ,3~4 which is employed in the event ~he additive is not soluble therein. The fibrous article to which the additive has been applied by such a spray method may be heat treated, as dis-cussed previously, to improve the oil and/or water repellency propertie.s of the treated fibrous article.
Especially beneficial results have been achieved by in-clusion of a difunctional or trifunctional epoxide or isocyanate compound in the liquid medium containing the selected additive for additives of the present invention containing at least one hydroxy group. Suitable additives are therefore Class A additives (CH2)fl(CHOH)f2(CH2)f OH; Class B additives wherein Y is selected from the group consisting of >C(CH2OH)~

>C~OH, and -COH; Class G additive isomers, provided that Q" is -OH
when x2=0; Class H addit1ve lsomers~wherein R'2 is -(CH2)x (CHOH)x CH2Q" or -(CH2)(CHO~)CH2OCH2CH(OH)CH2OH, pro-vided that Q" is OH when x2=0; Class I additives wherein M1 is -O(C~2) (CHOH) CH2Q", provided that Q" is -O~ when x2=0; and Class K additives, wherein M' is~-(CH2)x (CHOH)X CH2~". Enhanced stability observed with this system is believed due to reaction of hydroxy groups of the additive with the epoxide or isocyanate functional group. Suitable difunctional and trifunctional epoxides are those con-taining two or more epoxide groups per molecule, and are known classes of compounds. Thus, for example, suitable epoxides include members selected from the group consisting of / 0 / 0\ :
(i) CH2 - CHCH2O(G')CH2CH - CH2 wherein G' is selected from the group consisting of ~(CH2CHO)g~, - ~ O-, -CH2 ~ CH2O-, and ~(CH2O)g-, wherein 30 g is an integer of 1 to 10, and L' is hydrogen, alkyl, -CH2OH, -CH2Cl 1~2~

or aryl, and O
( ii) CH2 - CE3CH20CH2 0 CH-G"
/ \ ~

CH2 - CHCH2CH2 ~ S
wherein G" is -OH, -CH2CH(OH)CH20H or -OCH2 H - CH2-Suitable difunctional and trifunctional isocyanates are those containing two or more isocyanate groups per molecule, and i ~
are also known classes of compounds. Thus, for example, suitable -isocyanate compounds include those selected from the group con-sisting of (1) difunctional isocyanates having the formula T3(NC0)2 in which T3 is a diradical selected from the group consisting of ~r.
alkyl of 2 to 8 carbon atoms, aryl of 6 to 10 carbon atoms, alkyl~
substituted aryl of 7 to 14 carbon atoms, cycloalkyl of 3 to 8 ~ . :
carbon atoms, heterocyclic radicals of the formula -T4'0T4'- and -T4'NHT4'- in which T4' is divalent alkyl of 2 to 8` carbon atoms or divalent aryl, and ~2) trifunctional :isocyanates having the formula T4(NC0)3 wherein T4 is a triradical selected from the group con-sisting of alkyl of 3 to 8 carbon atoms, aryl of 6 ~o lO~ carbon atoms, 20 alkyl-substituted aryl of 7 to 14 carbon~atoms, cycloalkyl of 3 to 8 carbon atoms, heterocyclic radicals of the formula -T4'NT4'-, T '-wherein T4 is as defined above. Examples of diunctional and tri-functional isocyanates are: toluene-2,4-diisocyanate, OCNCH2CH2CH2NC0, -~
OCNCH2CH2(CH2CH20)4CH2CH2NC0 and 0CNCH2CH2NcH2cH2Nco CH2CH2NCO.
When an epoxide or isocyanate compound is used in combination ; with a suitable hydroxy-containing additive of the present invention, an amine should also be employed in the liquid medium containing the additive and epoxide or isocyanate to catalyze the reaction of the additive and epoxide or isocyanate in the subsequent annealing step.

g Suitable amines which may be used include tertiary amines, and aminoacids such as 6-amino caproic acid, glycine~ lysine, etc. Suitable tertiary amines include tertiary amines wherein the N-H hydrogens are substituted by alkyl, aryl and mixtures thereof (e.g. tribenzylamine) and heterocyclic amines (e.g. pyridines and piperidine wherein the N-H hydrogen is substituted by alkyl, aryl or mixtures thereof).
The selected hydroxy-containing additive, tertiary amine and epoxide and/or isocyanate may be employed in an organic or a substantlally neutral aqueous medium and may be employed in a wide variety of concentrations. Generally, however, the additive and functional reactant (i.e. the epoxide and isocyanate reactants) are employed in an additive~reactant molar ratio of from about 2:1 to about 1:3, and tertiary amine is generally in an amount of from about 0.1 to 5 weight percent, based on the total weight of additive and functional reactant in the liquid meclium. The temperature at which the fibrous article is contac~ed with a liquid medium contain-ing the additive, epoxide and/or amine may vary widely, but is preferably from 0 to 50C, with room temperature being quite satisfactory.
It will be appreciated that the fibrous article may be contacted with the liquid medium containing the hydroxy-containing additive either before, during or after the article is contacted with a liquid medium containing the functional reactant and/or amine.
Thus, for example, sequential dipping of a fibrous article into separate liquid media containing the additive~ functional reactant or amine may bé employed. It has been found that use of the additive/
reactan~amine system provides a higher starting oil repellency and requires lower annealing temperatures than results from the use of the additives of the present invention alone.
Both the aqueous and organic liquid mediums may also contain a dye to enable concurrent dyeing and additive absorption.

The dye selected is not critical and dy2s such as dispersed dyes * * .
(e.g. Resolin Blue FBLB and Nacelan Blue FFRN (C.I. Disperse Blue Three) have been found quite satisfactory. The quantity of dye employed is not critical, and may be used in the amounts convention-ally employed to obtain the desired shade. Use of a suitable conven-tional swelling agent and/or dye bath temperature greater than about 75C is preferred to enhance the absorption of the dye by the fibrous article.
, : , Following treatment of the fibrous article with the selected .
liquid medium, the article may be optionally air dried and then sub-jected to a~heat treatment in order to achieve further ~ower~ng of the surface tension of the untreated article and/or enhanced durabil- ~
ity of the modified fiber surface to wear, home laundering and dry ~-cleaning. While air drying of the fibrous article is not generally critical, when the article is treated with an aqueous medium containing the additive together with a difunctional or trifunctional epoxide, -the article-must be air dried prior to annealing to prevent premature reaction of moisture with the epoxide compound absorbed in the fiber and thereby inactivating it. The heat treatments, in general, may be performed by treating as with steam at temperatures of from about 100to about 220C., by heating the article in water or in an aqueous emulsion of carrier solvent, e.g~ methyl salicylate for polyethylene terephthalate, at temperatures up to the boiling point of the liquid, or by annealing the fibruus article in a circulating or static air oven at a temperature of from about 90to 230C., and preferably from about 120 to 150C. The time of such heat treatment is not critical, but is generally from about 1 to 240 minutes.
Likewise, the pressure in whlch the annealing heat treatment is per-formed is not critical and atmospheric pressure has been found to be quite satisfactory.
The embodiment of this invention wherein the additive is *Trade r~ark -51-, ~

~,~,............ .
!i `- ":

~2~9L91 introduced into a ~ibrous article by absorption from a liquid medium containing the additive, is generally applicable to filaments pre-pared from any fiber-forming thermoplastic resin, such as polypropy-lene, polyethylene, polybutylene, polyamide, polyester, polyacrylo-nitrile and blends thereof. Particularly good results are obtained with polyamide and polyester fibers (including blends thereof) and articles ~abricated therefrom, especially with polyamide fibers and fabricated articles. When nylon-6 and nylon-66 is the fiber, espec-ially preferred results are obtained using the additives of Class G, I, J and K. When polyethylene terephthalate is the fiber, the pre-ferred additives of the present invention are those of Class B, G and H.
SYNTHESIS OF ADDITIVES

. . . ~
Example 1. - Preparation of the methyl amide of 1,7-Bis-(4-perfluoroisopropoxy-perfluorobutyryl)-1,4,7-triazaheptane .
monoglutaramide.
To a dry reactor is added 9.4 gms. of 1,7-bis(4-perfluoro isopropoxy-perfluorobutyryl)-1,4,7-triazaheptane monoglutaramide, 100 parts by volume of dry acetonitrile and 0.6 ml. of methyl isocyanate. The reaction mixture is heated to reflux (82C) for a period of 0.5 hours and the acetonitrile is then distilled out to a pot temperature of 120C. Carbon dioxide is evolved and heating i5 continued at a temperature of 120C for about an hour to complete the reaction. Traces of the solvent, i.e., acetonitrile, are removed on a ~lash evaporator at about 1 mm Hg and a maximum temperature of 80C. The recovered product is a light brown viscous oil weighing 9.4 gms. Analysis of the product confirms that the pendant carboxyl group has been converted to the methyl amide group, so that the product comprises a Class I additive wherein Rl and R2 are ethyl, Z3 is n-propyl and Ml is -NHC~3.
Example 2. Preparation of the 1,6-hexamethylenediamide of 1,7-Bis(~-perfluoroisopropoxy-perfluorobutyryl)-1,4,7-triazaheptane _.. .. _ . _ . .. . .
monoglutaramide.
. _ ... ..
-51a-~2~

- To a dry reactor is added 9.4 gms. of the monoglutaramide ~f 1,7-bis(4-perfluoroisopropoxy-perfluorobutyryl)-1,4,7-triazaheptane and 25 ml. of dry acetonitrile to ~orm a suspension. To this suspension at room temperature is added 0.8 ml. of 1,6-diiso-cyanatohexane, and the resulting mixture is then stirred for one hour and refluxed at a temperature of 82C for an additional period of 1/2 hour to ensure complete reaction. The solvent is then removed on a roto-vap apparatus at a maximum temperature of 125C and pressure of ^-1 mm Hg. Heating of the resulting residue is continued for a two hour period at 120 to 125C and about 2 mm ~g until carbon-dioxide evolution has ce~sed. The product is re- -covered as a light brown solid (9.6 gms) that has a flow point of from 64 to 66C. Analysis of the product confirms the str~ucture of a Class J additive wherein Rl, R2, R3 and R4 are each . .
4 perfluoroisopropoxy-perfluorobutyl, M2, M3, M4, M5, M6 and M7 are each hydrogen, 21, Z2' Z6 and Z7 are each ethyl, Z3 and 25 are each -(CH2)3 and Z4 is -(CH2)6 ~
Example 3. Preparation of the_tetramethylated 1,6-hexamethylenediamide of 1j7-Bis(4-perfluoroisopropoxy-perfluorobutyryl)-1,4,7-triazaheptane monoglutaramide.
One gram of the product obtained in Example 2 is dissolved in 10 mlO of dry acetone. Potassium carbonate (0.35 gms) and di-methyl sulfate (0.19 ml.) are added and the reaction mixture is heated at reflux temperature (approximately 56C) for a period of four hours. After this period of time, the reaction mixture is cooled to room temperature and filtered and acetone is removed by flash evaporation at 100C and 1 mm Hg. Analysis by NMR indicates the presence of four methyl groups per molecule. The methyl groups are found to be randomly attached to amide linkages, displacing 2/3 of the hydrogens which comprise the M2, M3, M4, M5, M6 and M7 groups in the product of Example 2.

~¢~

Example 4. Preparation of the methyl ester of 1,7-Bis(4-perfluoroisopropoxy-perfluorobutyryl)-. . . ".,,. _ . , _ _ . . .
1,4,7-triazaheptane monoglutaramide.
_ To a dry reactor containing 18.8 gms. of 1,7-bis(4-per-fluoroisopropoxy-perfluorobutyryl)-1,4,7-triazaheptane monoglu-taramide is slowly added 8 ml. of trifluoroacetic anhydride. The reaction mixture is stirred at room temperature for a period of two hours and then is heated to a temperature of 40C which is maintained for an additional hour. A light-colored viscous li~uid is formed which is then allowed to cool to room tempera-ture. Anhydrous methanol (30 mls) is then slowly added, and an exothermic reaction is noted which increases the temperature to 70C. The volatiles are removed by flash evaporation at 50C
and approximately 1 mm Hg pressure, thereby resulting in 19 gms.
of a very light brown viscous product. Infrared analysis of the product reveals the absence of the carboxyl absorption and the presence of a very strong ester band. The product is thus con-firmed to be a Class I additive wherein Rl and R2 are each 4-perfluoroisopropoxyperfluorobut~Yl~2l and Z2 are each -(CH2)2-~
Z3 is -~(CH2)3- and Ml is -OCH3.
Example 5. Preparation of the chlorohydrin of 1,7-Bis(4-perfluoroisopropoxy-perfluorobutryl)-1,4,7-triazaheptane monoglutaramide.

-To a dry 250 ml. flask is added 30 gms. of 1,7-bis-(4-perfluoroisopropoxy-perfluorobutyryl)-1,4,7-triazaheptane monoglutaramide, 30 ml. dimethylformamide, 15 ml~ epichlorohydrin and 0.1 ml. of triethylamine as catalyst. The reaction mixture is heated to a temperature of 60C. for a period of 23 hours.
The reaction is followed by periodically determining the unreacted carboxyl groups by titration of a sample taken from the reaction mixture. The ~z~

volatiles are removed by flash operation employing a temperature of 75C and less than about 1 mm Hg, yielding a product which is a clear, light yellowish brown oil weighing about 35 gms.
~nalysis of the product confirms the structure as being a Class I additive wherein Rl and R2 are each 4-perfluoroisopropoxy-perfluorobutyryl, Zl and Z2 are each-(CH2)2- , Z3 is -CH2)3-, and Ml is -OCH2CH(OH)CH2Cl.
Example 6. Preparation of the chlorohydrin of 1,7-Bis-' (perfluorooctoyl)-1,4,7-triazaheptane monoglutaramide.
Following conventional procedures 1,7~Bis(perfluorooctoyl)-1,4,7-triazaheptane monoglutaramide is produced from an iodide having the formula CF3(CF2)6I. To a 250 ml. dry flask is added 2 gms. of this monoglutaramide precursor, together with 25 ml. of dimethylformamide, 10 ml. of epichlorohydrin and 0~08 ml.
triethylamine as catalyst. The reaction mixture is heated to a temperature of 60C. for a period of 24.5 hours, with the reaction mixture being periodically analyzed for carboxyl concentration. ~-At the end of the above period, the volatile components are removed by flash evaporation employing a temperature of 75C and a pressure of 1 mm Hg. The product which is obtained is an off-white solid and is found to comprise 24.5 gms. of a Class I additive wherein Rl and R~ are each CF3(CF2)6-, Zl and Z2 are each -(CH2)2- Z3 is -CH2)3~ and Ml is -OCH2CH(OH)CH2Cl.
Example 7~ Preparation of the difluoroester-dichloro-_ hydrin of pyromellitic acid.
,~, . -In a 3 liter reactor, 1,535 gms. of 4-perfluoro-isopropoxy-perfluorobutyl iodide is mixed with 25 gms. of benzoyl peroxide~ The system is thoroughly purged with ethylene to remove oxygen, and the reaction mixture is heated to about 80C. in an oil bath, at which temperature there is an exotherm to about 105C.

The reaction is continued for a period of 24 hours and the quantity ~1~23~

of ethylene above the reaction mixture is maintained at an excess over that required to react with the iodide starting material.
At the end of the above period, the reaction mixture is cooled to C and an additional 5 gms of benzoyl peroxide is added. The reaction is then continued at 80~C (in the absence of oxygen) in an ethylene atmosphere for an additional 36 hours to complete the conversion, as determined by gas chromatography. The product is flashed from the benzoic acid by-product and 1,317 gms of pure product are recovered by fractionation through an 18 inch spinning band column operating at a temperature of from 62 to 64C and about ; 9 mm Hg pressure. The product is found to be the partially fluor inated iodide, 6-perfluoroisopropoxy~ 2,2-tetrahydroperfluoro-hexyliodide.
The partially fluorinated iodide (269 gms) is then added dropwise with continuous stirring over a period of 1.5 hours to 300 ml. of 20~ by weight oleum at a temperature of from 60 to 70C.
The reaction mixture is then heated to a temperature of 100C.
Eor one hour to complete the reaction. The reaction mixture is then cooled and the excess of SO3 therein is quenched by slowly addlng 75 gms. of ice with continuous stirring~ so as to maintain the temperature of the mixture below about 100 C. After the SO3 is quenched, as is indicated by the absence of an exotherm on the addition of ice, the resulting mixture is hydrolyzed ~y the slow addition of 500 ml. of cold water. Hydrolysis is completed by heating to a temperature of 100to 110C for three hours. After cooling to room temperature the product is extracted with 500 parts by volume of ethyl ether and the ether solution is washed in se-quence with several 500 ml. portions of water, a 10% by weight aqueous sodium sulfite solution, water, a 2~ by weight aqueous sodium carbonate solution and two portions of water. The ether solution is then dried over magnesium sulfate and substantially all ~2~

the ether i5 removed by flash evaporation at 25C. The crudeproduct (160 parts) upon subsequent analysis by gas chromato~
graphy is found to comprise about 90% by weight of a partially fluorinated alcohol, 6-perfluoroisopropoxy-1,1,2,2-tetrahydro-perfluorohexanol, with the principal contaminant being the unreacted iodide. The product is purified by fractionating through an 18 inch spinning column, thereby producing 111 gms. of the pure alcohol.
Into a dry flask is added 52 gms. of pyromellltic an-hyride, 200 gms. of the above alcohol, and 30 ml. of dry dimethyl-formamide. The reactor is vented through a drierite tube and the reaction mixture is then heated to temperature of 60C. with continuous stirring for a period of 24 hours. The course of the reaction is followed by the disappearance of the anhydride carbonyl (about 5.5 microns) on an infrared spectrometer. Following the conclusion of the above period of time, 200 ml. of ice and an equal amount of water are added to the reaction mixture, to cause crystallization of the product. This mixture is then filtered and the filtered sollds thus obtained dried in a vacuum oven overnight at a temperature of 70C and one mm Hg pressure. The product ~250.5 gms.) is a white solid melting at from 130 - 140C. Titra-tion with an alcoholic KOH indicates 1.88 mmoles COOH/gram (theoret-ical = 1.86 mm/gram). The product is a 50:50 mixture of an isomeric intermediate having the formula corresponding to the additives of Class G wherein E1 is -CO2CH2CH2(CF2)40CF(CF3)2 and E2 is -COOH.
The interrnediate obtained from the previous step (30.7 gms.) is then added to a dry flask, together with 8.9 ml. of epichlorohydrin, 40 ml. of dry acetonikrile and 0.22 ml. of pyridine. The reaction mixture is heated to 65C. wi-th continuous stirring for a period of 2~

30 hours. ~he ~our~e o~ the re~ction ~ ~ollowed by titration of carboxyl ~nd groupR with an ~lcoholic solution of ba~e. At the ~onclusion of the ~bo~o perio~ of ti~, the reaction nlxture i~ fo~nd to compri8e t~o l~ght brown liquld phases with a ~all a~ount of un-i~solved 801id. ~he vol~tile~ Are then re~oved by flosh evapora-tlon ~t 80C ~nd 1 ~m ~9 pre~8ure and ~ viBcou8 prod~ct ~o~-pri~in~ 34 g~s. of 11qu1d i8 recovered. The ~tructure of the de-~lred difluoroesterdlchlorohydrin add$ti~e of Class G is confirmed, that ~8~ a~ deflned aboYe for the i~ter~ediate and E2 i8 10 -C02C~2C~ ) ca2cl .
~he-fc~lowin~ difluoroe~ter di~hlorohydrin pyromellitates ~re prep~red in ~ o~mil~r ~nner ~ploying the indicated p~rti~lly 1uorinat~d ~lcohol~: ~
Partially Floorinated ~ Cla~ ~ Additive Al~ohol ~ ~:CO C~ CH~OH)CH Cl ~:~
2~ 2 - 2 _ 2 - ;~

tl1 ~CF3j2CFOCF2CF2C~12C~320 ~ o2cE~2c}~2cF2cF2ocF(cF3~2 ~ 2 ) CF3 ( CF2 ) 5C~2C~2 a~l CO2C132C~32 ( CF2 ) 5CP3 ( 3 ) ~F3 ~ CP2 ) 7CE12CB2 1~1 n --C~2C~2C~2 ~ CF2 ) 75~F3 20 ~4) CF3~CF2~ 2C~(O~)c~3 ~ ~3 02C~C~;! ( C~F2 ) 7CF3 ~5) c~3~cF2)sc~2~H(o~cH3* CB3 CO2C~R ~CH3~ C~2 (CP2) 5C 3 E3ample 8.

Pollowing the procedure of 8~ample 7, an isomer~c difluoro-: ~ster lntermediate i~ obt~lned whloh ~omprises a compound correspondins ~ n~ hii~~D;a procedur~ di~closed in ~o-pendinq application of FL
Mare~ ~nd B. Oxenrider entitled ~Proce~s for Preparing Partially ~a1D9enated Alcohols , 6eri~1 No. 256,124 filed ~une 30, 1976.
- 57 - .

~L~C2~

to Class G additives wherein El is -CO2CH2CH2CF2CF2OCF(CF3)2 and E2 is -CO2H. To 30 ml. of dry acetonitrile is added 25 gms. of the foregoing difluoroester intermediate for dissolution of the inter-mediate. Bromohydrin (9.7 ml.) is then added and the reaction mix-ture heated to 60C with the addition of 0.22 ml. of pyridine as catalyst. At the conclusion of 16 hours, titration indicates that the reaction is complete. After flash evaporation is employed to remove the volatiles, 32.6 gms. of product are recovered, with the structure of the product determined by infrared analysis as compris-ing 50:50 mixtures of Class G isomers wherein El is as definedabove for the difluoroester starting material and E2 is -C02CH2CI~OHCH2Br-2xample 9. Preparation of the epoxide of 1,7-bis(perfluoro-octoyl)-1,4,7-triazaheptane.
To 10 parts of 1,7-bis(perfluorooctoyl)-1,4,7-triaza-heptane obtained by conventional methods is added 50 ml. of isopropanol and an aqueous solution containing 0.5 parts sodium ~ -hydroxidein five parts by volume of water. The reaction mixture is cooled to from 0 to 5C in an ice-water bath~ Carbon disulfide (0~7 ml.) is slowly added with continued stirring and the reaction mixture allowed to warm to room temperature. The reaction mixture is then stirred at room temperature for 18 hours, producing a ; hazy, pale yellow solution with a small amount of undissolved solids. The solution is filtered and used directly in the next step without purification.
The reaction mixture from thePreVius step is added over a 15 minute period to a solution containing 25 ml. isopropanol and 25 ml. of epichlorohydrin and is allowed to react for one hour at room temperature and then for two hours at 50C. After cooling to room temperature the mixture is filtered, and the filtrate is treated by flash evaporation to remove the volatile 2.~

solvents. The product (11.4 gms.) thereby obtained is ound to meltat approximately 125 to 135C. The structure is confirmed by subse-quent analysis to comprise a Class I~ additive wherein Rl and R2 are each -(CF2)6CF3, Zl and Z2 are each -(CH2)2- and ~' is -CH2C~-CH2.

Example 10. Following the procedure of Example 9 a Class K
additive wherein Rl and R2 are each 4-perfluoroisopropoxyper-fluorobutyryl, Zl and Z2 are each -(CH2)2- ~ and M' is -CH2C -CH2 O
is obtained employing 1,7-bis(4-perfluoroisopropoxy-perfluorobutyryl)-1,4,7-triazaheptane as starting material.
Example 11. Preparation of the difluoroesterchlorohydrin of trimellitic acid. - -To 30 ml. of dry acetone is added 34.3 gms. of the difluoroester of trimellitic acid and 6.43 ml. of epichlorohydrin.
The reaction is catalyzed by 0.2 ml. of trlethylamine. The reaction mixture is allowed to react at from 50 to 55C for 42 hours, ~ ~
after which period the solvents are removed by flash evaporation ~ -and 34O7 gms. is recovered. Analysis of the product shows the structure as comprising 50:50 mixture of isomers of Class H wherain -DlRl is 4-perfluoroisopropoxy-3,3,4,4-tetrafluorobutyl, and -R'2 is ~CH2CH(OH)CH2Cl.
The difluoroester of trimellitic acid employed as start-ing material comprises a 50:50 mixture of isomeric intermediates having the formula of Class H additives wherein -DlRl is 4-perfluoroisopropoxy-3,3,4,4-tetrafluorobutyl, and R'2 is -COOH, and may be produced by reacting a suitable fluorinated alcohol with 4-chlorocarbonyl phthalic anhydride in the presence of a base.

~z~

Example 12~ Preparation of the difluoroesterdichloro-hydrin pyromellitate of 1,1,1,2,3,3-hexahydroperfluoroundecan 2-ol.
To a dry reactor is added 24 gms. of the partially fluorinated alcohol, 1,1,1,2,3,3-hexahydroperfluoroundecan-2-ol, together with 5.45 gms. sublimed pyromellitic anhydride and 25 ml. dry dimethyformamide. With continuous stirring,they are re-acted at a temperature of 43C for about 22 hours. An aliquot of the yellow reaction mixture is titrated with alcoholic KOH
It is determined that the aliquot contains 0.928 meq/gram carboxyl groups (0.934 meq/gram Eor the diester theoretically). This indicates the reaction is complete. An aliquot is dissolved in ethyl ether, extracted with water and the product recovered by flashing off the ether. Analysis of the product confirms the structure as comprising a 50:50 mixture of isomeric intermediates having the formula corresponding to ves wherein El CO2 lRl in which D1Rl is -CH(CH3)CH2(CF2~7CF3 and E2 To the reaction residue obtained as above is added about 12.8 gms. of epichlorohydrin and 0.15 gm. of triethylamine as catalyst. The mixture is reacted at 60C, with the extent of re-action determined by titration of epoxide groups using hydrobromic acid in acetic acid to a crystal violet end point. The reaction is completed after about 5.8 hours. The product is recovered by water washing and then drying the extracted residue in a vacuum oven at room temperature and 1 mm Hg. The yellow, slightly tacky product (27.2 gms-,) is recovered and is determined by analysis to comprise a 50:50 mixture of the Class G isomeric additives wherein ~1 is ~CO2DlRl in which -DlRl is -CH(CH3)CH2(CF2)7CF3, and E2 is CO2CH2CH(OH)CH2Cl-Example 13. Preparation of Class A Additive No. 5.
___ ___ _ Thionyl chloride (300 ml) is added to methyl potassium 3~

terephthalate (100 g, 0.458 mole) over a period of 20 minutes.
The mixture is then refluxed 1/2 hour. Excess thionyl chloride is distilled off in vacuum, and ether (200 ml) is added to the residue. The insoluble portion is filtered off and the ether evaP-orated, yielding 90.2 g, (0.455 mole, 99.3%) of methyl 4-chloro-carbonyl benzoate, m~p. 48-50, ir: 1780 cm 1 and 1710 cm 1 (~ C=0).
Part of the chloride (11.2 g, 0.0565 mole) is treated ~;
with a solution of 4-perfluoroisopropoxy-3,3,4,4 -tetrafluorobutanol (20 g. 0.0607 mole) and pyridine (3 g, 0.038 mole) in dioxane (60 ml).
After 2 hours, the mixture is poured on ice. A common isolation procedure yields 26.3 g (0.0534 mole, 94.5~) of the desired Class A additive #5, m.p. 38-39, ir: 1725 cm 1 (~ C=0), 1100 cm 1, 990 cm 1, 730 cm 1 (C-F), 877 cm 1 (~ C-H for p-substituted benzene ring); ~ -nmr: ~ 8.1 (4H,s),a4.7 (2H,~ 3.97 (3H,s),~2.65 (2H,t of t); or C16H11FllO5 (492.25) Calc: 39.04 %C,~2.257 %H, 42.46 %F, Found:
39.00 %C, 2.21 %H, 42.6 %F.
Example 14. Preparation of bis(4 perfluoroisopropoxy .
3,3,4,4-tetrafluorobutyl) terephthalate (Additive No. 10) ~
~ .. ~ ............................................... ~
To a solution of terephthaloyl chloride (203 g, 1 mole) in benzene (1000 ml),~a mixture of 4-perfluoroisopropoxy-3,3,4,4-tetrafluorobutanol (660 g, 2 moles) and pyridine (160 g, 2 moles) is added during half an hour. The mixture is warmed by the reaction heat to reflux and reflux is continued one hour by external heating.
The precipitate of pyridinium hydrochloride is then filtered off, and the solvent from the filtrate is evaporated in vacuum yielding the desired Class A additive, bis ( 4-perfluoroiso-propoxy-3,3,4,4-tetrafluorobutyl) terephthalate (748.8 g, 99.2~), m.p. 45-57;
nmr~ 8. 0 (4H,s),~ 4.6 (4H,t),~ 2.6 (4H, t of t). For C22H12O6F22 (790 3) Calc: 33.43 %C, 1.53 %H, 52.89 %F;
Found: 33.28 %C, 1.53 %H, 53.8 %F.

: - . - .
:, ' ' .

~Z3~g~

Example 15. Preparation of Class A Additive No. 9.
_ _ ____ _ ___ _ __ A solution of KOH (25.6 g, 0.456 mole) in perfluoroiso-propoxy-3,3,4,4-tetrafluorobutanol (300 ml) is added to an eficiently stirred solultion of bis(4-perfluoroisopropoxy-3,3,4,4-tetrafluorobutyl) terephthalate (398.1 g, 0.504 mole).
When the temperature decreases to -34~, ether,^(500 ml) is added in order to facilitate stirring. The mixture is refluxed 6 hours. The precipitated~potassium salt is-then filtered off, washed by ether and dried in vacuum oven at 60~-/0.~2 mm~Hg. There is isolated 207-.8 g (80~) of an intermediate salt. For al5~18O5FllK (5~16.3~ Calc: 34.89 ~C,~1.56 ~H,~60.48 %F; Found:
34.51 %C, 1.53 %H, 60.4 ~%F. i~
Distillation of the filtrate in vacuum yields a liquid ., .
and a residue (90 g) which crystallizes on standing. The residue is mixed wi~h ether and~the insoluble part is filtered off, affording an additional 0~5 g of the salt. The ether filtrate is evaporated in vacuumj and the residue is crystallized from methanol.
The starting ester 187 g, 20%), m.p. 45-57 is recovered.
The potassium salt (218~g) is ground and dispersed in dry ether (400 ml). To the suspension, cooled by a water bath, a solution of dry HCl (16.5 g) in ether (120 ml) is added. The mix-ture is refluxed during the addition. It is washed with water until pH 7 is reached and then dried over MgSO4. Evaporation of ;
ether yields mono(4-perfluoroisopropoxy-3,3,4,4-tetraEluorobutyl terephthalate (200 g, 99%), m.p. 155-6; ir: 1680 and 1720 cm 1 (~ CO), 1100-1200 cm , 990 cm (C-F), 800 cm (C-H p-substitution); nmr ~8.2 (4H,s),~4.67 (2H,t),~2.62 (2H, t of t); For C15HgO5Pll (478.2) Calc: 37.67 ~C, 1.90 %H, 43.7 %F, 2.09 meq. CO2H/g; Found: 37.96 %C, 1.89 %H, 42.9 %F, 2.10 meq. CO2H/g.

~ Z~4~

A mixture of the above monoester (12.8 g, 0.0268 mole) and 1 ml 2N Et3N in DMF is dissolved in 15 ml of DMF. Air is then evacuated from the vessel and the vessel is pressurized (1.5 atm.) by ethylene oxide (EO). After 48 hours at 50 the theoretical amount of EO is consumed, and the reaction mixture is analyzed.
Potentiometric titration shows 9.2% of the starting carboxyl concen-tration. The mixture is poured into water and the organic layer is dissolved in ether, with the ether layer being washed with 3% HCl, water, 10% Na2CO3, again washed with water, and then dried over ~ ~-MgSO4. The volatile portions are evaporated in vacuum leaving behind 10.54 g (75.5~) of the desired Class A terephthalic ester additive ~9 wherein n=0, DlRl is 4-perfluoroisopropoxy-3,3,4,4 tetrafluorobutyl and L is -~H2CH2OH:; ir: 3400 cm (~OH), 1720 ~; cm 1 (~C=0), 1100 cm 1, 990 cm 1, 730 cm 1 (C-P); 877 cm ~`
(~C-H, p-subst. benzene ring); nmr:3 &.15 (4a~s) ~ ~ 4.6~4H,m);
3.85-4.4 (lH,m);~ 3.8(2H,d),~a3~.27(2H,s~broad)~ 2.6(2H,t of t);
For C17H13PllO6 (522.3) Calc: 39.;09 %C,~2.51 %H; Pound~
38.77 %C, 2.55 %H.
~ _ A Additive No. 6 :
Mono-1-(4-perfluoroisopropoxy-3,3,4,4-tetrafluorobutanyl) -terephthalate produced as in Example 15 t10.0 g, 0.0209 molej is reacted with epichlorohydrin (9.67 g, 0.1045 mole) in acetonitrile (20 ml). The reactlon, catalyzed by triethylamlne (0.2 ml?, is -followed by potentiometric titration of the monoester. After 48 hours, the esterification is completed The solvent and excess of epichlorohydrin is distilled off in vacuum, and the chloro-hydrin ester thus produced (8 g, 0.014 mole) is dissolved in acetonitrile (20 ml), and 50% NaOH (1.07 g, 0.13 rnole) is added.
The resulting mixture is stirred one hour at room temperature, and then dried over MgSO4. The salts are filtered off and the solvent is evaporated leaving the desired Class A additive (7.45 g) nmr:

j - ~ , ~2.~

~8.15 (4H,s)~4.65 (4H,t & d), ~3.9-4.4 (lH,m),c)3.75(2H,d) ~3.3(2H,s) a 2.6(2H,t of t).
Example_17. Preparation of Class B Additive No. 11 A mixture of phthalic anhydride powder (29.6 g, 0.2 mole) and 4-perfluoroisopropoxy-3,3,4,4-tetrafluorobutanol (66 g, 0.2 mole) is heated 10 hours at 110-120. The crude product is poured into a solution of Na2CO3 (24 g) in water (2 l~)o The resulting solution is filtered, washed with benzene and acidified. The acidified solution is extracted with chloroform. The organic layer is washed twice with water and dried over MgSO4. Evaporation of chloroform in vacuum yields 111.7 g (96.5%) of the mono ester:
mono(4-Perfluoroisopropoxy-3,3,4,4-tetrafluorobutyl) phthalate: ;
m.p. 64-68. Crystallization from n-heptane affords 85.2 g (88.2~) of the pure; m.p. 67-68, nmr:~l2.3 (lH,s), a 7.5-8.2 (4H,m), a4.65~2H,t), 3 2.6(2H,t of~t). Evaporation of solvent from the mother liquid results in 12.2g of an oil which crystallizes on standing. The crystals are found to be a mixture of the monoester and bis(4-perfluoroisopropoxy-3,3,4,4,-tetraEluorobutyl)phthalate.
For C15HgO5Fll (478.2) Calc~ 37.67%C, 1.90% H, 43.7~F, 2.09 meq. of 20 CO2H/g. Found: 37~23%C, 2.09%H, 45.8%F, 1.98 meq. Co2H/g.
A mixture of the monoester: mono(4-perfluoroisopropoxy-3,3,4,4-tetrafluorobutyl) phthalate (20 g, 0.0419 mole), and thionyl chloride is stirred two days at room temperature. The excess of thionyl chloride is evaporated in vacuum and a solution of diethylene glycol (2.12 g, 0.02 mole) in pyridine (20 ml) is added. The resulting solution is stirred four hours at room temperature, and is then poured on ice; the organic layer is dissolved in ether. The ether layer is next washed with water, diluted HCl and a solution of sodium carbonate. The ether layer is then dried over MgSO4. Evaporation of the volatile portions yields 19.5 g (95.2~) of an oily product comprising the desired Class B phthalic ester additive No 11 wherein n is zero, t is 2,Z is -(CH2)~ Y is oxygen, and DlRl is 4-perfluoroisopropoxy-3,3,4,4-tetrafluorobutyl; nmr:~ 7.2 - 7.8 (8H,m)~ 4.5(8H,5), a3.7(4H,t),~ 2.5(4H,m).

Acid chloride is prepared from the monoester produced in Example 17 (60 g, 0.125 mole) and thionyl chloride (80 ml) as in the preceeding Example, and is then treated with a solution of glycerine (5.50 g, 0.0598 mole) and pyridine (10 ml) in dioxane (80 ml). After two hours of stirring at room temperature the reaction mixture is worked up as in Example 17 giving 61.0 g (100%) of the desired Class B phthalic ester additive No. 12; nmr:
~ 7.7 (8H,m)~ 6.0 (lH,s);a 4.7(8H,t);~ 4.0(1H,m),~ 2.~(4H,m);
For C33H22F22Oll ~1012.5) Calc: 39.14 ~C, 2.19 ~%Hj 41.3 %F; ~;
sap. no. 222~ Found: 38.26 ~C, 1.72 %H;;41.1 %F, sap. no. 217. ~ `
B Additive No. 13 Acid chloride prepared from the~monoester of Example 17 (20, 0.0~19 mole) and thionyl chlorlde (40 ml) IS miYed :.
with a solution of 2,2-dimethyl-5,5-bis~hydroxymethyl)-1,3-20 dioxane (3.69 g, 0.021 mole) in pyridine (20 ml)O After 3 hours of stirring at room temperature, the mixture is poured on ice.
The workup procedure described in Example 17 yields 21.2 g of an oil. The oil is dissolved in acetone (200 ml) and treated with 12% HCl (20 ml). This mixture is efficiently s~irred for 5 minutes and is then allowed to stand 2 hours at room temperature. Acetone is evaporated in vacuum and the organic layer is dissolved in ether. The ether layer is then washed with water and a solution of Na2CO3. After drying, the solvent is evaporated in vacuum yielding the desired Class B phthalic 30 ester additive No. 13, nmr:~ 7.5 (8H,m),~ 4.25 (8H,m),a 3.65 .
' ~
.

z~

(6H,m),~ 2.5 (4H,m).
~ ~ = ~
A mixture of thionyl chloride (80 ml) and the mono ester of Example 17 (60 g, 0.126 mole) is heated 3 hours to 80, at which point the heating is stopped and the mixture stirred over-night. Thionyl chloride is then distilled off in vacuum, causing crystals of phthalic anhydride to appear. The product is dissolved in n-hexane and the crystals (1.1 g) are filtered off. The solvent is then evaporated and the acid chloride formed is dissolved in dioxane (80 ml). This solution is then treated with a solution of pentaerythritol (4.27 g, 0.0314 mole) in pyridine (60 ml), and the resulting mixture heated 15 hours at 80. Most of the pyridine and - dioxane is then evaporated in vacuum, and the residue is poured into water. The organic layer is dissolved in ether, and the ; ester layer is extracted with diluted HCl (1:1~, water, Na2CO3 solution, and dried over MgSO4. Evaporation of ether in vacuum gives 59.1 g (95.2 ~) of oil which crystalliæed on standing; nmr: ~ -(H2578) 3 7.5 (16~,m),~ 4O5(16H,t),a 2.4(8H,m), yielding the desired Class B phthalic ester additive No. 15.
In an alternative procedure, a mixture of the mono-ester of Example 17, pentaerythritol (1.42 g, 0.0104 mole) and trifluoro-acetic anhydride (20 ml) is stirred one hour at room temperature.
The excess of trifluoroacetic anhydride and acid is distilled off in vacuum, and the residue is dissolved in benzene and then washed with 10% NaOH solution. The product obtained (21.5 g, 100%) has analogous ir and nmr spectra as the product prepared by the fir~t method;nmr: ~7.7 (16H,m), ~4.7 (16H,t), ~2.6 (8H,m).

34~

.
A mixture of 8-perfluoroisopropoxy-1,1,2,2-tetrahydroper-fluorooctanol (20 g, 0.03% mole) and phthalic anhydride (5.6 g, 0~0378 mole) is heated 20 hours at 110. The crude product is crystallized from benzene yielding 20.9 9 of the pure product, m.p. 67-69, 1.46 meq. of Co2H/g theory 1.475 meq. of CO2H/g), ir 2500-3300 cm (~OH and CH), 1740 cm , 1680 cm (~C=O), 990 - cm (C-F); nmr:~ 11.8(1H,S3,37.4-8.2 (4H,m),3 4.7(2H,t) ~2.7 (2H,t of t).
A mixture of this mono-ester (19.2 g, 0.0283 mole), pentaerythritol (0.89 g, 0.0655 mole), and trifluoroacetic anhydride (20 ml) is stirred 3 hours at 30~ Employing isolation ; procedure described in Example 20 yields 14.09 g (77.5~) of the desired Class B phthalic ester, nmr: ~ 7.6(16H,m),a4.65(16H,t), 2.6(8~, t of t), unreacted CH2OH groups~ 3.8(~2H).

A mixture of potassium benzyl terephthalate ~19.5 g, 0.0665 mole), ~prepared from dlbenzyl terephthalate and KOH ln benzyl aloohol) and thionyl chloride (60 ml) is stirred and refluxed 2 hours. The excess of thionyl chloride is evaporated in vacuum, and the residue extracted with ether. The undissolved precipitate of KCl is filtered off under N2. Evaporation of ether yields 16.3 g (89.2%) of a chloride intermediate. -~
A solution of 8-perfluoroisopropoxy-1,1,2,2-tetrahydro-perfluorooctanol (28 9, 0.044 mole) and pyridine (3.5 g 0.0445 mole) in dioxane (30 ml) is added to a solution of the acid chloride inter-mediate (12.2 g, 0.044 mole) in dioxane (30 ml). When the exothermic reaction ceases, the mixture is refluxed 2 hours and then poured on ice. The resulting crystals are recovered by filtration, washed with water and dried in vacuum. The crystals are found to comprise crude benzyl(8-perfluoroisopropoxy-.
,:, '; ' :

r-~
~23~

1,1,2,2-tetrahydroperfluorooctyl) terephthalate (44.21 g).
A solution of this terephthalate ester in dioxane (200 ml) is hydrogenated at room temperature and 30 psi of H2 over 3 g of 5~ Pd on alumina. In 20 minutes 1.1 liter of H2 is consumed (theory 1.0 1.). The reaction is continued one hour longer, but no more H2 is consumed. The resulting crystals are ; dissolved in refluxing dioxane and the catalyst is filtered off.
The volume of dioxane is then reduced to 100 ml by distillation and the ester, mono (8-perfluoroisopropoxy-1,1,2,2-tetrahydroperfluoro-10 octyl) terephthalate (26.3 g, 88.2% yield on the alcohol), crystal-lizes out; m.p. 177-8, ir: 1680 and 1710 cm (~CO) 1100-1200 cm 985 cm (C-F); nmr:a 8.0(4H,s),~ 4.53 (2 H,t),a 2.53 (2H,t of t);
1.47 meq. CO2H/g (theory 1.475 meq. CO2H/g).
A mixture of this ester (15.0 g, 0.0221 mole) and thionyl chloride (60 ml) is refluxed 3 hoursO The excess of ~hionyl chloride is evaporated, and the residue is treated with a solution of pentaerythritol (0.75 g, 0.0055 mole) in pyridine (30 ml). The resulting mixture is heated 15 hours to 80 (bath). Af~er cooling, it is poured on ice. The crystals are filtered off and aft~r drying, recrystallized from toluene, affording pure Class B
terephthalic ester additive No. 14 (15.7 g, 100~), m.p. 95;
ir: 1740 cm (~C=O), 1100 cm , 995 cm , 730 cm (C-F); nmr:
8.06 (16H,s), a 4.7(16H,m); ~2.7(8H,t of t); For C81H40F76O
(2777) Calc: 35.03 %C, 1045 %H; 52.00 %F; Found: 34.87 ~C, 1.35 %H, 52.10 ~F.

The diacid, HO2C~ ~ CO2CH2CH2O2C ~ C02H, obtained as by the method described in H. Zahn, et al., Makromol. Chemie., 30 29, 50(1959), (4 g, 0.0136 mole) is refluxed 24 hours with thionyl chloride (40 ml). The excess of thionyl chloride is then distilled ~234LgL

off in vacuum. A solution of 4~perfluoroisopropoxy-3,3,4/4-tetra-fluorobutanol (8.5 g, 0.0258 mole) and pyridine (10 ml) in dioxane (60 ml) is added to the distillation residue, and the resulting mixture is heated three hours to 70~ The crude product which precipitates after addition of water is filtered off and washed with water. After drying at 100/1 mmHg, 9.3 g (73.5%) of additive No. 30 is isolated; m.p. 101-102, ir: 1730 cm (~C=O), 1100- ;
1200 cm , 990 cm , 723 cm (C-F); nmr:~ 8.16 (8~1,s),a 4.7 (8H m) ~ 2 6 (4H,t of t); For C32H20F22 10 39.12 ~C, 2.05 %H, Found: 39.26 %C, 1.93 %H.
Example 24. PreParation of Class C Additive No, 31 - The diacid H2C ~ -C2(cH2)22c ~ CO2(CH2)2 2 ~ 2 prepared by the method of H. Zahn et al., supra, (11 g, 0.0184 mole, m.p. 281) is converted into its chloride with thionyl chloride (40 ml) and is then treated with 4-perfluoroisopropoxy 3,3,4,4-tetrafluorobutanol (15 g, 0.045 mole). Following the procedure of Example 23, the crude product is crysta]lized from dioxane and dried at 80/1 mm Hg affording 18.4 g (35%) of additive #31 m.p.
156-159; nmr: ~ 8.16 (12H,s), ~ 4.7 (12H,m), ~ 2.6 (4H, t of t);
For C42H28F22O14 (1174.6) Calc: 42.94 %C, 2.40 %H, 35~58 %F;
Found: 43.47 ~C, 2.32 ~H, 35.7 %F.
Example 25. P ~ of Class D_~di~ , 32:
A mixture of mono-ester as prepared in Example 17 (20 g, 00419 mole), hydroquinone (2.3 g, 0.0209 mole), and tri-fluoroacetic anhydride (20 ml) is stirred 2 hours at room tempera-ture, and the product is isolated following the second procedure described in Example 20. During the extraction with 10% NaOH, NaCl is added in order to break the emulsion~ There is then isolated 20.2 g (90.7%) of the desired additive No. 32a, m.p. 69-71;

.

.. . . .

nmr (3796):~ 7.8 (8H,m),~ 7.4 (4H,s), ~ 4.7 (4Fl,t), ~ 2.6 (4H, t oft).
Exam~le 26. Preparation of Class D Additlve No.35.
a. Preparation of 2-(5-perfluoroisopropoxy-5',5',4',4'-j tetrafluoropentyl) phenol. A mixture of 2-allylphenol (50 g, 0.373 mole), l-iodo-2-perfluoroisopropoxy-perfluoroethane (200 g, 0.483 mole), and azobisisobutyronitrile ~ABN) (2 g) as starting material is refluxed under N2. The formation of an iodide intermediate is followed by gas chromatography. ~fter 6 hours 55.4~ conversion is obtained. Additional ABN (1 g) and iodide (50 g) starting materials are added. In 5 hours the conversion increases to 60% and more ABN
(1 g) is added. The conversion to the product improves to 71.5% in 16 hours, and to 79% in another 4 hours (85 hours total reaction time) after addition of additional iodide (3.0 g) and ABN (1 g) starting materials. The distillation of the reaction mixture yields the desired iodide intermediate, b.p. 125/2 mm Hg - 145/4 mm Hg (133.5 g, 72%).
The iodide intermediate (133.5 g, 0.246 mole) is mixed with zinc (100 g) and ethanol (200 ml), and the mixture is heated to 80, and dry ~Cl is introduced. When all the zinc disappears (8 hours) the mixture is cooled and poured on ice. The organic layer is extracted by ehter, and the ether layer is washed by i~
water and dried over MgSO4- Distillation yields the desired ~2~ 4 ~

phenol; nmr:~ 6~4-7.2 (4H, m)~4.97 (lH, s), ~ 2.65 (2H, t), 1.6-2.4 (4H, m).
b. Preparation of additive No. 35. To a suspension of Na~l (0.9 g, 60~ activity, 0.0225 mole) in dioxane (20 ml) is slowly added 2-(5'-perfluoroisopropoxy-4',4',5',5'-tetrafluoro-pentyl) phenol produced as above (10 y, 0.0238 mole). When evolution o~ ~ ceases, a solution of tetramethylterephthaloyl chloride (3.1 g, 0.0119 mole) in dioxane (50 ml) is added. The resulting mixture is refluxed 24 hours, allowed to cool to room temperature and then poured into water. The precipitate formed is filtered off, washed with water and dried in vacuum yielding 10.9 g ~94.7%) of the desired Class D additive #35; m.p. 131-3~ ir-1750 cm (~ C=O), 1100-1200 cm , 990 cm , 727 cm (C-F);
7~8 cm (~ C-H, o-substituted benzene ring); nmr: a 7.4 (BH, m), a 2.45 (12H, s)~ a 1 7-2.9 (12H, unresolved). For C40H32F22O6 (1027) Calc: 46.75 %C, 40.70 %F. Found: 46.03 %C, 40.00 %F.
D Additive No.~ 35a -~
To prepare 2-(5'-perEluoroiso~propoxy-5',5',4',4'-tetra-fluoropentyloxy)phenol, a mixture of 2-allyloxyphenol acetate 20 (46 g, 0.37 mole), the iodide starting material of Example 26 (140 g, 0.338 mole) and ABN heated 3 days at 80 under N2. Lower boiling materials are removed by distillation. The residue (the ~;
iodide intermediate, 80 g, 57%) is treated with a solution of KOH
(40 g) in methanol (200 ml). An exothermic reaction occurs raising the temperature of the mixture to 50 even with an external cooling . ,; :' ." .

~ -71-r--234~L

by cold water. After 24 hours the mixture is neutralized with diluted HCl, and the organic layer is extracted with ether. The ether layer is washed by a solution of NaHCO3 and dried over MgSO4. Distillation on a spinning band column results in the pure phenol (b.p. 78-80/0.4 mm Hg, 33.6 g.) (GC analysis); ir: 3550 cm (~ OH), 1690 cm (C=C) 1500, 1~10 cm (~ C-H), 1100-1200 cm 1, 990 cm 1, 723 cm 1 (C-F) 745 cm (a C-H), (a benzene ring substituted in ortho posikion.
Employing the procedure of Example 26, the desired additive NOr 35 is prepared from the 2-(5'-perfluoroisopropoxy-

5',5',5',5'-tetrafluoropentyloxy)phenol produced above (12.5 g, 0.0287 mole), NaH (1.1 g, 60~ activity, 0.0275 mole) and tetra-methylterephthaloyl chloride (3.4 g, 0.0131 mole). The crude pro-duct (14.3 g, 100%) is crystallized from n-heptane; affording 12.3 g (88.5%) of the desired Class D addit~lve No. 35a, m.p. 163-5, ir:
1740 cm (~ CO), 1100-1200 cm , 9BS~cm , 723~cm (C-F) 750 cm (~ C-H, ortho-substituted benzene ring); nmr:
~ 7.2 (8H, m),~ 4.2 (H, t) ~ 2.4 (12H, 5) ,~ 1.8-2.3 (8H,m);
20 For C40H32F22O8 ~1059) Calc: 45.37 ~C, 39.48 %F; Found:
45.46 %C, 40.00 %F.

The partially fluorinated phenol, 2-(5'-perfluoroiso-propoxy-5',5',4',4'-tetrafluoropentyl)phenol prepared as in Example 26 (10 g, 0.0238 mole) is reacted with sodium methoxide (1 3 g) in dioxane (40 ml). To this solution is added RI (3 g) and a solution of p-bis(chloromethyl) benzene (2.07 g, 0.0118 mole) in dioxane (20 ml). The mixture is skirred and refluxed for 24 hours, and is then cooled and poured on water. The crystals , 2;3'~L

formed are filtered off and recrystallized from ethanol, yielding 3.4 g of crystals, m.p. 63-64. Ethanol is evaporated and the residue is analyzed; ir shows a strong OH peak; nmr a 7.4 (4H, s),~ 6.6-7.3 (8~r m),a 5.05 (1.7H, s),a 4.9 (l.lH, broad), ~ 4.53 (2.1H, s),~ 2.7 (4H, m),~ 1.6-2.5 (8~, m). The residue is mixed with KI (3.8 g), K2co3 (3.2 g) and acetone (60 ml), and the resulting mixture is stirred and refluxed 48 hours. After this period, the mixture is cooled and poured on water, and the crude product (6.3 g) is recovered by filtration, washed with water and dried. Recrystallization from ethanol yields 5~1 g of the desired additive No. 41, m.p. 63-64. The total yield is 8.5 g (76%); nmr: ~-7.47 (4H, s),~ 6.8-7.3 (8H, m), a 5.12 (4H, s) ,a 2.78 (4H, t), 1-7-2-5 (8H, m); For C36H28F2~O4 (942.6) Calc: 45.86 %C, 2.99 ~H, 44.34 %F; Found: 45.95 %C, 3.2 %H, 45.0 %F.
D Additive No 40c aO Preparation of 4-(5'-perfluoroiisopropoxy-5',5',4',4'-tetrafluoropentoxy)phenol. A mixture of allyl phenyl ether (100 9, 0.747 mole), the iodide starting ma~erial of Example 26 (350 g, 0.845 mole) and AsN (1 g) is heated three days at 80 under N2.
20 Distillation is performed to recover unreacted iodide (250 g, 0.604 ~~
mole) and allyl phenyl ether (61.0 g, 0.45% mole 60%). Only 0.241 ~ `
mole of the iodide is consumed, giving 32.3% conversion. The distil-lation residue is treated with a solution of KOH (30 g, 0.535 mole) ` in methanol (300 ml), and the resulting mixture is heated 2 hours at 50 and allowed to stand overnight at room temperature. Most of the methanol is then evaporated in vacuum and the residue mixed with 200 ml of water. The aqueous mixture is extracted three times with ether. The combined ether layers are washed with water and dried over MgSO4. Distillation gives 93 g (92% yield based on 30 consumed starting iodide) of 5-perfluoroisopropoxy-4,4,5,5-tetra-fluoro-2-pentenyl phenyl ether; b.p. 67-78/0.2 mm Hg, ir: 2850 3~L4 3030 cm 1 (~C-H), 1670 cm (~C=C), 1490 cm and 1600 cm (~CH), 1100-1200 cm , 985 cm , 722 cm (C-F), 750 cm 687 cm 1, (~C-H monosubstituted benzene ring).
The solution of the above product in methanol (100 ml) is hydrogenated for 3 days at room temperature and atmospheric pressure using 5% Pt on alumina (1.5 g) as a catalyst; 5350 ml of ~2 (theory 5410 ml) is absorbed. The catalyst is filtered off and the filtrate distilled giving 5-perfluoroisopropoxy-4,4,5,5-tetràfluoropen~y~ phenyl ether (85-4 g, 91. 5%) b.p. 68-77/0.1 mm Hg; ir does not show any absorption at 1670 cm 1.
Acetic anhydride (20 g, 0~2 mole) is added to a reflux-ing mixture of AlC13 (67 g, 0.5 mole), 5-perfluoroisopropoxy-4,4,5,5-tetrafluoropentyl phenyl ether (85 g, 0.2 mole)~ and carbon disulf~ide (100 ml). The resulting mixture is stirred and refluxed 2 hours. Most of the carbon disulfide is then distilled off and the residue is poured onto a mixture of ice and ~ICl. The organic material is extracted twice with ether. The ether layers are then combined, washed with water, 10% NaOH and twice with water.
After drying the ether is distilled off in vacuum giving a ketonic 20 intermediate (60 g, 65~) m.p. 47-48; ir: 2B50-3030 cm (~C-H), 1680 cm (~C=O), 1500 cm (~C-H), 1600 cm ,1100-1200 cm 1, 985 cm , 723 cm (C-F), 833 cm-l (~C-H, p-substituted benzene ; ring). A solution of this intermediate (i59 g, 0.127 mole) and m-chloroperbenzoic acid (35 g, 0.2 mole) in chloroform (300 ml) is refluxed 20 hours. After cooling, water is added and the mixture is treated with NaHCO3. The chloroform layer is then extracted with water and dried over MgSO4. The solvent is distilled off in vacuum yielding 60 g of the crude acetate intermediate; ir shows loss of ~C=O at 1680 cm 1 and presence of a new ~ C=O
30 peak at 1760 cm 1.
A solution of the acetate intermediate (60 g, 0.12 mole) 3;Z3~

.a ~o~ ~209, 0.357 ~ole) ~n laethanol t300 Il~l) iB alloldcd to re~ct r~ per~t~re o~e~night, ~ollowed by evaporatlon of ~ost of 1~erlt. ~he r~$due 1B ~ e~ ~/lth water an~ n~utral~zed by te~ IICl. A co~on i~ol~tion procedure yîeldfi the de~ired ~4stla~1~y ~l~t>rln~t~d phenol t3C.59, 69.7~ 3350 c~ C-B~, g~00-304~ C-I~) 1605 cm ~ 2md 1505 ~ C-~) 1100-1200 cm 1, 97~5 ~ 1~ '~20 ;1 ~C-r), 825 cm 1 ~C-B~ ub~t~tuteD benz~ne xtl3re o this phenol (109, 0~023 ~ol~ bis(chloro-Wl ~ tlbyii benzene l2-0 9, O~ olel, X2C03 ~3.17 gl, ~ad ~ 3.~1 9) ton~ (10;~ luxed 24 Iou~ e~rj~st~lliYa'c~n yields-3.1 ~ s~ ad t)le a~ired class D ad~itiL~e 2~o. ~Oc~ .2 9, ~3~3~ rp~ 1~0-122~ rl~ 7.~ Elt~ 6.9 (811,81, ~ 5.0 ~Ui sj 2~3 97 (U~,t~ 1.8-2.7 ~8EI,~); For C3~ 2B~2206 t ~4.373; 1, 2.90~ ~S Pound: ~4.68~ C, 3.00~ B.
~}~3 ~ ~ Additi~re 11~2 The ~os~o-ester produced in Ex~ple 17 ~10 ~, 0.0206 ~ole) c~ed ~tb thioFIyl chlor~de ~30 ~ a~ desc~ibed in Exa~ple 20. Tlbs r~ulti~g e8ter l:~lori~e ~ tre~tea ~lth ~ ~olution c~f - .
ao tl~et~yluDIr~e (3.04 9, 0.043 ~ole) 11- chloro~o~DI 6tO ~1) at -20~.
~e ~l~turë ~ the~ ~lowly ~r~ed to roo~ temper~ture. APter ~5 ~In~to~ ~at~r ~as ~ded, ~n~ the c~u~e proauct (10.0 g~ 1~
tecry~tall~e~ ~o~ ~-hept~ne7 ylel~ng puse ~aait~ve ~o. ~2. ~.p.
5~-S~-t ~r~a 7.1-~.0 l4~ .4~ (2~ 2.~-3.7 t6~, ~"~80l~e~ 6~* )- ~or C19~1 : ~2.97~ ~t.3-40~ ~ Founa: 42.~5~ C, 3.57~ ~, 33.0% F~

~onotlO-per~luoroisopropoxy-1,1,2,2~tetr~hydroper1uoro-40~yl) pbth~late ~ pr~p~red ro~ pe~f1uorol~opropoxy-1,1,2,2-tet~ahydroperfluoso~ecanol t20 9, 0.0324 ~ole~ and phthal10 ~nhydr~de l~.8 g, 0.324 ~ole) ~ ~escribed ~or the ~ono-ester .

~ ~2~

of e~ample 17. ~he crude e~es 1~ crystallized ~rom ben~ene, ~ielding 21.8 9 of the de~red mono-ester, ~.p. 85-8B; ir:
~500-3300 c~ ~ ~nd C~), 1740 c~ 1, 1680 c~ 1 t~C-0), 1100-1200 c~ 990 c~ 1 (C-F); For C21~9O~p23 ~77B.3) Calc: 32.~1~ C, 1016% 8~ ~.285 oeqO Co2~q; Found: 32.33% C, 1.25~ n, i.29 ~eq.

8~ploy~ng tbe pro~dure of ~x~ple 17, the ~bove ~ono-~-ter ~12.2 9, 0.0245 ~ole) 1~ ~on~erted into acld ohloride by a rea~t~on ul~h thionyl chloride. The ~c~d chlor~de i~ ~hen reacte~
10 ~lth ~iethylamine ~3.6 g, 0.049 mole) in benz~ne ~30 ~1), yielding 13 ~ ~99~ o~ the d~ir~d additi~e No. ~5a; ~r5~7.9 9 ~,g), .62 ¦a~,t),~ 3.4 ~4H, broad~,~ 2.6 (2~,t of t~,~l.2 t6~,t).

~x~ le 32 Pre aration of Class F hdditive No. 46 _ _ Dur~ng a 1/2 bour perlod ~-perfluoroisopropoxy-3~3,4,~-tetr~fluos~butyl iodide ~410 g, 0.892 ~ole) i5 ~dded to 8 solu-tion o~ ~o~lu~ ~yanide ~50 g, 1.22 ~ole) in D~SO (200 ~1). The t~e ~8 0tirred 30 ~nute~ and allowe~ to stand oYernight.
~he reaction ~ixture 1~ then poured ~nto water and extracted t~ree ti~es ~ith ethe~. ~he co~bined ether l~yers a~e washed with Yater ~n~ ~r~ed o~er Mg5O4~ Di~t~llation ~ves 8109 9 (19.7%) o~ the ~t~rting lodide and 4-per~luoroisopropoxy-3,3,~,4-tetra-~l~oropento n~trile, b.p. 91-9~-/30 ~m ~9 ~223.5 g, 70.8~).
~ he n~trlle ~150 9, 0.~2 ~ole) ~s dissolved in ~o~tic ~s~a t200 ~1) and hydrogenated in a ~ 1. autocla~e ~ 900 psi o~er PtO2 II.S 9). ~he reaction ~ixture ~s neutr~lized by 30 ~0~, and the water lay~r $s extracted three times with ether.
~he ~ther 13yers are then oombined, washed w1th water and dried ~ver NsSO4. Distill~tion yields three ~r~otions: the f~rst ~ra~tlon b.p. 61~/27 ~ Ng 146.6 g, 30.9~) ~s pure 5-perfluoro-i, 23~g isopropoxy 4,4,5,5-tetrafluoropentyl amine, nmr:~2.94 (2H,t) ~1.5-2.6 (4H,m), ~1.09 (2H,s). The second fraction is bis(5-perfluoroisopropoxy-4,4,5,5-tetraEluoropentyl3 amine, b~p. ~6-90/0.2 mm Hg (73.4 g, 50.5%), nmr:~ 2.74 (4H,t), ~1.5-2.5 ~8H,m),a0.77 (lH,s). The third fraction b.p. 121-123~/0.2 mm Hg (9.0 g, 6.2~) contains only tris(5-perfluoroisop~opoxy-4,4,5,5-tetrafluoropentyl) amine; ir: no. N-H peak; nmr:
~2.5 (6H,t),~ 1~5-2.2 (12H,m).
From the above bispentyl secondary amine (15 g, 0.0224 mole), acid chloride having the formula ClOC ~ O ~ COCl (3.31 g, 0.0112 mole~, and triethyl amine (2.5 g, 0.025 mole) in acetone (60 ml~ the desired amide additive No. 46 is obtained in a quantitative yield as an oil; nmr:~7.5 (8H,g),~ 3.5 (8H~t) r ;
~1.6-2.5 (16H,m).

Example 33. Preparation of Class G Additives ~64 ~
~ .
A mixture of pyromellitic anhydride (B.40 g, 0.0385 mole) and the secondary amine HN[(CH2)3CF2CF2OCF(CF3)2]2 (50.63 g, 0.0757 mole) and DMF (8 ml) is stirred and heated one hour to 90. After cooling, the reaction mixture i5 dissolved in ether (200 ml) and the ether solution is washed by 10% HCl and water and dried over MgSO~. The volatile portions are evaporated in vacuum yielding 58.3 g (99~ of an amide intermediate, m.p. 60-95~, 1.302 meq. of CO2H/g (theory 1.305 meq. -CO2H/g); ir: 1740 cm 1 (~C=O
in -CO2H), 1630 cm (~ C=O in ~ CON), 1100-1200 cm , 995 cm 1, 727 cm (C-F); nmr:~ 11.2 (2H, broad),~ 8.7 (lH, s), ~7.4 (lH, s),~3.0-4.0 ( H, m), ~ 1.5-2.5 ~16HI m) ; For C42H28F4~N2Olo (1556.7) Calc: 32.40 ~C, 1.81 %H, 53.70 ~F; Found: 32.01 %C, 1.83 %H, 53.50 %F.
A mixture of the amide intermediate (20.1 g, 0.0128 mole), triethyl amine (1.5 mmole), and DMF 11 ml) is reacted with 34~L

ethylene oxide yielding 21.2 g (100%) of a 50:50 mixture of isomers of Class G wherein El and E2 are as defined for additive No.
64; ir: 3430 cm (~OH), 1750 cm and 1660 cm (~C=O)~
1100-1200 cm , 995 cm (C-F); titration shows no -CO2H; For C46H36F44N2Ol2 (1648.8) Calc: 33.59 %C, 2.21 %H; Found:
33.92 %C~ 2.30 %H.

TREI~TMENT OD . I~I~OJ~ 1 1'111:1 I~R
In the following experiments coating of fabricated cloth samples with an additive from an organic solution of the additive is effected either by dipping the cloth into a dioxane solution containing the indica~ed quantity of additive or by boiling the cloth for the indicated period of time in a dioxane solution of the additive~ The cloth is then removed and squeezed between a ; metal plate and aluminum foil to achieve a constant pick-up of solution. The samples are air dried and subsequently annealed in either a static or forced air oven at a temperature ranging from lQ0 to 250C. The concentration of the additive is adjusted according to the pick-up of dioxane by the different types of clothes to assure that the treated cloth contains the desired amount of fluorine.
Aqueous dispersions of additives are prepared by ad-mi~ing the selected quantit~ of additive with water and an appro-priate dispersing agent. This admixture is agitated on a blender ~ ;
to create the dispersion, and then poured into a plastic bottle filled with ceramic rings. The bottle is attached to an ultra-sonic vibra-tor and shaken for a period of 24 hours. The disper-sion thereby obtained is then filtered in order to remove any larger particles remaining therein.
Emulsions of additives are prepared by dissolving the additive in the appropriate organic solvent, which may be either a solvent which is miscible with water, such as acetone, or one which is immiscible with water, such as methyl salicylate 3~
for polyethylene terephthalate cloth samples. The organic solvent containiny the dissolved additive is then poured into a solution of hexadecyl trimethyl ammonium bromide and Igepal in water and rapidly agitated to effect emulsification.
Dye baths containing additives of the present invention are prepared by dissolviny a dye paste in an aqueous solution con-taininy from about 3 to 5% by weight of a 10~ NaH2PO4 solution as a buffer. The resultiny dye solution is heated to a temperature of 60C and a carrier solvent is added. If an additive emulsion is used instead of an addi~ive dispersion, no carrier solvent is added since the carrier solvent will already be present in the emulsion.
The heating and stirring is continuous until boiling is reached; the additive dispersion or additive emulsion is then added. The mixture ~ is stirred for a few minutes more and stirring is then ceased and ; the desired cloth sample is dipped in this bath. Boiling is con- -tinued for approximately 1 to 2 additional hours. At the conclusion of the above period of time, the cloth is removed, thoroughly rinsed with water, and air dried or ironed. The cloth is then annealed at temperatures ranging from 100 to 250C. for a period of from 3 to ~ minutes in a static or circulating air oven.
Surface energy screening tests of the additives are ;~
performed by preparing a mono-layer of the additive on a glass plate and measuring the surface energy of the additive monolayer.
A solution containing 1 weight percent of the additive in ace one is prepared and employed to wet a glass plate. The wetted plate is air dried and then annealed in an oven at a temperature of 100C for a period of 5 minutes. The contact angle, alpha, of an organic liquid drop is measured by means of a telescopic goniometer. The surface energy is read from a plot of cosine alpha vs~ surface energy of the liquid used for the measurement, after extrapolation to cosine alpha = 1. The following liquids *Trade Mark 79_ ~'f~'~ .

,3~4 are chosen: n-nonane (22.9 dynes/cm), 2--methyl-heptane (18.1 dynes/
cm) and 2,3-dimethylbutane (16.9 dynes/cm).
The surface energies of fibers is determined by using the apparatus described by W. C. Jones and N. C. Porter in J. Chem.
Phys. 64, 519 (1960). However, the procedure is modified in such a way such that the fiber is passed through a droplet of the test liquid supported about a luire loop. Movement of the fiber back and forth throkugh the droplet produces an advancing or receding contact angle when the test liquid does not wet the fiber surface.
Test liquids are selected for use in decreasing order of surface tension within the range of from 18 to 53 dynes/cm. The surface energy of the tested fiber is determined to be equivalent to the surface tension of the liquid having the lowest surface tension of test liquids which does not wet the fiber.
Dip-coating of fabric in testing a selected additive is performed by dlpping the fabric sample into a solution of an addi-tive in a solvent at such a concentration that 0.1 to 0.2~ by weight of fluorine is contained on the fabric. The fabric is then air dried and annealed at 180C for a period of 3 minutes in a circulating air -~
oven. Oil repellency of the fabric is then measured employing thescale established by the American Association of Textile Chemists and Colorists in its publication "Technical Manual of the AATCC", volume 46 [Research Triangle Park, North Carolina)(1970).
In the examples to follow, a home laundry (HL) cycle is defined to be one washing in a heavy duty, 6-cycle automatic washer ~Sears Kenmore) using a 12 minute hot (105F) wash cycle with one cup of Dash detergent (manufactured by Proctor & Gamble). The washing is done at a constant load of 3 pounds and with a double rinse.
Samples are dried for 30 minutes in an automatic dryer (Sears Ken-more) at a temperature of from 80 to 85C.

A dry-cleaning (DC) cycle is defined to be the test estab-*Trade Mark 80-~ ~c, 3g~ :

lished by the American Association of Textile Colorists and Chemistsas AATCC Test No. 86~1970. The sample is put without detergent in a Launder-Ometer containing 150 ml of perchloroethylene and 100 steel balls having a diameter of 1/4 inch. The sample is washed for a period of 10 minutes at a temperature of 27C. In a second step, the solvent is then replaced with an equal amount of Stoddart solvent, and the sample is again washed for a period of 10 minutes.
In a third step, the first step wherein the perchloroethylene is employed as solvent, is repeated. The sample is ihen removed, air dried and hand pressed using a damp muslin cloth and an iron having a temperature of between 135 to 150C until dry. Testing of surface properties is then performed. ~ ~
; The oll repellency of the fiber and fabric in the ex- ~ -- amples is defined as the ability of a textile fiber or fabric to resist wetting of oily liquids, and is tested in accordance with the AATCC Test No. 118 1966. Standard test liquids employed are as follows~

SVRFACE
AATCC OIL REPELLENCY COMPOSITION OF T~E TENSION
RATING NUMBER STANDARD TEST LIQUID (Dynes/cm) : . *
1 Nujol 32.8 2 65:35 Nujol: n-hexadecane 31.1 (by volume at 21C) 3 n-hexadecane 28.0 4 n-tetradecane 26.7 n doedecane 25.4 ~ ;

6 n-decane 24.0

7 n-octane 21.8

8 n-heptane 20.0 Drops of the standard test liquids of selected hydrocarbons with varying surface tension are placed on the smooth fabric surface and observed for a period of 30 seconds. The oil repellency is *Trade rlark -81-¢,.~ ' ~' ~234~

then the highest numbered test liquid which does not wet thefabric surface. The higher the oil repellency rating, the better the repellent surface. If the fabric is wetted by Nujol, the rating is 0. In a few cases, the 3M oil repellency rating is usedc This scale employs a range of from 50 in which only Nujol is employed, to 150, in which pure n-heptane i5 employed. The points between 50 and 150 are tested by mixtures of n-heptane and Nujol (mineral oil) in different ratios as shown by the following table:

10 STANDARD LIQUIDS_FOR 3M OIL REPELLENCY TEST
3M Rating ~ n-heptane in mineral oil r _ 150 ~ 100 14t) 90 130 ~0 Q

0 no hold out to mineral oil The water repellency of the fabric is tested by a ~pray test employing the standard set up by AATCC Test No.

22-1967~ The fabric is fixed into a 6 inch hoop attached to a AATCC Spray Tester and the hoop is placed on a stand at an angle of 45 with the horizontal. Water (250 ml) is poured into a funnel and allowed to spray on the sample through a nozzle (having 19 holes, each 0.035 inch in diameter) which is placed 6 inches above the cloth sample. Upon completion of the *Trade Mark -82-, ~ ' ' 3~4 spraying, the hoop of the sample is tapped twice on khe opposite sides of the hoop against a solid object. The rating ranges from 0 to 100 in which a rating of zero is intended to mean complete wetting of the upper and lower surfaces and 100 corres-ponds to no sticking or wetting of the upper or lower surface.
A rating of 70 to lO0 is good, and a rating of 90 to 100 is out-standing. ,~
Soil release tests in the Examples to follow are per-formed in accordance with AATCC Test Method No. 130, employing a standard release rating of from 1 to 5, with a rating of 5 representing complete release of soil and a rating of 1 rep-resenting no release of soil by the tested fabric. ~ -Exam~les 34-42 To determine the thermal stability of the additives of the present invention, thermal gravimetric analysis (TGA) are car-ried out on certain of the additives in order to determine the weight - loss as a function of temperature. The results of these tests are summarized in Table I below:
TABLE I
Surface Ex. Melting Loss of Weight at 280C Energy No. Additive Point C ~ Dynes/cm 34 11oil 6.7 14.7 12oil 14.8 13.0 - 36 13oil 13.6 14~4 37 15oil 14.8 11.7 38 22 63 3.6 15.0 39 21106-lOg 4.8 13.4 1996.7 1.1 14.1 41 16oil 13 23 42 17oil 11.2 24 The additive employed in Ex. No. 40 is tested in an additional thermal gravimetric analysis in which the additive was heated at a rate of 10C per minute under a nitrogen atmosphere~ Substantially no weight loss is observed to occur until a temperature of approximately 310C is reached.
The ability oE additives of the present invention to pack on a surface is determined by measuring the surface energy of a mono-layer of the additives on a glass plate in accordance with the procedures described above. The results of these runs are shown in Table I above. As control, an untreated glass plate is dipped in a solution of dioxane and annealed under similar condi-tions. The untreated control is found to have a surface energy of ~40 dynes per cmO Thus, the additives in Examples 34-42 significantly lowered the observed surface energy.
Examples 43-51 .
Selected additives are coated on polyethylene terephthalate pellets from an ether solution in concentrations of 1~ by weight based on the weight of the polymer. The pellets are dried on a flash evaporator at a bath temperature of 80C and a pressure of 20 l mm Hg, and thence in a vacuum oven at 100C and 0.2 mm Hg for 30 hours. The dried pellets are then extruded into a fiber employing a conventional MPM extruder using a 30-hole 120 mil/hole) spinnerette with a length:diameter ratio of 3.5:1. The extrusion is observed to be performed at a noticeably lower pressure than required for extrusion of pellets of the same material not containing an addi-tive.
The extrudate is quenched by an air stream having a temperature of 16C and the fiber is taken up at a rate of 60 feet per minute on conventional take-up apparatus. ~ conventional spin finish is applied to the fiber, and fibers so obtained are first drawn at a drawing ratio of from 1:4 to 1:5 at a pin temperature .
~23~

of 80C. and a block temperature of 110C. and then drawn at adrawing ratio of 1.25:1 at a pin temperature of 80C and a block temperature of 190C. The surface energy of the undrawn fiber is determined, the results being summarized in Table II below. Samples of the extruded fibers are drawn at a ratio of 1:5 to yield a fiber having a denier of from 10 to 12 per filament. The surface energy of the drawn fibers are determined and are summarized in Table II. Also shown in Table II are results of tests wherein the drawn treated fibers are annealed at a temperature of 150C
for a period of one hour, resulting ln the lowering of surface energy. The water repellency testing is performed upon a sleeve made from a cloth sample in each of the runs indicated.
As a measure of the stability of the additives of the present inventicn in the melt of the polymer during extrusion, the fiber upon extrusion is analy2ecl for the fluorine content~thereof to determine the percent of the original amount of fluorine adcled to the polymer in the form of the additive which remains in the fiber following extrusion. The data thereby obtained, expressed as weight percent of the extruded fiber, is shown in ; 20 Table II.

`" 11(~23~4 TABLE II Annealed Fiber ~150~, 1 hr.) Weight % Surface Ex Fluorine Surface Energy (Dynes/cm) Energy Oil Rep-No. Additive Retained Undrawn Fiber Drawn Fiber Dynes/cm ellency 46 1590 ~18 28 23 6 49 1975 <18 28 23 4 Control - 45 45 45 o Example 52.
A drawn, extruded fiber prepared as in Example 46, employ-ing the Class B phthalic ester additive (No. 15) of that Example, is : tested in accordance with standard methods to determine the strength, elongation and modulus of the fiber and a comparison is made from the data obtained with similar tests performed upon a control fiber to which no additive has been added prior to extrusion. The data thereby obtained are summarized in Table III below:
TABLE III

Intrinsic Tensile :
Viscosity Strength Elongation Modulus Fiber (dclg) (g/denier) (%) (g/denler) Control 0.73 4.277 15.54 128.91 Treated Fiber 0.72 4.624 16.58 139.52 :
As is indicated in Table III, the additive does not affect intrinsic viscosity and results in a higher tensile strength, elongation and modulus when compared with the untreated control fiber.

~1~23g~4 ~

Fiber prepared as in Example 46 is fabricated into sleeves which are annealed at a temperature of 150C for a period of 1 hour.
(a) One sleeve i5 washed and dried repeatedly in home laundry cycles with the oil repellency beiny measured following each laundry cycle. The oil repellency is observed to gradually decrease from the original value of 5 to the unwashed sleeve to a value of 0 after the 4th cycle. The oil repellency value of 5 is found to be restored by either steam ironing, dry ironing and/or by anneal:ing the sleeve at a temperature of 150C for 1 hour.
(b) A dry-cleaning cycle is simulated by placing a -second such sleeve into trichloroethylene for a period of 1 hour at room temperature with continuous stirring. The oil repellency is noted to drop from 5 to 4.
(c) A third sleeve prepared from the treated fiber is subjected to a staining test in which the selected soilant is applied to the sleeve and the tendency of the stain to spread and penetrate the fiber is observed. The results are compared to a stain test performed on a sleeve knitted from untreated fiber. The data obtained shows that the additive prevents spread-ing and penetration of water (hot coffee) and oil-borne stains (corn oil, french dressing and motor oil) into the surface of the sleeve.
Examples 54-62 Thermogravimetric analyses are performed on samples of Class D and F additives to determine their thermal stability, yielding the data set forth in Table IV below. Extruded fibers of polyethylene terephthalate are prepared from a resin mixture containing the desired additives in a concentration of 1~ by weight~ based on the Z3~4 weight of the untreated resin. It is again noted that the pressureneeded for extrusion of the coated samples is lower than that needed for extrusion of polyethylene terephthalate resin to which no such additive has been introduced. The extruded fiber is drawn at a ratio of 1:4 to give a fiber having a per filament denier of from 13 to 14. Both the undrawn and drawn fibers are scoured in at a temperature of 40C for a period of 60 minutes and the surface energies are measured. The results are summarized in Table IV.
An analysis of the treated fibers indicate that in all cases at least 80% of fluorine to the resin in the form of the additives remains in the extruded fibers.

TABLE IV
:
Thermal Stability Surface Energy ~x. Melting at 280C. - Wt. (Dynes/cm) ; No. Additive Point (~C) Loss, ~5 min.Undrawn Drawn 54 38 183 4.0 28 >28 131 3.1 28 5~ 36 164 1.7 28 28 57 39 197.5 1.7 >28 Z0 58 40a 184-185 1,0 >28 2B
5g 41 67 6.g >28 40b 74-75 3.5 >28 28 61 40 120-122 2.1 >28 -62 46 oil 2.9 28 ~8 Examples 63-86.
Dip coating tests are performed on polyethylene tere-phthalate cloth samples (Dacron 54, fine weave, 100 sq. inch samples) to determine the oil repellency imparted to the fiber yielding the data summarized in Table V below. The untreated cloth sample used as control is found to have an oil repellency rating of 0.
*Trade ~lark -88 f~

34~ :

TABLE V
, Ex. Oil No. Additive Melting Point (C) %Fluorine Repellency -63 5 38-39 Q.14 0 16 oil 0.14 4 66 21 oil 0.17 67 12 oil 0.14 1 68 lg 96-97 0.14 6 69 22 oil 0.14 6 17 oil 0.1~ 0 ~; 71 16 oil 0.14 2 ~;~ 72 30 101-102 ~0.18 2 : 73 30 101-102 : 0.
74 3i 156-159 - ~ : ~ 0.15 ~ 2 32 ~9-71 :~ ~ 0.13 1 76 34 94 95 ~ 0.18 6 77 38 182-1~4 : ~ 0:.13 ; 7R 35 131-133 0.16 0 ~20 7g 36 ;163-165 0.16 3g 202-20~ 0.16 0 81 - 40a 184-185 0~15 ~2 41 63- ~ ;0.18 :0 ;~ 83 40b 74-75 0.18 0 84 40 12~-122 ; : 0.18 2 42 54-56 0.13 0 86 45a oil 0.14 0 es 87-89.
To determine the ability of fibers to absorb additives 30 from an a~ueous emulsion, a selected additive is emu~sified at ~ :
a concentration of 0.002 g/ml in an aqueous solution containing 0~002 g/ml Nacconol (a synthetic detergent manufactured by Allied Chemical Corp.) *Trade rqark "

by introduciny the additive to the soap solution with continuousstirring at the boiliny temperature (about 100C) of the solution.
In each run, a 5 sq. inch cloth sample (Dacron 54, fine weave) fabricated from polyethylene terephthalate fiber is immersed in 250 ml. of the boiling solution containing the selected additive for a period of from 1 or 2 hours without the presence in the solution of any carrier solvent. The cloth samples are then carefully rinsed in hot water and annealed for 5 minutes at 180C. Testing of these samples shows a marked improvement in oil. repellency for the treated samples over the control. These data are summar-ized in Table VI.
TABLE VI
Exam~le Additive Boiling Time (hrs.) Oil Repellency 8~ 32 2 3 Control - 1 0 Exam~le 90.
To determine the ability of fibers to absorb the additives 20 of the present invention from an aqueous dispersion employed as a ~ ;
component of a dye bath, dispersions are prepared comprising about 30 weight percent of Marasperse N tmanufactured by American Can Co.) or Tamol (manufactured by Rohm and Haas Co.) as dispersing agent, about 30 weight percent of water, about 20 weight percent of the selected additive from the present invention, from about 5 to 10 * *
weight percent of Sorbitol, Ganax (manufactured by GAF Corporation) *
as humectants and from about 2 to 10 weight percen~ of Igepal (nonionic emulsifying agent manufactured by GAF Corporation) as a composition with synergistic effect. The additive selected for use is additive No. 19. The dispersion is prepared by adding the additive to the selected amounts of other constituents and boiling the aqueous ~' ~ *Trade Mark P23~

solution with contin~ous stirring. Fluorine analysis of a sample of the dispersion thus produced shows i~ to contain 17.6 weight percent additive ~based on fluorine content).
Dye baths having varying concentrations of additive are then prepared by admixing from about 0.007 to 0.05 gram of the aqueous additive dispersion with approximately 50 grams ; of water, about 0.01 gram of dye paste (Polynal Yellow), l ml of 10% aqueous NaH2PO4 solution and from about 0.05 to 0.1 gram of o-phenylphenol type solvent (manufactured under the trademark Carloid by Tanatex) as carrier solvent. A l g.
sample of polyethylene terephthalate fabric (Dacron 54, fine weave) is immersed in the selected dye bath for a period of one hour while boiling the dye bath at a temperature of 100C. At the end of this point, the cloth sample is removed, dried to remove some of the water and then annealed at a temperature of 150 to 180C for a period of 2 minutes. The concentration of addi-tive present on the treated cloth is determined by analysis and is compared to the concentration of additive remaining in the bath following treatment of the cloth. The exhaustion of the additive from the dye bath is found to vary from 70 to 90% by weight of initi~l additive content of dye in the bath. The data thereby . obtained are summarized in Table VII below:

- *Trade ~lark i(~ .

~23~4 TABLE VII

Additive in Additive On Percent Dye Bath(l) Cloth Sample Exhaustion (Wt. ~) (Wt. %) of Additive from Bath .35 0.26 74 0.50 ~.43 8~

0-~4 0.80 95 0.84 0.73 87 1.6 1.1 69 , ............
_ _, ~1) Percentage relative t~ the weight of cloth sample.

Simil~r results are obtained when the above procedure is ; repeated employing the following carrier solvents: the diphenol type solvents Carolid ELFC (manufactured by Tanatex Corporation) * ~ , .
and Charlab ~P-3 (manufactured by Charlotte~Chemical Laboratories), *
respectively; Tanarol, a halogenated benzene solvent manufactured by Tanatex Corporation, and Latyl, an ester amide type solvent manufactured by E. I. du Pont de Nemours & Co~
- :
Exampl e 91 ' In order to determine the~stability of the low energy surfaae developed by absorption of an additive from a additive dispersion followed by annealing, cloth samples of polyethylene terephthalate fiber tDacron 54, fine weave) are~prepared con taining varying amounts of additive, expressed as weight percent fluorine. The additive selected for use is a Class B
terephthalic ester additive No. 15. Each sample is subjected to a number of home laundry cycles, and the oil repellency of the samples is determined following the completion of the desired number of cycles. The data thereby obtained, which are summarized in Table VIII, demonstrate that the oil repellency remains high even ~fter the samples are subjected to as much as 40 home laundry cycles. Following completion of the above tests, the *Trade ~lark -92-.,~ , .
, , 3~4 cloth samples were thoroughly rinsed with hot running water andthen ironed at a temperature of 150C with a standard home iron.
On all the studied samples, the starting oil repellency is essen-tially restored.
TABLE VIII
. ~ . .
Heat Treated Additive Oil Repellency after Indicated Cloth:
Run Content of No. of Home Laundry Cycles Oil No. ~ 0 10 20 30 40 Repellency 1 0.04-0.06 10~ 90 2 0.125 110 80 50 -- -- ~0 3 0.21 100 70 ~ 90 4 0.3~ 100 9~ go S 0.42 100 70 ~ 90 6 1.05 100 80 g0 80 70 ~~0 To determine the durabillty of the low energy sur~face ko abrasion, an aqueous dispersion is prepared as in Example 90 con-taining Class-B additive No. 19. The dispersion is added in an~

:
amount to provide a dye/additive bath similar to that used~in Example 90. A one g. sample of cloth fabricated from polyethylene *
terephthalate fiber (Dacron 54, fine weave) is-immersed in the dye/additive bath at a temperature of 100C for a period of one hour, and the cloth subsequently removed and annealed at a tempera- ~-ture of 180C for a period of 2 minutes. The surface durability on abrasion is then measured on a Wyzenbeck apparatus with Satgen abradent cloth under a pressure of 3 pounds and a tension of 4 pounds. The cloth i5 then subjected to a number of abrasion cycles, with khe oil repellency being determined horizontally. The data summarized in Table IX, indicates extremely good durability of khe low energy surface of the treated sample.

*Trade rlark ~,,, ., ' r.
' ~2~^44 TABI,B IX
No. of~ a~~s .
O 110 ~ ' _3.
:~
A polyethylene cloth sample prepared as in Example 92 and containing 0.13 weight percent fluorine, is stained, to~
gether with a controlled sample with oil and water-borne stains, yielding results summarized in Table IX. The results indicated , that treatment of the sample cloth according to the process of the present invention prevents both the water and oil-borne : ~ :
stains from spreading, while bad spreading is observed to occur upon stainlng of the controlled sample. It is~observed that most of the staining material can be~removed from the treated~sample by blotting with a paper towel, and that water-borne stalns, ~-~
e.g. hot coffee, can be easily washed out by one home laundry cycle.
It is also observed that the used motor oil stain is not removed from the stained controlled sample even after 25 home laundry cycles, whereas 3 home laundry cycles are sufficient to remove these stains from treated cloth samples.

TABLE X
STAINING l~ST

Laundry Stain Control Sample Treated Sample ~ No. _ Spread Penetr. St ~ read Penetr.
; O l-corn oil bad bad complete slight no no 2-french dressing bad bad complete slight no no 3-used motor oil bad bad complete very na no slight 4-hot coffee bad bad complete trace no no 1 1 bad slight 2 very slight no 3 very bad trace 4 no no , ... .
2 1 very sli~ht trace 2 no ~ no 3 bad ~ trace . ~ .
~ .. ~
3 1 no ~ no 3 bad no A 100 square inch sample clo h fabricated from polyethylene terephthalate fiber (either Dacron 54, coarse weave or~Dacron 56,~
double knit) is treated with a dioxane solution containing dissolved therein an additive of the present invention. The additive that is employed is the Class B terephthalic ester derivative No. I5. The cloth is contacted with the dioxane solution at a temperature of 25C
for a sufficient period of time to incorporate the desired quantity of additive into the cloth. The cloth is then removed from the solution and annealed at a temperature of about 185C. for about 2-1/2 minutes, and then tested to determine the initial oil repel-lency, abrasion resistance and water repellency ratings. The sample *Trade Mark 95~

'' .,~' ' "~,. . .
'''''' ~z~

la tben ~ubjected to a nu~ber of ho~e l~undry cycle~, wlth the o~l r~pell~ncy, nbr~sion ~e~istanoe ~nd w~ter repellency rotings being ~niD dete~ined ~ter 5 ~nd 15 ~ ~ycles. Test resul~s ~re ~et o~tb in T~ble XI. The Eesul~6 ~how the cloth ~amples treated ~it~. th~ ~dditive o~ the present invention to ~ompare favorably 1~ o~l repellency, ~bc~sion re~i~tance ~nd water r~pellency r~tings ** **
~o the co~erc~lly ~v~ ble 8cotchgar~ and ~C-321 1uoroc~rbon eo~pounas.
- ~S XI , **
Aæter 5 A~te~ 15 ~niti~1 Iaundry Cycles Laundry Cycles Fl~ kcn ~ ~R~ 20 ~ Oil A~r. ~2u : ' Additive: D.05 5 2 75 S ~ 70 3 1 ~0 ~.10 6 ~ 40 5 5 75 4 ~ ~0 0.~5 5 5 . - 5 5 - 5 3 ** eCl~NGUC~ 0.1 6 ~ 80 5 3 ~0 4 3 8** E~ 321~ 0.2 6 C . 80 5 ~ 80 5 4 80 ~!L~
Addi~ive: 0.~5 . 5 ~ 75 3 2 60 2 0 50

9.10 6 ~ ~0 5 ~ 79 3 1 60 ** ~CI~ON~P 0,1 ~ 5 ~5 5 ~ 80 4 2 80 ** ~C 321~ 0.2 6 5 90 S ~ B0 ~ a 80 ep. - oll repellen~y r~ ; Abr. RRP. ~ abrasi~n resistance rating; and ~2 rep. - A~er repellency rat~.
e a¢e o~n~rcial product~ produoed by 3M Co.; cloth ~amples are prepared the ~anufacturer's recxn~Y~ed pr~ures.
Cloth ~amples of Dacron 54, coar~e ~eave, ~re ~epared n~ ~n exa~ple 9~ to incorp~rate therein the ~elected qu~ntlty of the desired ~luotocarbon compound. Each ~ample ls then ,, * * Trademark ! - 9 6-~ . /.

23~L~

subjec-ted to a soil release test employing salad oil and a soiling mixture. The results thereby obtained are summarized in Table XII.

TABLE XII

Soil Release Rating Ist HL 2n~-HL -Fluorocarbon Soiling Soiling __ %F Mixture* Salad Oil Mixture Salad Oil _._ . , .
Untreated -Control 2.5 2.5 3.5 3.5 Class B
Additive 0.05 2.5 2.5 3 3 ~10 0.10 2 2 2 2 0.25 2 2 ~ 2 Scotchgard 0.1 2 2 2.5 2.5 ** ~ .
FC 321 0~2 2 2 2.5 2.5 *Soiling Mixture: 3 PartS Mustard 2 Parts Ketchup 2 Parts Mayonnaise 1 Part Salad Oil 1 Part Used Motor Oil ~ ~
Examples 96-100. To determine the effect which annealing conditions have upon cloth treated with additives of the present **
invention, 100 square inch cloth samples (Dacron, 54, coarse and fine weave) fabricated from polyethylene terephthalate fiber is dipped for a period of 2 minutes into 200 ml of a dioxane/
additive solution having a temperature of 25C. and containing sufficient additive to provide the desired quantity of additive in the cloth samples. Each sample is air dried and annealed in a static oven at a temperature of from; about 180 to 230C.
Each sample i5 then analyzed for additive content, and tested to determine the initial oil repellency, water repellency and abrasion resistance. Similar tests are made after 1 home laundry cycle. Each Example employs 2 runs to insure accurate results. Data obtained are set forth in Table XIII:

**Trade Mark ~g7-a~

.

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, .. . .

.
.
. .

INT=initial testing values; 1 HI.=after one home laundry cycle; oil=oil repellency rating; Abr=abrasion resistance ratings;
and H2O=water repellancy rating~ Additives in ~xample 96 to 100:-50:50 mixt~re of isomers of Class G wherein El and E2 are as de-fined for additive No. 49.

~ 2~
The annealed sample cloth prepared in Example 100 con-taining 0.4~ by weight fluorine is subjected to a series of home laundry cycles with oil repellency and abrasion resistance ratings being determined initially and after each additional five HL cycles The data obtained are set forth in Table XIV.
Table XIV

No. of Oil Abr.

Examples 102-103.
Staining tests are performed on double knit cloth samples (~acron 56) fabricated from polyethylene terephthalate fibers after incorporation of the selected additive into the cloth fiber by dip-coating the cloth into a dioxane solution of the additive. The tests, summarized in Table XV, show all stains to have been removed by home laundering from stained samples containing additives of the present invention, compared to the badly stained control sample which could not be adequately cleaned by home laundering.

~ *Trade Mark _gg_ ~
.

3~4 ~ample e~mple 102~ . 103~
Control A~ter l~t BL Cycle 1 Corn Oil none none bad 2 ~r~nch Dres~ing none none b~d 3 ~ed M~tor Oil er~ce 'tr~ce ~ad 4 ~ot C~fee none none a After ~
1 Corn Oil none ~one ~a 2 Prench Dres31ng ~one ~one very ~light 3 ~sed ~oto~ Oil trace tr~ce very b~d 14 ~ ~ot Co~oe ~one ~one none 1 Corn O~l none :none very slight 2 ~ed Notor Oil ~one ; non~ :bad 02: 50:50 m~%tu~e of~ iomer~ of Cl~ G:additives ~here~n E ~nd S ~re as defined ~or additive ~o. 51;2f,lbric contains 0.16 ~eight peroent ~dditive~
. 103: 50:50 mixture~of isomer5 of Cla6s G addi~ives wherein E1 and E are a8 defined for ~d~tive go. 49;2fabric contains 0.17 weight percent additive.
. ~x~pl~s 104-120.
Dip coat~ng test~ are performed on 100 squ~re lnch poly-. etbylene terephthalate ~l~th ~mples tD~ ~on 54, ~ine Ye~ve), ~ving the re~ult~ 2et forth in Table XV~. The untreated control ~a~ple i~ ound to ~ve ~n oil ~epellency r~tlng of 0.

:
' ** Trademark ' ' .
.

-~30- .

.

' . . ':

~2~

Table XVI
Ex. No. Additive* %F Oil Repellency -- ~ , 105 ~ 0.12 o 106 ~9 O.lS 4 107 71 0.15 S
108 72 0.15 6 109 73 0.15 6 110 75 0.15 7 111 49 0.10 112 49(1)0.10 4 113 49(2)0.10 1 : . ~
114 51 0.1~ 4 - ` 115 53 0.1~ 5 '~ ' 116 50a 0.15 4 . 117 . 55 0.12 6 i :`
118 54 0.lS 6:
l 113 57 0 . 15 6 ~ . !
120 64 0.10 4 ;
~ 20 I:
: ~r~ Z~Dlbb~Vr77~lndicated, Class G and H additives are 50:50 molar mixture~ of their respective isomers.
(1) meta-isomer only (2) para isomer only ., .

, . :

. . .

. .

-101- :

Examples 121-127.
To determine the stability of additives of Class G and H polyethylene terephthalate cloth samples (Dacron 54, fine weave are either dip-coated in an additive solution or boiled for one hour in a dioxane solution containing the additive in such a concentration that the desired additive concentration in the cloth is obtained. The samples are then air dried and annealed in a circulating air oven at the selected temperature for a period of about 5 minutes. Each sample is then subjected to a series of DC or HL cycles and the water and oil repellency ratings of each sample is determined, as summarized in Table XVIII:

~0 *Trade ~lark r ~ .

1~2~49~

o I ' ~ ' ' .
X~ o , , . o o ' ~ ~r o ~
VC~, C, o o I `~` G C~ O

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o 1~~ ~ c, o o o o o O
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1 ~ ~ 0 ~ ~ ~D r- ~ .

. :3 a O ,,~ a I t . ~
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~
PJ h . . ~ ~ . ~, .
E~ ~ o ~ ~ ~ o o o ~ o J- ~ N ~'1 N ~`1 ~ ~I ~ ' Z Z '¢ W

b 3~

Example 12~. .
To determine the effect which annealing at different temperatures in either a forced air or static oven has upon the home laundry stability of the additives of Class G, polyethylene *
terephthalate cloth samples (Dacron 54, fine weave) are dip-coated in an additive/dioxane solution, air-dried and annealed in the selected oven at the desired temperature. The additive employed in each Run is additive No. 49. The water and oil repellency ratings of the tested samples are summarized in Table XIX:

' ~:

.

*Trade Mark ~ :

.

-10~-'.y,'~
g~ f~

~ , , ~1 er , ~3 o , , I
o .~ I
o ", ~.,, o dP~ ~ O
10H m a~
O
æ o ~ ~ o o m ~ o ~ m a) E~ ~ I I

O H

~ ~ O
,~; ~ ~ I ~ I o :o ~ dP O
n~ : er:
O
N I I

Z ~
O O O
o ~:1 0 . ~:

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o ~1 ~ ~ ~11 : ` . ' E-~ O 1 `~

.

--105~

xample 129.
To determine the relative soil release properties of polyethylene terephthalic cloth treated with additives o the present invention and commercially available polymeric fluorocarbon fiber additives, 100 square inch cloth samples of the selected weave are dip-coated with additive solutions, air-dried and annealed at a temperature of 230C in a circulating air oven- The commer-cially available fluorocarbon additives, Zepel D formulated (manu-*
factured by DuPont), Zepel D unformulated (manufactured by DuPont), Scotchgard FC214, FC321 and FC220 (manufactured by 3M) are applied to separate cloth samples of the selected weave by the manufacturer's recommended procedure. Samples are then either stained with a soiling mixture, salad oil or lipstick, followed by several home laundry çleaning cycles. The soiling mixture used comprises (in . ~ , parts by weight): 3 parts mustard, 3 parts catsup, 2 parts mayonnaise, 1 part salad oil and 1 part used motor oil. The stained cloths are measured for soil release after 1 and 2 ~L cycles. Data obtained are set forth in Tables XX-XXIV. The additives employed in the indicated Runs are: Run No. 1 - Untreated control; Runs 2-4 - 50:50 mixture of Class G additives wherein El and E2 are as defined for additives No. 49; Runs 5-? = 50:50 mixture of Glass G
additive isomers wherein El and E2 are defined for additlve No. 51.
Runs B and 9 = Zepel D, formulated; Runs 10 and 11 = Zepel D; Runs 12 --* *
and 13 ~ Scotchgard FC214; Run 14 = Scotchgard FC220; Runs 15 a~d *

~ 16 (Table XXIV) = Scotchgard FC321.
:
.
*Trade Mark ' ~ . ,~ ,;", ~, ~ a ~ .

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C

2~

Table XXII
SOIL RELEASE 0~ SCOURED D~CRON (54) C~)ARSE WEAVE
- ' ' ' ''- , ~ 2 HL C~cles Run Soiling Salad Soiling Salad No %F Mix Oil Mix OilCanments - 3 3 3.5 3.5Stains wicked du~ing washing 2 0.10 2.5 2.5 2.5 2.5 3 0.20 2.5 5 3 5 4 0.40 2.5 5 3 5 0.10 2.5 3 3 3 0 . 20 2 2 2 . 5 2 . 5 7 0.40 2.5 `5 3 5 0 . 10 2 2 2 2 : ~
9 0.20 2 2 2 2 ~ :
1~ 0.10 2.5 3.5 3 3.5 11 0.2~ 2.5 3.5 3 ~ 3.5 ~, :

12 0.10 2.5 3.5 3 3.5 :

13 0.20 2.5 3.5 3 3,5 .
~ 14 0~15 4 5 4.5 5 ~
, ' ' *Trade Mark ,r~
~ }~

~Z3~

Te~le XXIII
SOIL RELEASE ON UNSCOURED DAC~ON (54) COARSE WEAVE

1 HL Cycle 2 HL Cyc1es Run Soiling Salad Soiling Salad ~:
No. %F Mix Oil Mix Oil Co~ments 1 - 3.5 3.5 3.5 3.5 2 0.10 2.5 3.5 2.5 3.5 `: ;
3 0.2~ 2.5 5 ~.5 5 ~ 0.40 2.5 3 2.5 3 0.10 2.5 ~.5 2.5 2.5 ::
9 0.20 2 2 2 2 .
- 10 ~.10 3 3 3 3 (2) :
11 0.20 3 3 3 3 : ~ :
12 0.10 3 3 ~3 3.5 (3) 13. 0.20 3 : 3 3 3.5 ~-

14 0.15 4 ~ 4 4 4.5 icked during staining and washing t2) Stains wicked during washing .
', *Trade Mark ~ ~

. .

, I

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o .~ ~ ~ ~r ~ 'D
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- P:æ
-111- ' ;.
The procedure of Example 99 is repeated with various annealing conditions in either a static oven or a Benz machine.
Samples are subjected to a number of HL cycles or a number of DC
cycles, and oil and water repellency rating are determined before and after laundering. The results are tabulated in Tables XXV-XXIX.

~ C ' r~ r- ~n ~ o Jn, o ~ r~ m ~ r ~r~ ~ ~ o "~ ~ g o ~ u~ u~ ~ n tg~ ~ ~ tn ~v c~ ~ ~n ~ c~ n o u~ r~ ~n q~ZI~' ~ ~ ~ ,~ o ~ ~ ~ ~
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¦ ¦ Df N~

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-117- .

.....

3g~g 131-150.
To determine the stability to additives of the present invention to home laundering, 100 square inch nylon-6 cloth samples are dip-coated with the selected additive solution (employing acetone or isopropanol as solvent). The samples are then air dried and annealed for 0.5 hour at the selected temperature in a circulating air oven. The samples are then subjected to a number of home laundry cycles, with oil repellency of the samples being periodically determined. The data obtained are set forth below in Table XXX:

~ ~ Z349~
CO o ~1 h t~7 , .
I_ ~ m 4~ ~) U~ o ~ ~9 o L~ ~ , ,~
U~ :~1 Q
a ~r '`I ~ E3 ~ a O
O ., o, I o a~
Z
~1 0 ~1 O~:
a~
c> ~~r ~r Ln ~ u~ u~
~rl ~ ~ ~ ~
~U
H OLn ~r Ln ~ ~r o Ln ~ ~ s o ~1 .,1 ~rl h h a c~'l a~~ Ln ~ Ln ~ ~ ~ ~ ~r ~ ~a ~
~ ~ ~3 Ln ~ Ln ~r Ln ~ Ln~r ~9 ~ o o t~ z ~ Ln ~ ~9 ~r LO ~ ~
c) ~aJ o ~D ~O ~ o ~r Ln ~ g Ln ~ D O ~D 1~ 0 ~ ~ ~
~ : ~ x a) Ln ~ ~r Ln ~r ~ Ln ~ ~1--~ ~ t~ ~ o ~
p:; E~ S ,-, - "
~r ~ ~ Ln ~ ~ ~ u~ L~ D ~ Ln U
O o's.~ 3 ~r Ln ~ ~D ~ ~ Lrl r~ o o ~ ~ 9 ~ Ln rl ::
~n er Ln ~ ~ r~ ~ ~ r~ ~ ~ ~1~1~ d~ ~ ~o Ln ~: u~
x :' ~ X ~1~ ~ Ln 1~ 9 ~ i~ ~ ~ Ln ~ r ~ Ln ~ Ln ~ .
~ -~ o ~ ~~ ~n ~ z ~ ~

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H t~~10 '1:1 , _ O ~ ~O
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~: ~3 o Ln = _ -: = ~ - _ Ln ~r Ln _ o C e o:: _ U
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J~ `h C~ U) o ~ m m m m m m m m m ~ m m m ~ 9 au o o 3~ o ~ o U
a) ~ Ln c s a Ln Ln o O O rl rl ~rl ~ ~rl ~5 ~ W W ~~ Ln~
3 . .
~C O O UE4 ~> ro I` o o ~ ~ r--~ ~ o ~ ~7 o ~ ~ ~ ~
.,, Ln Ln Ln Ln Ln Ln Ln ~D--1` CO 1` ~ ~ CO ~ ~--0~ ~7 ~ m ~ O~o ~
U~ .-1 0 ~1 U~

P ~1 ~
. ~ ~ Ln ~ ~ ~ o ~ ~ ~ ~ Ln ~ ~ n o _ _ X O ~ ~ ~ rn ~ ~ ~ rn ~ ~ ~ r er ~ Ln !, , ~ ~23~

Examples 151-152.
Cloth samples fabricated from nylon-6 fiber are dip-coated with a selected additive solution, air dried and annealed or 0.5 hr.
at the desired temperature in a circulating air oven. The samples are then subjected to a number of dry cleaning or home laundry cycles with oil and water repellency of the clo~h samples being periodically de~ermined. The data ob~ained are summarized in Table XXXI below:
Table XXX
Example 151 Example 152 AdditiveNo. 82 No. 59 (wt. %) 0.5 0.5 Anneal Temp. 140 160 ( C) Cloth A A [Table XVI]

No. of Cycles* Oil Water Oil Water Rep. Rep. Rep.Rep.

Initial 8 80 7 100 ~ 7 70 5 100 * Oil Rep. based on DL cycles; Water Rep. based on HL Cycles A = modified nylon 6 taffeta cloth 2~
Exa 153 To sho~ the effect of additive concentration, cloth samples of modified nylon 6 oxford cloth are dip-coated with additive No. 57, air dried and annealed for 0.5 hr. at 155C
in a circulating air oven~ Oil repellency of the samples to a series of HL cycles, yielding the data in Table XXXII.
TabIe XXXII

Run No. 1 2 3 Additive (wt. %) 0.1 0.25 0.5 Oil Repellency after No. of HL Cycles:

4 ~ 6 6 ~ 6 6 g 2 4 4 Example 154.
To determine the effect of annealing temperature on laundry stability, cloth samples of modified nylon 6 oxford cloth are dip-coated with an additive solution, air dried, and annealed at the desired temperature in a circulating air oven Oil repellency of the samples are then determined during a series of HL cycles, as shown in Table XXXIII:

g~

Table XXXIII

Run 1 2 Additive (wt. ~) 0.5 ~.5 Anneal Temp.
(C) 140 155 Oil Rep. after No. of HL
Cycles ~ 6 `
6 ~ 6 6 Additive = No. 57 .
Example 155.
Abra~ion tests are performed on modified nylon 6 oxford cloth samples to determine the stability of additives to abrasion.
The cloth samples are treated by dip-coating in an additive solution, ~.
air-dried and annealed for 0.5 hr. at 150C in a circulating air oven. Data obtained are set forth in Table XXXIV:
Table XXXIV
Oil Repellency Run Additive Initial After Abrasion Additives employed: Run 1 = 50:50 mixture of Class G isomers 3~

wherein El is 4-perflurorisopropoxy-3,3,4,4-tetrafluorobutyl and E2 is -CO2CH2CH(OH)CH2Cl; RUD 2 = same as Run 1 except that El is 6-perfluoroisopropoxy-1,1,2,2-tetrahydroperfluorohexyl; and Run 3 = same as Run 2 except that E2 is -CO2CH(OH)CH2Br.
Example 156.
__ To determine the effect of dyeing on laundry stability of the additives of the present invention, 100 square inch modified nylon 6 oxford cloth samples are fabricated, dip-coated in a liquid medium of the selected additive, air-dried, annealed for 0~5 hr.
at 140C, dyed with an acid blue dye using either a competitive or comparative dyeing technique (bath temperature = 100C). The ; competitive technique involves dyeing cloth samples having different additive concentration together in the same dye bath. The samples compete for the dye. When this technique is employed, the samples ~ ;
containing the higher concentration of additive did not dye to as deep a shade as the lower additive content samples~ In cont~ast, when samples are dyed using the compara~ive (separate bath) tech- ~ -nique, the desired color shade is obtained in each sample. The dye bath used comprises an aqueous solution employing a cloth sample ratio of 40 ml. solution per gram of fabric, which contains 0.5 - weight percent (based on the weight of fabric) Kiton Fast Blue CB-Concentrate (C.I. Acid Blue 45), 0.6 gpl (grams per llter) sodium acetate and 0.5 gpl glacial acetic acid, giving a buffered aqueous solution of pH 4.5 to 5Ø Samples are boiled in the dye bath for one hour, rinsed with water and air dried. Oil repellency tests are made for the dyed samples periodically after a desired number of HL cycles, yielding the data set forth below in Table XXXV:

*Trade Mark 3~4 , ~ABL
aL Cycles O 1 2 3 ~ 5 6 7 8 9 10 11 CompetltiYe DYinq ~;~rF) 0.1 5 5 ~ 2 .25 6 ~ 6 6 6 5 4 ~ 4 ~.5 7 7 ~ ~ 6 6 5 5 Co~parative DYing ~F;~) ' ' 0.1 . 5 5 5 ~ 4 2 0.25 7 7 6 ~ 6 6 5 5 5 ~ 4 0.5 7 7 ~ 6 6 C 6 6 5 5 5 5 ~Additive No. 57 The untreated control ~amp].e dyed ln accordance with th~ competitive technique d~d not int:rea~e in oil repellency after dyeing, ~how~ng that no additi~e migrated ~to:the control fro~ the ~ples ~n the b~th which cont~ined additive.
~
~o ~e~onstrate the.~tabllity of fiber 6ur~nce properties effected by use of ~n additi~eJepo~ide system of the pre~ent lnventioD, a 50:50 ~i~ture o~ the i~o~erio Cl~s G additive No. 51 ~0,1 9) ~nd the trimelliti~ triepoxlde hav~ng the ormula 1 1 R2 CH2CH CH2 ~0.3 9) ~re dissolved in dioxane ~100 ~1~. Tri-n-butyl am~ne ~0.09 9) ifi ~dded to the 301ution as c~t~ly~t. Cloth ~amples ~100 ~q~ in., ~cron 5~) are dip-coated ln this ~o1ut~on, ~ir dried and annealed 5 ~inutes at 160C., pro-viding each sa~ple with 0.14~P. She treated cloths are then t~sted or oil repellency, before and after a ~eries of DC cycles ~Run 1) or ~ cycles ~Run 2) yielding the data set forth in ~able XXXVI below:

*Trademark .~, /,, .

Z34~

:
TABLE XXXVI

Type of Oil Repellency After Indicated No. of Cycles RunLaundry No.Cycles 0 1 2 3 4 5 10 11 18 The first two runs are repeated with the cloth sample being dipped in a dioxane solution of the additive and epoxide, in the absence of an amine as catalyst. No stability on HL and DC is achieved.
Example 158 10Cloth samples of nylon 6 (spun woven, scoured) and nylon 6r6 (oxford cloth, scoured) are dip coated with the selected addi- ~;
tive to provide treated cloth samples having 0.5 weight percent additive incorporated therein. The samples are air dried and annealed at 160C. for 0.5 hour. Following the desired number of HL or DC cycles, the water repellency and oil repellency are determined, giving the data summarlzed in Table XXXVII below~
-:
1~ ~
', -,:

~' T~3LE ~
Additive No. 54 54 57 57 Nylon Cloth Type: 6 6,6 6 6,6 No. of Cycles Cycles Cycles Cycles Cycles Cycles Cycles Cycles Cycles -Z~ 2~ 2- - Oil _20 ~ 2-: 7 ~ 5 - - 4 - 5 5 - 5 Since various changes and modifications may be made in the invention without departing from the spirit thereof, it is intended that all matter contained in the description shall be interpreted as illustrative and not in a limiting sense.

Claims (12)

We claim:
1. Compounds of the formula:

(A) , wherein n is an integer of from zero to 4; L is D2R2, hydrogen or -(CH2)f1(CHOH)f2(CH2)f3OH, wherein f1 and f3 are the same or different and are integers of from 1 to 4 and wherein f2 is either zero or 1, Q is a member selected from the group consisting of methyl, chlorine, bromine, fluorine and iodine; D1 and D2 are divalent radicals independently selected from the group consisting of alkylene of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)p1CH(OH)(CH2)p2O-, -C6H4(CH2)p1-, -C6H4O(CH2)p1-, -C6H4-, and -C6H4O-, wherein p1 and p2 are integers and are independently selected from the group consisting of 1 to 4; and R1, R1' and R2 are independently selected from the group consisting of -(CmF2m+1), -(CmF2-1) and -(CF2)mOX, wherein m is an integer of 2 to 20 and X is selected from the group consisting of perfluorinated alkyl of 1 to 6 carbon atoms;

(B) wherein n, Q, D1 and R1 are as defined above; Z is alkylene of 1 to 4 carbon atoms, and t is an integer and is 2, 3 or 4; Y, when t is 2, is selected from the group consisting of:
(i) >O, (ii) >C(CH2OH)2 (iii) >CH2 (iv) >CH(CH3) Claim 1 continued (v) >C(CH3)2, (vi) , (vii) >CHOH, (viii) -CH2(OCH2CH2)rCH2-, and (ix) -(CH2OCH2O)r-wherein r is an integer of 1 to 10; Y, when t is 3, is -?H or -?OH;
and Y is when t is 4; provided that Z is not -CH2- when Y is oxygen;
(C) wherein q is 1 or 2, Z' is alkylene of 2 to 4 carbon atoms, and n, Q, D1 and R1 are as defined in paragraph (A) above;
(D) wherein A1 and A2 are independently selected from the group consisting of -R2, -OR1, -OD1R1, -D1R1 and -CO2D1R1, wherein n, member selected from the group consisting of:
(i) , (ii) , (iii) , and (iv) Clalm 1 continued wherein Q is a member selected from the group consisting of CH3 and halogen and n' is an integer of from 0 to 4;

(E) wherein B is a member selected from the group consisting of:
(i) (ii) , and (iii) where D3 and D4 are divalent radicals independently selected from the group consisiting of alkylene of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)p1 CH(OH)p2CH2)p2O-, -C6H4O(CH2)p1-, -C6H4-, and -C6H4O-, R3 and R4 are independently selected from the group consisting of -(CmF2m+1)-, -(Cmf2m-1)- and -(CF2)mOx, Zm is alkyl of 1 to 4 carbon atoms, wherein p1, P2, m, D1, D2, R1, R1', R2 and X are as defined in paragraph (A) above, with the proviso that when -D2R2 and -D3R3 are different, then at least one of D2 and D3 must contain at least 3 methylene groups;

(F) wherein R1 and D1 are as defined in paragragh (A) above and Y' is selected from the group consisting of oxygen and alkylene of 1 to 6 carbon atoms;
(G) wherein two E groups are E1, and two E groups are E2, in which E1 is CON(D1R1)2 or -C02D1R1 and E2 is -CO2(CH2)x1(CHOH)x2 CH2Q"
wherein x1 is an integer of 1 to 5, x2 is an integer of 0 to Clalm 1 continued 4, Q" is -OH or halogen and D1 and R1 are as defined in paragraph (A) above, (H) and wherein R2' is selected from the group consisting of -(CH2)x1, hydrogen, -(CH2)x2(CHOH)x2 CH2Q" and -(CH2)(CHOH)CH2OCH2CH(OH)CH2OH, wherein x2 is an integer of 0 or 1 and wherein D1, R1, x1 and Q"
are as defined in paragraph (G) above;
(I) wherein Z1, Z2 and Z3 are the same or different and are alkylene of from 1 to 4 carbon atoms; and M1 is selected from the group consisting of -OZ, -NHZ, OCH2 and -O(CH2)x1(CHOH)x2CH2Q"',wherein Z is alkyl of 1 to 4 carbon atoms, Q"' is -OH, halogen, or hydrogen and wherein x1 and x2, R1 and R2 are as defined in paragraph (G) above, with the proviso that if Q"' is hydrogen, then x1 and x2 are each 1;
(J) wherein M2, M3, M4, M5, M6 and M7 are independently selected from the group consisting of hydrogen and Z, in which Z is alkyl of 1 to 4 carbon atoms; Z1, Z2, Z3, Z4, Z5, Z6 and Z7 are the same or different and are alkylene of from 1 to 4 carbon atoms; and R1, R2, R3 and R4 Claim 1 continued are the same or different and are as defined for the R groups of paragraph (A) above; and (K) wherein M' is selected from the group consisting of and -(CH2)x1(CHOH)x3CH2Q", and Y" is oxygen or sulfur, wherein x1, R1, R2, Z1, Z2 and Q" are as defined in paragraphs (1G) and (1I) and x3 is 0 or 1.
2. A fibrous article having incorporated therein a fiber additive selected from the group consisting of compounds having the formula:

(A) wherein n is an integer of from zero to 4; L is D2R2, hydrogen or -(CH2)f1 (CEO8)f2(CH21)f3OH, wherein f1 and f3 are the same or different and are integers of from 1 to 4 and wherein f2 is either zero or 1;
Q is a member selected from the group consisting of methyl, chlorine, bromine, fluorine and iodine; D1 and D2 are divalent radicals inde-pendently selected from the group consisting of alkylene of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)p1CH(OH)(CH2)p2O-, -C6H4(CH2)p1-, -C6H4O(CH2)p1-, -C6H4-, and -C6H4O-, wherein P1 and P2 are integers and are independently selected from the group consisting of 1 to 4; and R1, R1' and R2 are independently selected from the group consisting of -(CmF2m+1), -(CmF2m-1) and -(CF2)m)OX, wherein m is an integer of 2 to 20 and X is selected from the group consisting of perfluorinated alkyl of 1 to 6 carbon atoms;

Claim 2 continued (B) wherein n, Q, D1 and R1 are as defined in paragraph (2A); Z is alkylene of 1 to 4 carbon atoms; and t is an integer and is 2, 3 or 4; Y, when t is 2, is selected from the group consisting of:
(i) >O, (ii) >C(CH2OH)2 (iii) >CH2 (iv) >CH(CH3) (v) >C(CH3)2, (vi) , (vii) >CHOH, (viii) -CH2(OCH2CH2)rCH2-, and (ix) -(CH2OCH2O)r-wherein r is an integer of 1 to 10; Y, when t is 3, is -?H or -?OH;

and Y is -?- when t is 4; provided that Z is not -CH2- when Y is oxygen;

(C) wherein q is 1 or 2, and Z', n, Q, D1 and R1 are as defined in
1. claim 1(C):
   
   (D) wherein A1 and A2 are independently selected from the group consisting of -R1, -OR1, -OD1R1, -D1R1 and -CO2D1R1, wherein n, D1 and R1 are as defined in paragraph (2A), and T is a member selected from the group consisting of:
   
   ?aim 2 continued (i) (ii) (iii) , and (iv) wherein Q' is a member selected from the group consisting of CH3 and halogen and n' is an integer of from 0 to 4;
   (E) wherein B is a member selected from the group consisting of:
   (i) -CO2D1R1 (ii) , and (iii) -CON(Z")2 where D3 and D4 are divalent radlcals independently selected from the group consisting of alkylene of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)p1CH(OH)(CH2)p2O-, -C6H4O(CH2)p1-, -C6H4-, and C6H4O-, R3 and R4 are independently selected from the group consisting of -(CmF2m+1)-, -(CmF2m-1)- and -(CF2)mOX, Z" is alkyl of 1 to 4 carbon atoms, wherein P1, P2, m, D1, D2, R1, R1', R2 and X are as defined in paragraph (2A), with the proviso that when -D2R2 and -D3R3 are different, then at least one of D2 and D3 must ?laim 2 continued contain at least 3 methylene groups;
   
   (F) wherein R1 and D1 are as defined in paragraph (2A), and Y' is selected from the group consisting of oxygen and alkylene of 1 to 6 carbon atoms;
   
   (G) wherein two E groups are E1, and two E groups are E2, in which E1 is -CON(D1R1)2 or -CO2D1R1 and E2 is -CO2(CH2)x1 (CHOH)x2CH2Q"
   wherein x1 is an integer of 1 to 5, x2 is an integer of 0 to 4, Q"
   is -OH or halogen and D1 and R1 are as defined in paragraph (2A);
   and wherein R2' is selected from the group consisting of , hydrogen, -(CH2)x1(CHOH)x2CH2Q" and -(CH2)(CHOH)CH2OCH2CH(OH)CH2OH, wherein x2 is an integer of 0 or 1 and wherein D1, R1, x1 and Q"
   are as defined in paragraph (2G);
   (I) wherein Z1, Z2 and Z3 are the same or different and are alkylene of from 1 to 4 carbon atoms; and M1 is selected from the group consisting of -OZ, -NHZ, and -O(CH2)1 (CHOH)x2CH2Q, wherein Z is alkyl of 1 to 4 carbon atoms; Q"' is
2. Claim 2 continued -OH, halogen, or hydrogen and wherein x1 and x2, R1 and R2 are as defined in paragraph (2G), with the proviso that if Q"' is hydrogen, then x1 and x2 are each 1;
   (J) wherein M2, M3, M4, M5, M6 and M7 are independently selected from the group consisting of hydrogen and Z, in which Z is alkyl of 1 to 4 carbon atoms; Z1, Z2, Z3, Z4, Z5, Z6 and Z7 are the same or different and are alkylene of from 1 to 4 carbon atoms; and R1, R2, R3 and R4 are the same or different and are as defined for the R
   groups of paragraph (2A);
   (K) wherein M' is selected from the group consisting of and -(CH2)x1(CHOH)x3CH2Q", and Y" is oxygen or sulfur, wherein x1, R1, R2, Z1, Z2 and Q" are as defined in paragraphs (2G) and (2I), and x3 is 0 or 1.
3. 3. The fibrous articles of claim 2 wherein the fiber additives are incorporated therein in an amount of up to about 2.5 percent by weight of the fibrous article.
4. 4. The fibrous articles of claim 2 wherein the article comprises filarnents prepared from a fiber-forming theromoplastic resin.
5. 5. The fibrous articles of claim 4 wherein the fiber-forming thermoplastic resin is selected from the group consisting of polypropylene, polyethylene, polybutylene, polyester, polyamide, polyacrylonitrile and blends thereof.
   6. A process for producing a water and/or oil repellent fibrous article which comprises contacting the fibrous article with a liquid medium containing a fiber additive selected from the group consisting of compounds having the formula:
   (A) wherein n is an integer of from zero to 4; L is D2R2, hydrogen or -(CH2)f1(CHOH)f2(CH2)f3OH, wherein f1 and f3 are the same or differer and are lntegers of from 1 to 4 and wherein f2 is either zero or 1, Q is a member selected from the group consisting of methyl, chlorine, bromine, fluorine and iodine; D1 and D2 are divalent radicals inde-pendéntly selected from the group consisting of alkylene of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)p1CH(OH)(CH2)p2O-, -C6H4(CH2)p1-, -C6H4O(CH2)p1-, -C6H4-, and -C6H4O-, wherein P1 and P2 are integers and are independently selected from the group consisting of 1 to 4; and R1, R1' and R2 are independently selected from the group cons;sting of -(CmF2m+1), -(CmF2m-1) and -(CF2)mOX, wherein m is an integer of 2 to 20 and X is selected from the group consisting of perfluorinated alkyl of 1 to 6 carbon atoms;
   (B) wherein n, Q, D1 and R1 are as defined in paragraph (6A); Z is alkylene of 1 to 4 carbon atoms, and t is an integer and is 2, 3 or 4; Y, when t is 2, is selected from the group consisting of:
   
   (i) >O, aim 6 continued (ii) >C(CH2OH)2 (iii) >CH2 (iv) >CH(CH3) (v) >C(CH3)2, (vi) (vii) >CHOH, (viii) -CH2(OCH2CH2)rCH2-, and (ix) -(CH2OCH2O)r-wherein r is an integer of 1 to 10; Y, when t is 3, is or ;
   and Y is when t is 4, provided that Z is not -CH2- when Y is oxygen;
   
   wherein q is 1 or 2, Z' is alkylene of 2 to 4 carbon atoms, and n, Q, D1 and R1 are as defined in paragraph (6A);
   (D) wherein A1 and A2 are independently selected from the group consisting of -R1, -OR1, -OD1R1, -D1R1 and -CO2D1R1, wherein n, D1 and R1 are as defined in paragraph (6A), and T is a member selected from the group consisting of:
   (i) , (ii) , laim 6 continued (iii) , and (iv) wherein Q' is a member selected from the group consisting of CH3 and halogen and n' is an integer of from 0 to 4;
   
   (E) wherein B is a member selected from the group consisting of:
   (i) -CO2D1R1 (ii) , and (iii) -CON(Z")2 where D3 and D4 are divalent radicals independently selected from the group consisting of alkylene of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)P1 CH(OH)(CH2)p2 O-, -C6H4O(CH2)p1-, -C6H4-, and -C6H4O-, R3 and R4 are independently selected from the group consisting of -(CmF2m+1)-, -(CmF2m-1)- and -(CF2)mOX, Z" is alkyl of 1 to 4 carbon atoms, wherein P1m P2, m, D1, D2, R1, R1 ', R2 and X are as defined in paragraph (6A), with the proviso that when -D2R2 and -D3R3 are different, then at least one of D2 and D3 must contain at least 3 methylene groups;
   
   (F) wherein R1 and D1 are as defined in paragraph (6A), and Y' is selected from the group consisting of oxygen and alkylene of 1 to 6 carbon atoms;
   
   (G) laim 6 continued wherein two E groups are E1, and two E groups are E2, in which E1 is -CON(D1R1)2 or -CO2DlR1 and E2 is -CO2(CH2)x1 (CHOH)x2 CH2Q"
   wherein x1 is an integer of 1 to 5, x2 is an integer of 0 to 4, Q" is -OH or halogen and D1 and R1 are as defined in paragraph (6A);
   (H) ? and wherein R2' is selected from the group consisting of -(CH2)x1 , hydrogen, -(CH2)x1 (CHOH)x2 CH2Q" and -(CH2)(CHOH)CH2OCH2CH(OH)CH2OH, wherein x2 is an integer of 0 or 1 and wherein D1, R1, x1 and Q"
   are as defined in paragraph (6G);
   (I) wherein Z1, Z2 and Z3 are the same or different and are alkylene of from 1 to 4 carbon atoms; and M1 is selected from the group consisting of -OZ, -NHZ, and -O(CH2)x1(CHOH)x2 CH2Q"', wherein Z is alkyl of 1 to 4 carbon atoms; Q"' is -OH, halogen, or hydrogen and wherein x1, x2, R1,R2 are as defined in paragraph (6G), with the proviso that if Q"' is hydrogen, then x1 and x2 are each 1;
   
   (J) wherein M2, M3, M4, M5, M6 and M7 are independently selected from
6. Claim 6 continued the group consisting of hydrogen and Z, in which Z is alkyl of 1 to 4 carbon atoms; Z1, Z2, Z3, Z4, Z5, Z6 and Z7 are the same or different and are alkylene of from 1 to 4 carbon atoms; and R1, R2, R3 and R4 are the same or different and are as defined for the R groups of paragraph (6A); and (K) wherein M' is selected from the group consisting of and -(CH2)x1(CHOH)x3CH2Q", and Y" is oxygen or sulfur, wherein x1, R1, R2, Z1, Z2 and Q" are as defined in paragraphs (6G) and (6I), and X3 is 0 or 1.
7. 7. The process of clalm 6 wherein the heated fibrous article is annealed at a temperature of from 90° to 230°C.
8. 8. The process of claim 6 wherein said liquid medium contains said fiber additive in an amount sufficient to provide a fibrous article having said fiber additive incorporated therein in a amount of up to about 2.5 percent by weight of said fibrous article.
9. 9. The process of claim 8 wherein said liquid medium contains said fiber additive in an amount of from about 0.1 to 50 percent by weight.
   10. The process according to claim 6 wherein said fiber additive comprises an additive selected from the group consisting of compounds having the formula:
   
   (a) wherein L is -(CH2)f1(CHOH)f2CH2f3OH, wherein f1, f2, f3, n, Q, D1 and R1 are as defined in claim (6A);
   
   laim 10 continued (b) wherein t is 2 or 3, and Y (1) is selected from the group consisting of >C(CH2OH)2 and >CHOH when t is 2 and (2) is >COH when t is 3, wherein n, Q, D1, R1 and Z are as defined in claim (6B);
   (c) mixtures of wherein two E groups are E1 and two E groups are E2 in which E2 is -CO2(CH2)x1(CHOH)x2CH2Q", and wherein E1, x1, x2 and Q" are as defined in claim (6G), under the proviso that where x2 is 0, Q" is -OH;
   
   (d) mixtures of and wherein R'2 is selected from the group consisting of -(CH2)x1(CHOH)x2CH2Q" and -CH2(CHOH)CH2OCH2(CHOH)CH2OH, wherein x1, x2, Q", D1 and R1 are as defined in claim (6G), with the proviso that Q" is -OH when x2 is 0;
   (e) wherein M1 is -O(CH2)x1(CHOH)x2CH2Q"', wherein x1, x2, Q"', Z1, Z2 Z3, R1 and R2 are as defined in claim (6I), with the proviso that Q"' is -OH when x2 is 0; and
10. Claim 10 continued (f) wherein M1 is -(CH2)x1(CHOH)x2(CH2)Q" wherein x1, x2, R1, Y", R2, Z1, Z2 and Q" are as defined previously, with the proviso that Q" us -OH when x2 is 0; and wherein said liquid medium contains (1) a functional reactant selected from the group consisting of epoxide compounds having at least two functional epoxide groups, isocyanate oompounds having at least two functional isocyanate groups, and mix-tures thereof, and (2) an amine selected from the group consisting of tertiary amines, amino acids and mixtures thereof.
    11. A process of producing a water and/or oil repellent fiber which comprises extruding said fiber from a fiber-forming thermoplastic resin containing an additive selected from the group consisting of compounds having the formula:
    
    (A) wherein n is an integer of from zero to 4; L is D2R2, hydrogen or -(CH2)f1(CHOH)f2(CH2)f3OH, wherein f1 and f3 are the same or different and are integers of from 1 to 4 and wherein f2 is either zero or 1, Q is a member selected from the group consisting of methyl, chlorine, bromine, fluorine and iodine; D1 and D2 are divalent radicals independently selected from the group consisting of alkyl of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)p1CH(OH)(CH2)p2O--C6H4(CH2)P1-, -C6H4O(CH2)P1-, -C6H4-, and -C6H4O-, wherein P1 and P2 are integers and are independently selected from the group Claim 11 continued consisting of 1 to 4: and R1, R1' and R1 are independently selected from the group consisting of -(CmF2m+1), -(CmF2m-1) and -(CF2)mOX, wherein m is an integer of 2 to 20 and X is selected from the group consisting of perfluorinated alkyl of 1 to 6 carbon atoms;
    
    (B) wherein n, Q, D1 and R1 are as defined above; Z is alkyl of 1 to 4 carbon atoms, and t is an integer and is 2, 3 or 4; Y, when t is 2, is selected from the group consisting of:
    (i) >O, (ii) >C(CH2OH)2 (iii) >CH2 (iv) >CH(CH3) (v) >C(CH3)2, (vi) , (vii) >CHOH, (viii) -CH2(OCH2CH2)1CH2-, and (ix) -(CH2OCH2O)r-wherein r is an integer of 1 to 10; Y, when t is 3, is or ;
    and Y is when t is 4, provided that z is not methyl when Y is oxygen;
    
    (C) wherein q is 1 or 2, Z' is alkyl of 2 to 4 carbon atoms, n Q, D1 and R1 are as previously defined;
    
    (D) Claim 11 continued wherein A1 and A2 are independently selected from the group consisting of -R1, -OR1, -OD1R1, -D1R1 and -CO2D1R1, wherein n, D1 and R1 are as previously defined, and T is a member selected from the group consisting of:
    (i) (ii) (iii) , and (iv) wherein Q' is a member selected from the group consisting of CH3 and halogen and n' is an integer of from 0 to 4;
    (E) wherein B is a member selected from the group consisting of:
    (i) -CO2D1R1 (ii) , and (iii) -CON(Z")2 where D3 and D4 are divalent radicals independently selected from the group consisting of alkyl of up to 6 carbon atoms, alkoxy of up to 6 carbon atoms, -(CH2)P1CH(OH)(CH2)P2O-, -C6H4O(CH2)P1-, -C6H4-, and -C6H4O-, R3 and R4 are independently selected from the group consisting of -(CMF2m+1)-,-(CmF2m-1)- and -(CF2)mOX, Claim 11 continued Z" is alkyl of 1 to 4 carbon atoms, wherein P1, P2, m, D1, D2, R1, R1', R2 and X are as previously defined, with the proviso that when -D2R2 and -D3R3 are different, then at least one of D2 and D3 must contain at least 3 methylene groups;
    
    (F) wherein R1 and D1 are as defined previously and Y' is selected from the group consisting of oxygen and alkyl of 1 to 6 carbon atoms;
    (G) .
    wherein two E groups are E1, and two E groups are E2, in which E1 is -CON(D1R1)2 or -CO2D1R1 and E2 is -CO2(CH2)x1(CHOH)x2CH2Q" or -CO2H wherein x1 is an integer of 1 to 5, x2 is an integer of 0 to 4, Q" is -OH or halogen and D1 and R1 are a previously defined, (H) and wherein R2' is selected from the group consisting of , hydrogen, -(CH2)x1(CHOH)x2CH2Q" and -(CH2)(CHOH)CH2OCH2CH(OH)CH2OH, wherein x2 is an integer of 0 or 1 and wherein D1, R1, x1 and Q"
    are as defined above;
    (I)
11. Claim 11 continued wherein Z1, Z2 and Z3 are the same or different and are alkyl of from 1 to 4 carbon atoms; and M1 is selected from the group consisting of -OZ, -NHZ, and -O(CH2))x1(CHOH)x2CH2Q"', wherein Q"' is -OH, halogen, or hydrogen and wherein x1 and x2, R1 and R2 are as defined above, with the proviso that if Q"' is hydrogen, then x1 and x2 are each 1;
    (J) wherein M2, M3, M4, M5, M6 and M7 are independently selected from the group consisting of hydrogen and Z, in which Z is as defined previously, Z1, Z2, Z3, Z4, Z5, Z6 and Z7 are the same or different and are alkyl of from 1 to 4 carbon atoms, and R1, R2, R3 and R4 are the same or different and are as defined above; and (K) wherein M' is selected from the group consisting of and -(CH2)x1(CHOH)x3CH2Q", and Y" is oxygen or sulfur, wberein x1, R1, R2, Z1m Z2 and Q" are as defined above and x3 is 0 or 1.
12. 12. The process according to claim 11 wherein said additive is contained in said resin in an amount of up to about 3 percent by weight of the resin.