Note: Descriptions are shown in the official language in which they were submitted.
1277
2~;~
FATTY ACI~ ESTERS OF PHENOL DERIVATIVE
ALKOXYLATES AND THEIR USE AS FIBER FINISH COMPONENTS
. ~
Back~round of the Invention
1. Field of the Invention
7 ~ :. __ _ __
The invention relates to a fiber lubricant, a
fatty acid ester of an alkoxylated phenol derivative, which
has effective thermal and oxidative stability, non-
volatility, product stability and, in a preferred embodi-
ment, emulsification properties and which when applied to a
fiber, as a fiber lubricant formulation, exhibits effective
viscosity and lubricity.
2. Description of the Prior Art
. _ . . .
Traditionally, a fiber lubricant formulation
consists of a base material, or lubricant, such as mineral
oil, alkyl esters of fatty acids or vegetable oils; emulsi-
fiers that allow the lubricant to be applied from a water
solution; antistatic agents; antioxidants; bacteriocides;
friction modifiers; and buffering agents.
A fiber lubricant is critical to the conversion of
nylon or polyester fiber into useful yarn for textile
manufacturing. The fiber lubrlcant has several functions.
One function is to control friction. The fiber lubricant
may protect the newly spun fiber from fusion or breakage by
controlling the yarn-to-metal friction at frictional contact
points between the yarn and machine guides, rollers, draw
~19'~S~
plates, heater plate and texturing false twist spindles or
friction discs. The lubricant also functions to provide
yarn cohesion giving strength to the yarn by holding the
yarn bundled together and by allowing the yarn to build up
an acceptable package at the end of processing. Static
electricity that is formed as the yarn rapidly moves through
the processing equipment would also be controlled. The
lubricant must also protect machine surfaces from wear.
U.S~ ~,165,405 discloses fiber lubricants based
upon fatty esters of heteric polyoxyalkylated alcohols
wherein mononuclear, monofunctional initiators are alkoxy-
lated and then esterified. U.S ~,127,490 relates to
lubricating fibers with a major amount of lubricant and a
minor amount of a stabilizer, said stabilizer being the
reaction product of one mole of dicyclopentadiene and at
least one mole of p-cresol, further reacted with at least
one-half mole of isobutylene. U.S. 4,134,841 relates to a
fiber lubricant which is a composition comprising a non-
hindered polyphenyl stabilizer and a polyether lubricant.
U.S. 4,252,528 relates to a spin finish for synthetic fibers
of a thermally stable lubricant and a surfactant deri~ed
from an ethylene oxide-propylene oxide block copolymer
adduct of an alkylated phenol. U.S. 3,578,594 relates to a
fiber treating composition consisting essentially of about
90 percent to about 25 percent by weight of at least one
-2-
.
~2~25~
ester of an ethoxylated aliphatic alcohol and about 10
percent to about 75 percent by weight of at least one ester
of an ethoxylated arylphenol. The examples relate to ~-
methyl benzyl phenol or bis ~-methyl benzyl phenol as the
aryl phenol. A problem of the prior art fiber lubricants
mentioned above is that they are not disclosed as being
capable of being used alone or in a water emulsion as a
fiber lubricant formulation. None of the above references
discloses the use as a fiber lubricant of the products of
applicants' invention, nor do they suggest the use of
applicants' product alone or as a water emulsion.
A purpose of the invention was to provide a fiber
lubricant which may be used by itself in pure form as a
fiber lubricant formulation. Another purpose of the
invention was to provide a self-emulsifiable fiber lubricant
for use as a fiber lubricant formulation.
Summar~ of the Invention
. _
A fiber lubricant has been discovered having
effective thermal and oxidative stability, non-volatility,
product stability, and, in a preferred embodiment, emulsifi-
cation properties, and which when applied to a fiber, as a
fiber lubricant formulation, exhibits effective viscosity
and lubricity. The fiber lubricant is useful as a fiber
lubricant formulation in pure application to polyester or
nylon fiber during a drawing and texturing operation. The
~2~9;~
fiber lubricant formulation is used in a process of lubri- -
cating synthetic fibers which comprises applying the fiber
lubricant to the fiber in an amount between 0.05 percent by
weight and 5 percent by weight, based on the weight of the
lubricated fiber~ The fiber lubricant comprises a compound
selected from the group consisting of
O(A)nR
I
X ~ X ~ (I)
O(A)nR
R"~X~
( I I )
f (A,nR
~ R~ ~ "' (III)
: R""
and
: -4-
32~
(A)nR
X ~ R~ (IV)
R''
wherein A is an oxyalkylene radical having 2 carbon atoms to
4 carbon atoms or mixtures thereof, R is hydrogen or acyl
containing from 8 carbon atoms to 22 carbon atoms, R' is
alkyl containing from 1 carbon atom to 10 carbon atoms, R''
is alkyl containing from l carbon atom to 22 carbon atomst
R''' is alkyl containing from 4 carbon atoms to 8 carbon
atoms and R'"' is R'' or R''', X is an alkylidene radical
containing from 1 carbon atom to 3 carbon atoms and n is an
integer such that the molecular weight of the compound is
between 500 and 2500 and with the proviso that either R'7 or
R''' is ortho to the oxygen in Eormula III. In preferred
embodiments the oxyalkylene radical is oxyethylene or a
mixture of oxyethylene and up to 50 percent by weight of an
oxyalkylene radical having 3 carbon atoms to 4 carbon atoms
and provides effective hydrophilicity to the compound to
enable it to self emulsify in waterO
Description of the Preferred Embodiments
The lubricants of the present invention are
prepared from three essential ingredients, i.e., certaln
phenol derivatives, alkylene oxides and fatty acids.
--5--
. .
~2~925'~
Useful as the phenol derivatives are compounds
selected from the group consisting.of the following form-
ulas:
<~X~X-<~, tV)
R'' ~ X ~
r tVI)
~R t V I I )
~ R''''
~X ~) ( VI I I )
R~ R'
wherein X~ R', R'', R''' and R'''' are as described above.
Examples o X are alkylidene radicals such as methylene,
ethylene and propylidene. Examples of R' and R'' are methyl
lZ~9'~5~
and isobutyl. Examples of R''' and R'''' are butyl and
octyl. Preferably used as the phenol derivative of
formula V is a compound wherein X is
fH3
--c--
H
as the phenol derivative of formula VI is a compound wherein
x is
c~3
CH3
as the phenol derivative of formula VII is a compound
wherein R'' is C4Hg , R''' is C8H17- and R
is C8H17 - or C4Hg- or a compound wherein R''
is C4Hg-, R''' is C4Hg- and R'''' is CH3- and as the
phenol derivative of formula VIII is a compound wherein X is
ICH3
~C-
R' is CH3- and R'' is C4H9-.
Useful as alkylene oxides, from which the oxy-
alkylene radisal derives, are al~ylene oxides containing 2
carbon atoms to 4 carbon atoms such as ethylene oxide,
~Z~Z5~
propylene oxide and butylene oxide. Useful in a preferred
embodiment i9 ethylene oxide or a mixture of ethylene oxide
and other alkylene oxides which when used in a mixture with
ethylene oxide impart a hydrophilicity effective to self
emulsify the compound. In lieu of the other alkylene
oxides, other 3 or 4-carbon cyclic ethers such as
tetrahydrofuran, oxetane, and methyl oxetane may be used.
Preferaby used are mixtures of ethylene oxide and propylene
oxide.
The oxyalkylene is present in the fiber lubricant
in an amount, as represented by n, such that the molecular
weight of the compound is between 500 and 2500. Preferably
used is a block of between 5 and 20 moles, such as 5, 10 or
15 moles of ethylene oxide per mole of phenol derivative.
Also preferably used is a heteric mixture of about 70
percent by weight oxyethylene and about 30 percent by weight
oxypropylene.
Useful as fatty acids are those containing between
8 carbon atoms and 22 carbon atoms, preferably between 16
and 20 carbon atoms and more preferably 18 carbon atoms,
such as isostearic acid.
The phenol derivative is ethoxylated by adding the
phenol derivative and a basic catalyst to an autoclave
evacuated to a vacuum and pressurized with nitrogen and
equipped -~ith temperature, pressure and vacuum controls, and
thereafter heated. The alkylene oxide is added at a
;~ constant rate until all the oxide is added. The reaction
then proceeds at a temperature between 90C and 130C until
a constant pressure is observed. Esterification is then
~23~9J~S'~
accomplished by adding approximately equal molar amounts of
fatty acid and alkoxylated phenol derivative. Acid cata-
lysts, such as methane sulfonic acid and hypophosphorus acid
are added and the esterification reaction is allowed to
proceed at a constant temperature, such as 165C under a
nitrogen blanket.
The lubricants of this invention are applied to
the fiber in an amount between 0.05 percent by weight and
5 percent by weight~ based on the weight of the lubricated
fiber.
The lubricity of the products of this invention on
synthetic yarns may be determined using any reasonable
method One useful test method measures the lubricity, in
units of the coefficient of friction, of nylon filaments
having fiber lubricants applied to them at a concentration
of about 1 percent lubricant by weight of filament by the
procedure of the following two paragraphs.
A stable aqueous emulsion of the lubricant is
prepared. This emulsion is applied to the yarn, such as
nylon or polyester, using an apparatus in which the yarn is
passed at a controlled speed through a continually replen-
ished drop of finished solution or dispersion of specified
concentration. A suitable apparatus is the ATLAS*yarn
finish applicator sold by the Precision Machine and Develop-
ment Company of Wilmington, Delaware. The lubricant
* trademark
_g_
dispersion is metered to the continually replenished drop of
solution using a syringe pump. The yarn is fed over an
adjustable canter roller which functions to space the yarn
over a drying drum used to remove water. The yarn is
finally passed over a winding tube and subsequently con-
ditioned for 16 to 24 hours at 65 percent relative humidity
and 70F before being tested.
The coefficient of friction (f~ may be determined
on any suitable machine, such as a Rothschild F Meter
utilizing 0.313 inch diameter ceramic (Al Si Mg) and satin
chrome fric~on pins that has friction surface at a yarn
contact angle of 180. The yarn speed is varied, such as at
50, 100, 150, 200, and 250 meters per minute. The yarn
tension may be varied such as at 4 or 6 grams on the input
side as determined by tensiometers by the Rothschild*F
meter. The (f) values are determined directly by reading
the chart produced by the Rothschild*~ meter.
Viscosity may be determined by any standard
procedure, such as using a~Brookfield*viscometer or Ubelohde*
tube Eollowing ASTM D444 71/79 or D2161-79. The viscosity
of the fiber lubricants of this invention have a controlled
viscosity range, from 500 to 1500 Saybolt universal sec-
onds. A viscosity below this range i5 detrimental to
processing the fibers and a viscosity above this range
causes excessive add on to the fibers.
* trademarks
--10--
~`
~2~9~5~
Thermal and oxidative stability as well as non-
volatility of the fiber lubricant may be tested by a number
of suitable procedures such as the hot plate test, the
circulating air oven test, dynamic thermogravimetric
analysis and isothermal thermogravimetric analysis. The hot
plate test proceeds by placing metal cups, 3 for each
example, on a heater and maintaining the temperature at
240C for 24 hours. At intervals of time, the weight loss
for each of the 3 samples is determined and averaged and the
quality of residue determined. The hot plate test is
representative of thermal stability as measured by the
results at 240C for 24 hours and of oxidative stability by
the quality of the residue. The circulating air oYen test
proceeds as in the hot plate test except the hot plate and
samples are placed in a circulating air oven. The thermo-
gravimetric analyses proceed as follows: the dynamic
thermogravimetric analysis measures the temperature in
degrees centi~rade at which a specific percentage by weight,
such as 1 percent by weight and 10 percent by weight, of the
sample is lost in a test atmosphere, such as air or
nitrogen, while heating the sample at a constant heating
rate, such as 20 degrees per minute; and the isothermal
thermogravimetric analysis measures the percent by weight
loss of the sample at a constant temperature) such as 210C,
for a specific time interval, such as 40 minutes, while the
--11--
5~
sample is continuously weighed.
The product stability of the fiber lubricant may
be tested by any suitable method. The ability of the
product of the invention to be storage stable is excellent.
The emulsification properties of the fiber
lubricant may be tested by preparing a mixture containing 10
parts of fiber lubricant, 20 parts of mineral oil and 70
parts of water. The mixture is shaken vigorously and
allowed to stand for 24 hours. If separation of the
emulsion does not occur, the emulsion is considered stable.
The products of a preferred embodiment of the
invention are self emulsifiable with water and do not
require additives to make an emulsion.
Additional additives may, however, be added to the
fiber lubricants in preparing fiber lubricant formula-
tions. These additives are described in U.S. 4,134,8417
-12-
~2~9~S~
The followin~ examples will further illustrate the
various aspects of the invention. Where not otherwise
specified throughout the specification and claims, temper-
atures are in degrees Centigrade, and parts, percentages and
proportions are by weight.
Example 1
To an autoclave e~uipped with temperature,
pressure, and vacuum controls was added 780 parts of
butylated, styrenated cresol (WINGSTAY~ V - Goodyear
Company) and 8 parts of 45 percent potassium hydroxide
solution. The autoclave was heated to 125C after evacu-
ating to a vacuum of less than 10 millimeters mercury and
then pressurizing to 34 lbs./square inch with nitrogen.
Ethylene oxide was added at a rate of 250 parts/hour until
1921 parts were added. When constant pressure was observed,
the catalyst was removed by deionization and the mixture was
further stripped to remove volatiles. This ethoxylate,
Example lA, had a hydroxyl number of 66.2 and a viscosity of
883 Saybolt universal seconds at 100F.
To a 2 liter flask having temperature control,
stirrer and distillation apparatus were added 891 parts of
the above ethoxylate. Next, 279.1 parts of isostearic acid,
4.12 parts of methanesulfonic acid, (70 percent), and 4.0
parts of hypophosphorous acid were added. The temperature
was held at a constant 165C in a nitrogen atmosphere until
-13-
s~
the esterification reaction was complete. After catalyst
removal, the product of Example 1 of this invention, the
isostearate ester of ethoxylated butylated styrenated
cresol, a specific product containing compounds of formula
IV above, was obtained having a hydroxyl number of 4.4, an
acid number of 1.56 and a viscosity of 781 Saybolt universal
seconds at 100F.
Comparison Examples A, B, C and D
A is a polyoxypropylene block adduct of a polyoxy-
ethylene adduct of ethylene glycol of approximate average
molecular weight of the hydrophobe of 1000 and an oxy-
ethylene content of about 50 percent by weight.
B is a polyoxyethylene block adduct of a polyoxy-
propylene adduct of propylene glycol of approximate average
molecular weight of the hydrophobe of 950 and an oxyethylene
content of about 50 percent by weight.
C is a heteric ethylene oxide propylene oxide
adduct of a C12-C15 fatty alcohol, having an overall
approximate average molecular weight of 1280 and containing
about 50 percent ethylene oxide.
D is a polyoxyethylene block adduct of a polyoxy-
propylene adduct of bisphenol A of approximate average
overall molecular weight of 8350 and an oxyethylene content
of about 80 percent by weight.
-14-
~z~s~æs~
Lubricity, heat stability and emulsion properties
were obtained as follows: An aqueous emulsion of the
lubricant of Example 1 was prepared. This emulsion was
applied to yarn using an Atlas yarn finish applicator. The
coefficient of friction (f) was determined on a Rothschild F
meter utili~ing 0.313 inch diameter ceramic (Al Si Mag) and
satin chrome friction pins as the friction surface at a yarn
contact angle of 180. The ASTM procedure Standard Test
Method for Coefficient Friction, Yarn to Metal Designation
03108-76 was generally followed. The lubricity results,
using 40/12 denier nylon 6 yarn, are shown in Table I for
; the products of Example 1 and comparison Example A.
TABLE I
Input Speed Coefficient of Friction
Tension Meters/ Example 1Comparison Example A
(Grams)Minute f f
4 50 .70 .73
4 100 .71 .76
4 150 .71 .77
4 200 .71 .77
6 50 .64 .67
6 100 .66 .69
6 150 .67 .70
6 200 .67 .71
Thermal and oxidative stability of the products of
Example 1 and comparisons B and C, using a hot plate set at
240C and 3 gram samples, are shown in Table II.
-lS-
9~5~
TABLE II
Heat Stability
Hot Plate Test
Percent Residue
ExampleAfter 24 Hours Nature of Residue
1 76.7 Light brown liquid
B 2.9 Varnish
C 38.8 Dark Brown Liquid
Heat stability results for the products of
Example 1 and Comparison Example C, using a circulating air
oven set at 210C and 3 gram samples, are shown in Table
; IIIo
TABLE III
Heat Stability
Circulating Air Oven Test
Percent Residue
ExampleAfter 24 Hours Nature of Residue
187.6 Light Brown Liquid
C22.9 Dark Brown Liquid
Heat stability results for the product of Example
1 of the invention using thermogravimetric analysis and
isothermal percent weight loss are shown in Table IV.
-16-
!L9'2~
TABLE IV
Thermogravimetric Analysis
Dynamic C Weight Loss of
1% 10% 50%
Example Air/ N2 Air/ N2 Air/N2
1 150/31S 287/370 318/395
Isothermal ~ Weight Loss Smoke Point
at 210C -40 Minutes C
1 18.0/4~0 187
Stable emulsions, made with the product of
Example 1, and water and with the product of Example 1,
water and other materials are shown in Table V.
-17-
~'~19%S'~
TABLE V
Emulsions
Stable Emulsion
1 2 3 4
Component parts parts parts parts
Product of Example 1 12 5 2 20
Tridecyl Stearate36 - - -
Butyl Stearate - 15.0
Mineral Oil - - 8
(Crystosol TW)
KLEARFAC~ A270 - 3
~neutralized)
Water 52 77 90 80
,
-18-
~2~ 5~
Examples 2-20
Examples 3-10 and 14-19 were prepared using the
procedure to prepare Example lA. Examples 2, 11-13 and 20
were prepared using the procedure for preparing the product
of Example 1. EO is ethylene oxide, PO i5 propylene oxide,
product Yl is a commercial product of formula V wherein X is
ICH3
-- C -- ,
H
(WINGSTAY~ S - Goodyear Company), product Y2 is a commer-
cial product of formula VII wherein R" is
C4Hg-, ~"' is C8H17- and R"" is either C4Hg- or C8H17-
(WINGSTAY~ T - Goodyear Company) and product Y3 is a
commercial product of Eormula VI wherein X is
CH3
-- C --
and R" is C~Hg- (WINGSTAY~ C - Goodyear Company).
--19--
9~5~
The products are as follows:
Example Composition
2 Laurate ester of Example LA
3 5 mole ethoxylate of the butylated
styrenated cresol of Example 1
4 10 mole ethoxylate of the butylated
styrenated cresol of Example 1
5 EO adduct of product Y
6 10 EO ~
7 15 EO "
8 70/30 EO/PO "
9 11 PO ~ 9 EO + 11 PO "
25 EO "
11 isostearate ester of Example 7
12 isostearate ester of Example 10
13 isostearate ester of Example 9
14 5 EO adduct of product Y2
10 EO "
16 15 EO "
17 5 EO adduct of product Y3
18 10 EO "
19 15 EO "
the isostearate ester of Example lA
-20-
The physical properties of the fiber lubricants of
Examples 2-20 are shown below in Table VI.
_ ble VI
ExampleMolecular HydroxylViscosity
Weight No.SUS at 100F
2 1047 7~6 905
3 467 120 ~ 2 1406
4 680 82. 5 936
504 111 ~ 2 1570
6 742 75~6 1111
7 946 59~3 1088
8 1465 38~ 3 1320
9 1556 36~1 1243
1320 42~ S 1657
11 1200 6~0 974
1~ 1580 6~ 5 1320
13 1800 10~0 1162
14 576 97~ 4 1470
695 80 r 7 1159
20 16 1578 71.1 981
17 610 91~9 25g9
18 851 65~ 9 1139
19 1024 54~ 1094
1134 12~ 8 1096
Thermal properties of heat resistant lubricants of the
invention and comparison Example B, determined in an
aluminum pan test on a hot plate set at 240C are shown in
Table VII.
-21-
5'~
Table VII
Example rcent Residue, Hours Appearance*
0.5 2 4 8 24
2 99.4 98.6 97.0 93.3 78.2 b
3 97.8 93.6 89.1 82.7 76.1 b
4 99.6 97.6 95.0 89.4 71.9 b
99.3 97.3 95.2 91.6 86.1 a
6 99.8 99O3 98.8 97.6 93.0 b
7 99.7 99.2 97.9 94.8 84.5 b
8 99.5 98.3 95.9 90.7 80.4 b
9 98.7 95.0 89.6 79.2 62.9 b
14 92.9 85.2 79~6 72.1 61.0 b
98.9 96.7 94~3 89~0 64.8 b
16 97.6 95.7 93~3 88.4 65.5 b
17 94.1 88.8 85.5 78.9 71.0 b
18 95.9 93.0 90.0 83.7 57.0 b
19 96.6 94.9 92.3 86.2 65.0 b
B 97.3 80.8 41.4 6.6 2.4 c
* a-brown
b-light brown
c-varnish
Thermal properties of heat resistant lubricants of the
invention and comparison examples B and D as determined in
an aluminum pan in an air circulating oven at 210C are
shown below in Table VIII.
-22-
Iable VIII
Example Percent Residue, ~urs pearance*
0.5 2 4 8 24
2 98.1 90.3 78.8 60.7 4002 d
7 98.4 92.4 85.4 75~7 52.3 a
9 94.0 73.6 56.4 37.5 16.9 d
98.1 87.5 76.1 62.7 37.0 d
11 96.6 91.9 86.4 78.4 56.4 d
12 96.9 91.2 83.4 70~3 42.3 d
13 98.4 81~3 65.1 48.0 ?6.8 d
B 67.0 1.7 1.1 - - c
D 98.0 87.1 77.4 68.3 51.2 d
* a - brown
c - varnish
d - dark brown
-23- -
