U.S. patent application number 10/718910 was filed with the patent office on 2004-06-24 for triacylglycerol oligomer products and methods of making same.
Invention is credited to Franks, William A..
Application Number | 20040122245 10/718910 |
Document ID | / |
Family ID | 26865077 |
Filed Date | 2004-06-24 |
United States Patent
Application |
20040122245 |
Kind Code |
A1 |
Franks, William A. |
June 24, 2004 |
Triacylglycerol oligomer products and methods of making same
Abstract
The present invention relates generally to triacylglycerol
oligomer products and methods of making, using and producing
same.
Inventors: |
Franks, William A.; (Kansas
City, KS) |
Correspondence
Address: |
DUNLAP, CODDING & ROGERS P.C.
PO BOX 16370
OKLAHOMA CITY
OK
73113
US
|
Family ID: |
26865077 |
Appl. No.: |
10/718910 |
Filed: |
November 21, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10718910 |
Nov 21, 2003 |
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09732361 |
Dec 7, 2000 |
|
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6686487 |
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60169468 |
Dec 7, 1999 |
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Current U.S.
Class: |
554/9 |
Current CPC
Class: |
A61Q 1/06 20130101; D21C
5/02 20130101; Y02W 30/648 20150501; Y02W 30/64 20150501; D06P 1/46
20130101; A61Q 19/00 20130101; D06P 1/65125 20130101; D06P 1/667
20130101; C11B 3/001 20130101; C09D 11/06 20130101; D06M 13/224
20130101; A61K 8/375 20130101; A61Q 1/10 20130101; C09D 9/04
20130101; D06M 13/2243 20130101; A61Q 1/02 20130101 |
Class at
Publication: |
554/009 |
International
Class: |
C11B 001/00 |
Claims
What is claimed is:
1. A degummed triacylglycerol product produced according to a
process comprising the steps of: providing a degummer assembly
comprising a tank member having an inlet, an outlet and an interior
reaction chamber, the inlet and the outlet being in open fluid
communication with the interior reaction chamber; introducing a
liquid medium at a predetermined temperature into the interior
reaction chamber of the degummer assembly via the inlet;
introducing a triacylglycerol mixture into the liquid medium in the
interior reaction chamber of the tank member, wherein the
triacylglycerol mixture bubbles through the liquid medium to
thereby cause at least two reaction products to form; separating
the at least two reaction products resulting from the
triacylglycerol mixture and the liquid medium; and removing the at
least two reaction products from the interior reaction chamber of
the tank member via the outlet in the tank member.
2. The degummed triacylglycerol product of claim 1 wherein in the
step of introducing the liquid medium at a predetermined
temperature into the interior reaction chamber of the degummer
assembly via the inlet, the liquid medium is water.
3. The degummed triacylglycerol product of claim 2 wherein the
temperature of the water is substantially less than 25.degree. C.
and substantially greater than 60.degree. C.
4. The degummed triacylglycerol product of claim 1 wherein one of
the at least two reaction products contains a degummed
triacylglycerol.
5. The degummed triacylglycerol product of claim 1 wherein one of
the at least two reaction products contains a lecithin.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of application No.
09/732,361, filed Dec. 7, 2000, which is a non-provisional of U.S.
provisional patent application Serial No. 60/169,468 filed Dec.
7,1999, entitled "Vegetable Resin Products" and is hereby expressly
incorporated herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention relates generally to triacylglycerol
oligomer products and methods of making, using and producing
same.
[0005] 2. Description of the Related Art
[0006] Triacylglycerols(TAGS) are lipids of plant or animal origin.
They include such common substances as safflower oil, canola oil,
peanut oil, corn oil, cottonseed oil, sunflowerseed oil, linseed
oil, soybean oil, tung oil, etc. Those TAGS that are liquids at
room temperature are generally known as oils; those that are solids
are usually known as fats. TAGS are simply the fatty acid esters of
the triol glycerol. The general structure of TAGS is: 1
[0007] The fatty acids, R1, R2, R3, that are obtained by hydrolysis
of naturally occurring fats and oils are long, straight-chain
carboxylic acids with about 12 to 20 carbon atoms. Most fatty acids
contain even number of carbon atoms. Some of these common fatty
acids are saturated, while others have one or more elements of
unsaturation; generally carbon-carbon double bonds.
[0008] TAGS naturally occur in some plants and can be obtained in
relative pure forms by various processing methods. Substances such
as free fatty acids and phospholipids are removed during
processing. TAGS resulting from a single plant source after
processing is a mixture made up of TAGS with differing percentages
of saturated and unsaturated fatty acids. Table 1 lists the
approximate composition of the fatty acids obtained from hydrolysis
of some TAGS.
1TABLE 1 Fatty Acid Composition Obtained by Hydrolyhsis of Common
Triacylglycerols* TAG MYRISTIC PALMITIC STEARIC OLEIC LINOLEIC
ELEOSTEARIC LINOLENIC SOYBEAN 1-2 6-10 2-4 20-30 50-58 5-10 COTTON
1-2 18-25 1-2 17-38 45-55 CORN 1-2 7-11 3-4 25-35 50-60 LINSEED 4-7
2-4 14-30 14-25 45-60 SUNFLOWER 6-7 1-2 21-22 66-67 TUNG 80
[0009]
2 TABLE 2 list the supply of major TAGS produced in the United
States. TRIACYLGLYCEROL PRODUCTION (POUNDS) SOYBEAN 20,220,000,000
COTTONSEED 1,210,000,000 SUNFLOWERSEED 1,196,772,000 CORN
1,283,200,000
[0010] TAGS containing multiple double bonds within their
carboxylic acid moieties will undergo thermal polymerization to
form oligomers which are low molecular weight polymers.
Triacylglycerol Oligomers(TAGOS) were first described by Schieber
(1928).
[0011] Several investigators, Schieber(1928,1929), Kappelmier
(1933,1938), Kurz(1936), Bradley (1940), Phalnikar and Bhide
(1944), Bradley (1947), Barker, Crawford, and Hilditch(1951),
Wisenblatt, Wells, and Common (1953), Wells and Common(1953),
Pascual and Detera (1966), Boelhouwer, Knegiel, and Tels(1967),
Saha and Bandyopadhyay (1974), Sarma (1984)) have suggested
mechanisms for thermal polymerization of vegetable oils. Scheiber
(1928,1929) and Kappelmeier (1933,1938) proposed a Diels-Alder
diene synthesis as a basis for explaining the polymerization of
vegetable oils which is often referred to in the literature. Most
investigators agree with the formation of hydroxy unsaturated
dimeric acids during thermal polymerization which are connected by
means of a cyclic compound.
SUMMARY OF THE INVENTION
[0012] In one embodiment, the present invention is a method for
degumming triacylglycerols. This method includes the steps of: (A)
providing a degummer assembly including a tank member haveing an
inlet and an outlet, and an interior reaction chamber. The inlet
and the outlet are in open fluid communication with the interior
reaction chamber. Step B introduces a triacylglycerol mixture into
the interior reaction chamber of the degummer assembly via the
inlet. Step C introduces a liquid medium at a predetermined
temperature into the triacylglycerol mixture in the interior
reaction chamber of the tank member, thereby causing at least two
reaction products to form. Step D separates at least two reaction
products resulting from the triacylglycerol mixture and the liquid
medium. Step E removes at least two reaction products from the
interior reaction chamber of the tank member via the outlet in the
tank member.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0013] FIG. 1 is a perspective side view of the degummer assembly
of the present invention.
[0014] FIG. 2 is a second perspective side view of the degummer
assembly of the present invention.
[0015] FIG. 3 is a schematic flow diagram.
DETAILED DESCRIPTION OF THE INVENTION
[0016] Before explaining in detail at least one embodiment of the
invention in detail by way of exemplary drawings, it is to be
understood that the invention is not limited in its application to
the details of construction and the arrangement of the components
set forth in the following description or illustrated in the
drawings. The invention is capable of other embodiments or of being
practiced or carried out in various ways. Also, it is to be
understood that the phraseology and terminology employed herein is
for purpose of description and should not be regarded as
limiting.
1. Removal of Lecithin (Degumming)
[0017] Lecithin is a mixture of phospholipids, cephalin and
inositol phosphatides, glycerides, traces of tocopherols and
pigments. Phospholipids are lipids that contain groups derived from
phosphoric acid. The most common phospholipids are the
phosphoglycerides, which are closely related to common fats and
oils. A phosphoglyceride generally has a phosphoric acid goup in
place of one of the fatty acid groups of TAGS. The simplest class
of lecithin are the phosphatidic acids, which consist of glycerol
esterified by two fatty acids and one phosphoric acid group.
Phosphatidic acid is represented by the chemical formula given
below. 2
[0018] Lecithin can be hydrated with water which renders it
immiscible with oil and can brings about a separation of hydrated
lecithin and oil. However, hydrated lecithin when mixed thoroughly
with water and TAGS forms a very stable emulsion that separates
only on standing for long periods of time. Formation of the
emulsion can be avoided by bubbling TAGS through a container filled
with water. A bubble chamber (degummer) was developed for this
purpose.
[0019] The degummer assembly 10 of the present invention is show in
FIGS. 1 and 2. The degummer assembly 10 consists of a tank member
20 having an inlet 30, at least one outlet 40, and an interior
reaction chamber 50. The inlet 30 and the at least one outlet 40
are in open fluid communication with the interior reaction chamber
50. A plate 60 containing small holes 70 of known diameter is
placed at the bottom 80 of the tank member 20 and attached to inlet
30. The interior reaction chamber 50 is filled with a liquid medium
90 such as water or other liquids (bulk liquid) and maintained at a
temperature which can range from <25.degree. C. to
>60.degree. C. Water hydrates the lecithin.
[0020] TAG is pumped or gravity fed into the interior reaction
chamber 50 through the small holes 70 and form bubbles 100 or
"strings" on contact with the liquid medium 90 and do not form
emulsions. The small bubbles 100 or "strings" of TAGS rise to the
surface of the bulk liquid and burst forming at least two separate
liquid phases 110, (i.e. at least two reaction products) each of
which remain separated from the liquid medium 90. At least one
liquid phase contains degummed TAG 120, at least one liquid phase
contains lecithin 130, and the third is the liquid medium 90.
[0021] As more and more TAG is fed into the tank member 20, the
degummed TAG 120, which is less dense than the lecithin 130 rises
to the top 140 of the interior reaction chamber 50 and forms a top
layer 150. The lecithin 130 forms the middle layer. The lower layer
is the liquid medium 90. The top layer 150 containing the degummed
TAG 120 is allowed to reach a certain height to minimize
contamination from the lecithin 130 at which time it can be
continuously removed through the at least one outlet 40. The
lecithin 130 can be removed through a lower at least one outlet
tube 41. The volume produced depends on degummer assembly 10
variables such as the diameter of the small holes 70 of the inlet
30, size of the tank member 20, the flow rate, liquid medium 90
temperature, etc. Degummed TAG 120 was analyzed for phosphorous
content. The results are given in Table 3 below.
3TABLE 3 Phosphorous Content of Degummed Triacylglycerols(TAGS)
TRIACYLGLYCEROL PHOSPHOROUS, PPM* SOYBEAN 0.005
[0022] Van Nieuwenhuyzen (1976) has demonstrated that the viscosity
of lecithin at a temperature of 70.degree. C. increases as the
moisture content decreases. The viscosity of the lecithin continues
to increase until it achieves a moisture content of approximately
7%. The viscosity of the lecithin then begins to decrease rapidly
until it is dry. This property of lecithin was used to develop a
process to reduce the moisture content to less than 3%.
[0023] Lecithin can be separted according to the flow diagram shown
in FIG. 3. The lecithin 130 resulting from the degummer assembly 10
is passed into a separator or clarifier 160 to obtain a solids
content of 15%. The concentrated lecithin mixture is then fed onto
the porous cloth 170 of the conveyor system shown in FIG. 3. The
porous cloth 170 allows the water to pass through while retaining
the net lecithin 130. The net lecithin 130 is then passed through a
series of pressurized and heated rollers 180 which are in contact
with each other. The first 190 and second 200 roller systems are
made of stainless steel. The third 210 and fourth 220 roller
systems are made of hard rubber. As the lecithin 130 passes through
the series of pressurized and heated rollers 180 moisture is
removed bringing about changes in viscosity resulting in the
formation of a lecithin sheet 230 that contains less than 5%
moisture on exiting from the series of pressurized and heated
rollers 180. The moist lecithin sheet 230 is passed through an oven
240 heated with air and the moisture content of the lecithin sheet
230 is further reduced to less than 3%.
[0024] TAGS that have been degummed according to the procedure
given above are further refined by vacuum distillation of free
fatty acids. The first step in the process is to remove under
vacuum a large portion of the oxygen before heat is applied. Once
the oxygen is removed under vacuum heat is gradually applied until
the boiling point temperature of free fatty acids have been reached
at the operating vacuum. The temperature is maintained until all
fatty acids have been removed. TAGS are now ready for thermal
polymerization.
[0025] A continuous semi-plugged flow reactor has been designed for
the refining of TAGS. All columns are under the same vacuum.
Degummed TAG at room temperature is pumped into a first column and
removal of oxygen begins. As TAG flows upward through column once
the temperature increases to 60.degree. C., it exits into column
two. As it flows upward through column two oxygen is still being
removed as-the temperature gradually increases to 120.degree. C.
Columns three, four, and five are utilized for gradually increasing
the TAG to the boiling point of free fatty acids at the operating
vacuum and holding for a period of time depending on the flow rate
to allow complete removal of the free fatty acids. At a temperature
of 228.degree. C.-235.degree. C., TAG undergoes a color change from
"straw" to a light greenish tint.
4TABLE 4 Data for Refined Triacylglycerols TRIACYLGLYCER L Y* R B
FREE FATTY ACID - %* SOYBEAN 2.8 1.4 92.0 COTTONSEED SUNFLOWERSEED
CORN
[0026] TAGOS are prepared by thermal polymerization of TAGS that
have been degummed and refined according to the procedures given
above. Pre-polymerization and polymerization takes place in columns
six through ten shown.
[0027] Column six is the pre-polymerization reactor column wherein
the temperature is gradually increased from the boiling point of
the free fatty acids to polymerization temperature. TAG exits
column six and enters column seven at the polymerization
temperature. Columns seven, eight, nine and ten are the reactor
columns and are maintained at the polymerization temperature. TAG
remains in the reactor columns for a residence time depending on
the flow rate and exits into the storage tanks that are also under
the same vacuum. The viscosity attained will depend on the
residence time(flow rate) and the polymerization temperature.
5TABLE 5 Viscosities of Triacylglycerol Oligomers for Various
Residence Times and Temperatures. RESIDENCE TEMPER- TRIACYLGLYCEROL
TIME ATURE VISCOSITY SOYBEAN 24 hours 285 C. 32 p COTTONSEED 8 hrs
318 C. 154 p 50% 13.5 hrs 295 C. 22 p SUNFLOWERSEED + 50% SOYBEAN
CORN 13 hrs 295 C. 43 p 50% SOYBEAN + 50% 13 hrs 303 C. 11 p CANOLA
TUNG
[0028]
6TABLE 8 Viscosity and Molecular Weight of Triacylglycerols
Oligomers TRIACYLGLY- CEROL VISCOSITY, CP MOL. WEIGHT MWD SOYBEAN
12400 132785 57.5 SOYBEAN 3207 5569 3.7
[0029] Skin color of face strongly depends on the type and amount
of melanin and hemoglobin existing in the skin and varies widely
according to several factors such as race, physiological
conditions, age, sex, and seasonal variation. Face skin color is
not uniform. It differs depending on whether it is the color of the
forehead, forecheek, or sidecheek. Skin color was measured using
photoelectric colorimeters and with the aid of computers, cosmetics
were formulated using TAGOS to exactly match skin colors. The
formulation given below were used to prepare cosmetic colors.
7 Component % Standard No. 1 Cosmetic Brown-Lt 5.00 TAGOS Emulsion
95.00 Standard No. 2 Raw Sienna 5.00 TAGOS Emulsion 95.00 Standard
No. 3 85% cosmetic Green + 5.00 15% Cosmetic Red TAGOS Emulsion
95.00
[0030] An emulsion consisting of water and TAGOS was prepared using
a lecithin sludge as the emulsifying agent. Lecithin sludge is the
concentrated mixture of lecithin and water resulting from the
degummer. TAGO, 62.7 gms, and lecithin sludge (50-60%), 21.2 gms,
are mixed and heated to 70C. Water, 176.8 gms, is heated in a
separate container to 70 C. and then added to the TAGO and lecithin
sludge mixture. The solution is stirred and allowed to cool. The
pigment is added and the mixture is homogenized.
[0031] A Lovibond Tintometer was used to measure skin color. The
instrument was standardized according to procedure using a gray
scale and magnesium oxide standard. Measurements were made on the
right cheek, left cheek, and the forehead. The skin color of 234
females was measured using the Lovibond Tintometer. This data is
given in Table 12.
[0032] A thin layer of cosmetic preparation was placed on a filter
paper and allowed to dry. The probe from the Lovibond Tintometer is
placed directly on the dry cosmetic color preparation and the color
determined and recorded. This data is given in Table 11.
[0033] A computer program was written for a Radio Shack Tridos 80
Computer to perform the calculations. Color matching functions of
Banks (1977) were used to write the computer program. The program
is written in four parts and is given in Table 10. The program
produces tristimulus values, ratio of the standard cosmetic
preparation to match the the skin color, and the difference between
the skin color and the calculated color match formulation. These
results are given in Table 12.
8TABLE 10 Computer Program for Color Matching - Four Parts Part 1
`FORMULA` 1 DIM TR(39), TY(39), TB(39), E(39), EY(39), EZ(39) 10
REM CALCULTAION OF CHROMATICITY COORDINATRES AND TRISTIMULUS VALUES
CALL TRISTIM 20 REM READ LOVIBOND SPECTRAL INTERNAL TRANSMITTANCES
40 FOR I = 0 TO 39 50 READ TR(I), TY(I), TB(I) 60 NEXT 70 REM READ
CIE 1931 COLOR-MATCHING FUNCTIONS WEIGHTED BY RELATIVE SPECTRAL
POWER DISTRIBUTIONS OF CIE STANDARDS 80 FOR I = 0 TO 39 90 READ
EX(I), EY(I), EZ(I) 100 NEXT 130 DATA .90258, .02889, .99815 131
DATA .90352, .12593, .99809 132 DATA .90439, .25435, .99788 (10)
133 DATA .90603, .39957, .99711 134 DATA .90737, .52037, .99573 135
DATA .90824, .61634, .99363 136 DATA .90886, .70289, .99111 137
DATA .90858, .77822, .98800 138 DATA .90722, .84481, .98338 139
DATA .90444, .89471, .97459 140 DATA .89819, .92976, .96004 141
DATA .88633, .95277, .94109 142 DATA .86526, .96755, .92316 143
DATA .83257, .97738, .89900 144 DATA .79598, .98364, .87326 145
DATA .77392, .98754, .84574 146 DATA .78952, .99040, .83553 147
DATA .83317, .99195, .85049 148 DATA .87817, .99236, .86792 149
DATA .91300, .99247, .85702 150 DATA .93628, .99179, .81808 151
DATA .95268, .99073, .77002 152 DATA .96362, .98933, .76498 153
DATA .97109, .98768, .77420 154 DATA .97648, .98599, .77827 155
DATA .98053, .98438, .77386 156 DATA .98348, .98333, .76119 157
DATA .98572, .98287, .76656 158 DATA .98753, .98279, .78191 159
DATA .98892, .98330, .83172 160 DATA .99012, .98405, .88572 161
DATA .99117, .98449, .93507 162 DATA .99194, .98510, .96744 163
DATA .99247, .98627, .98466 164 DATA .99303, .98789, .99228 165
DATA .99336, .98912, .99587 166 DATA .99365, .99014, .99719 167
DATA .99402, .99108, .99770 168 DATA .99420, .99160, .99790 169
DATA .99430, .99210, .99800 180 DATA .004, .000, .020 181 DATA
.019, .000, .089 182 DATA .085, .002, .404 183 DATA .329, .009,
1.57 184 DATA 1.238, .037, 5.949 185 DATA 2.997, .122, 14.628 186
DATA 3.975, .262, 19.938 187 DATA 3.915, .443, 20.638 188 DATA
3.362, .694, 19.299 189 DATA 2.272, 1.058, 14.972 190 DATA 1.112,
1.618, 9.461 191 DATA .363, 2.358, 5.274 (11) 192 DATA .052,
.3.401, 2.864 193 DATA .089, 4.833, 1.520 194 DATA .576, 6.462,
.712 195 DATA 1.523, 7.934, .388 197 DATA 4.282, 9.832, .086 198
DATA 5.880, 9.841, .039 199 DATA 7.322, 9.147, .020 200 DATA 8.417,
7.992, .016 201 DATA 8.984, 6.627, .010 202 DATA 8.949, 5.316, .007
203 DATA 8.325, 4.176, .002 204 DATA 7.070, 3.153, .002 205 DATA
5.309, 2.190, .000 206 DATA 3.693, 1.443, .000 207 DATA 2.349,
.886, .000 208 DATA 1.361, .504, .000 209 DATA .708, .259, .000 210
DATA .369, .134, .000 211 DATA .171, .062, .000 212 DATA .082,
.029, .000 213 DATA .039, .014, .000 214 DATA .019, .006, .000 215
DATA .008, .003, .000 216 DATA .004, .002, .000 217 DATA .002,
.001, .000 218 DATA .001, .001, .000 219 DATA .001, .000, .000 300
REM CALCULATIONS OF TRISTIMULUS VALUES 310 U = 0 320 V = 0 330 W =
0 340 PRINT "INPUT Y" : INPUT Y 350 PRINT "INPUT R" : INPUT R 360
PRINT "INPUT B" : INPUT B 370 FOR I = 0 TO 39 380 RYB =
((TR(I))[R)*((TY(I)[Y))*((TB(I)[B)) 390 U = U + (RYB * EX(I)) 400 V
= V + (RYB + EY(I)) 410 W = W + (RYB + EZ(I)) 420 NEXT 430 UVW = U
+ V + W 440 UBAR = U/UVW 450 VBAR = V/UVW 460 WBAR = W/UVW 470 X =
U: LPRINT "X = ";X 480 Y1 = V: LPRINT "Y = ";Y1 490 Z = W: LPRINT
"Z = ";Z 500 OPEN "0",1, "VALUES" 510 PRINT#1,X;Y1;Z (12) 520 CLOSE
1 530 OPEN "0",1,"LOVIBOND" 540 PRINT#1,Y;R;B 550 CLOSE 1 560 RUN
"FORMULA1" Part 2 `FORMULA1` 10 DIM TR(15), TY(15), TB(15),
ME(16,3), T(16,3), Y(3), R(3), B(3), F(1), D(16,16) 40 FOR I = 0 TO
15 50 READ TR(I), TY(I), TB(I) 60 NEXT 132 DATA .90439, .25435,
.99788 134 DATA .90737, .52037, .99573 136 DATA .90886, .70289,
.99111 138 DATA .90722, .84481, .98338 140 DATA .89819, .92976,
.96004 142 DATA .86526, .96755, .92316 144 DATA .79598, .98364,
.87326 146 DATA .78952, .99040, .83553 148 DATA .87817, .99236,
.86792 150 DATA .93628, .99179, .81808 152 DATA .96362, .98933,
.76498 154 DATA .97648, .98599, .77827 156 DATA .98348, .98333,
.76119 158 DATA .98753, .98279, .78191 160 DATA .99012, .98405,
.88572 162 DATA .99194, .98510, .96744 330 FOR I = 1 TO 3 350 READ
Y(I), R(I), B(I) 355 LPRINT " ":LPRINT Y(I), R(I), B(I) 360 NEXT
365 LPRINT " ":LPRINT "T1", "T2", "T3" 367 OPEN "0",1,"DYES" 370 J
= 0 380 FOR I = 0 TO 15 385 J = J + 1 390 FOR N = 1 TO 3 410 Q =
(TR(I)[R(N))*(TY(I)[Y(N))*(TB(I)[(N)) 420 T(J,N) = (1-Q)[2/(2*Q)
430 NEXT 440 PRINT#1, T(J,1); T(J,2); T(J,3) 445 LPRINT " " :
LPRINT T(J,1), T(J,2) T(J,3) 450 NEXT 460 CLOSE 1 465 GOTO 600 470
J = 0 480 OPEN "0",1,"SAMPLE" (13) 505 LPRINT " ": LPRINT "F", "D"
510 FOR I = 0 TO 15 520 J = J + 1 530 Q =
(TR(I)[X2)*(TY(I)[X1)*(TB(I)[X3) 540 F(J) = (1-Q)[2/(2*Q) 550
D(J,J) = -((4*Q)*(1-Q)+((1-Q)[2)*2)/(4*(Q[2)) 560 PRINT#1,
F(J);D(J,J) 565 LPRINT " ":LPRINT F(J), D(J,J) 570 NEXT 580 CLOSE 1
590 RUN "FORMULA2" 600 OPEN"I",1,"LOVIBOND" 610 INPUT#1,X1,X2,X3
620 CLOSE 1 630 GOTO 470 700 DATA 1.9, 3.7, 0 710 DATA 3.6, 4.0, 0
720 DATA 1.4, 1.2, 0 Part 3 "FORMULA2" 100 DIM ME(16,3), D(16,16),
B(3,16), M(3,16), F(16,1), R(3,3), A(3,3), V(3,1), T(16,3), C(3,1)
105 LPRINT " ": LPRINT "EX-BAR, "EY-BAR", "EZ-BAR" 110 OPEN"I",1,
"FUNCTION" 120 FOR I = 1 TO 16 140 INPUT#1, M(1,I), M(2,I), M(3,I)
170 NEXT 180 CLOSE 1 190 OPEN "1",1,"SAMPLE" 200 FOR I = 1 TO 16
210 INPUT#1, F(I,1), D(I,1) 215 D(I,1), = 1/D(I,1) 220 NEXT 230
CLOSE 1 240 F0R 1 = 1 TO 3 250 FOR J = 1 TO 16 260 B(I,J) = 0 270
FOR K = 1 T0 16 280 B(I,J) = B(I,J) + M(I,K)*D(K,J) 290 NEXT K 300
NEXT J 310 NEXT I 315 FOR J = 1 TO 16 316 LPRINT " ":LPRINT
B(1,J),B(2,J),B(3,J) 317 NEXT 320 OPEN "I",1,"DYES" 330 FOR I = 1
TO 16 340 INPUT#1, T(I,1), T(I,2), T(I,3) (14) 350 NEXT 360 CLOSE 1
370 FOR I = 1 TO 3 380 FOR J = 1 TO 3 390 R(I,J) = 0 400 FOR K = 1
TO 16 410 R(I,J) = R(I,J) + B(I,K)*T(K,J) 420 NEXT K 430 NEXT J 440
NEXT I 445 GOSUB 1000 450 GOSUB 18000 460 FOR 1 = 1 TO 3 470 C(I,1)
= 0 480 FOR K = 1 TO 16 490 C(I,1) = C(I,1) + B(I,K)*F(K,1) 500
NEXT K 510 NEXT I 520 FOR I = 1 TO 3 530 V(I,1) = 0 540 FOR K = 1
TO 3 550 V(I,1) = V(I,1) + A(I,K)*C(K,1) 560 NEXT K 570 NEXT I 580
LPRINT "C1 EQUALS"; V(1,1): LPRINT" " 590 LPRINT "C2 EQUALS";
V(2,1): LPRINT" " 600 LPRINT "C3 EQUALS"; V(3,1): LPRINT" " 610
OPEN "0",1,"INVERSE" 620 FOR I = 1 TO 3 630 PRINT#1, A(I,1) ;A(I,2)
;A(I,3) 640 NEXT 650 CLOSE 1 660 OPEN "O",1,"CONCN" 670 PRINT#1,
V(1,1); V(2,1); V(3,1) 680 CLOSE 1 690 RUN "FORMULA3" 1000 PRINT
"THE MATRIX TO BE INVERTED IS: ": PRINT 1010 FOR I = 1 TO 3: FOR J
= 1 TO 3 : LPRINT R(I,J): NEXT J: PRINT : NEXT I 1020 RETURN 18000
CLS: REM SUBROUTINE TO INVERT AN N X N MATRIX. A(N,N) IS THE INPUT
18001 GOTO 18009: INPUT "DO YOU WANT DOUBLE PRECISION";A$ 18002 IF
LEFT$(A$,1) = "N" THEN 18009 18004 DEFDBL A-H, O-Z 18009 DEFINT
I,J,N 18010 N = 3 18050 FOR I = 1 TO N: A(I,1) = 1: NEXT 18052 CLS:
PRINT "YOUR MATRIX IS: ":PRINT (15) 18054 FOR I = 1 TO N: FOR J = 1
TO N: I3! = R(I,J):PRINT I3!; :NEXT:PRINT :NEXT 18060 I1 = I1 + 1:
IF I1 = N + 1 THEN 18210: REM WE'RE THROUGH! 18070 IF R(I1,I1) = 0
THEN GOSUB 18130 : REM INTERCHANGE ROWS 18080 REM NORMALIZE
DIAGONAL ELEMENT AND ZERO COLUMN IN OTHER ROWS. 18090 Q = R(I1,I1):
FOR J = I1 TO N: R(I1,J) = R(I1,J)/Q: NEXT 18095 FOR J = 1 TO N:
A(I1,J) = A(I1,J)/Q: NEXT 18100 FOR I = 1 TO N: IF I = I1 THEN
18117 18105 Q = R(I,I1) 18110 FOR J = I1 TO N: R(I,J) = R(I,J) -
Q*R(I1,J): NEXT 18115 FOR J = 1 TO N: A(I,J) = A(I,J)-Q*A(I1,J):
NEXT 18117 NEXT I 18120 GOTO 18060 18130 REM INTERCHANGE ROWS TO
PREVENT ZERO DIVIDE 18140 I2 = I1: IF I2 = N THEN 18170 18150 I2 =
I2 = I2 + 1: IF I2 = N THEN 18170 18160 IF R(I2,I1) = 0 AND I2<N
THEN 18150 18170 IF I2 = N THEN PRINT "DETERMINENT = 0 !!!": STOP
18180 FOR I = I1 TO N 18190 T = R(I1,I):R(I1,I) = R(I2,I): R(I2,I)
= T 18200 S = A(I1,I):A(I1,I) = A(I2,I):A(I2,I) = S:NEXT: RETURN
18210 GOSUB 18230; FOR I = 1 TO N: FOR J = 1 TO N: PRINT A(I,J):
NEXT J: PRINT: 18220 RETURN 18230 PRINT "THE INVERSE OF YOUR MATRIX
IS: ": PRINT:RETURN 19000 REM INPUT ELEMENTS BY ROW 19010 PRINT
"ENTER THE ELEMENTS ONE AT A TIME BY ROW AND PRESS ENTER" 19020 FOR
I = 1 TO N: FOR J = 1 TO N 19030 INPUT R(I,J): NEXT J,I 19040 GOTO
18050 Part 4 `FORMULA3` 100 DIM FM(16,1), TM(3,1), T(16,3), V(3,1)
M(3,16), RM(16,1) 110 OPEN "I",1, "DYES" 120 FO;R i = 1 TO 16 130
INPUT#1, T(I,1), T(I,2), T(I,3) 140 NEXT 150 CLOSE 1 160 OPEN
"I",1, "CONCN" 170 INPUT#1, V(1,1), V(2,1), V(3,1) 180 CLOSE 1 190
FOR I = 1 TO 16 200 FM(I,1) = 0 210 J = 1 TO 3 220 FM(I,1) =
FM(I,1) + T(I,J) + V(J,I) (16) 230 NEXT J 240 NEXT I 250 GOTO 500
260 OPEN "I",1, "FUNCTION" 270 FOR I = 1 TO 16 280 INPUT#1, M(1,I),
M(2,I), M(3,I) 290 NEXT 300 CLOSE 1 310 FOR I = 1 TO 3 320 TM(I,1)
= 0 330 FOR K = 1 TO 16 340 TM(I,1) = TM(I,1) + M(I,K)*RM(K,I) 350
NEXT K 360 NEXT I 370 OPEN " O",1, "TRISTIM" 380 PRINT#1,
TM(1,1);TM(2,1);TM(3,1) 390 CLOSE 1 400 LPRINT " " : LPRINT " " 410
LPRINT "TRISTIMULUS VALUES FOR MATCH": LPRINT " " 420 LPRINT " X =
"; TM(1,1):LPRINT " " 430 LPRINT " Y = "; TM(2,1):LPRINT " " 440
LPRINT " Y = " "; TM(3,1):LPRINT " " 450 RUN "FORMULA4" 500 FOR I =
1 TO 16 510 B1 = 2*(1+FM(I,1)) 520 B2 = B1[2 530 RM(I,1) = (B1 -
SQR(B2-4))/2 540 NEXT 550 GOTO 260 Part 5 "FORMULA4" 6000 REM
CALCULATIONS OF COLOR DIFFERENCE 6005 DIM DT(3,1), TM(3,1), A(3,3),
DC(3,1), V(3,1), VXS(1), VYS(1), VZS(1) 6010 PRINT "INPUT VX, VY,
VZ FOR SAMPLE" 6020 INPUT VXS(1), VYS(1), VZS(1) 6060 PRINT "INPUT
VX, VY, VZ FOR MATCH" 6065 INPUT MXV: INPUT MYV: INPUT MZV 6067 FOR
I = 1 TO 1 6210 DVY = ((0.23)*(VYS(I) - MYV))[2 6215 D1VXY =
((VXS(I) - VYS(I)) - (MXV - MYV))[2 6220 D2VZYY = (VZS(I) - VYS(I))
- (MZV - MYV) 6225 D3VZY = ((0.4)*(D2VZYY))[2 6230 DE = (DVY +
D1VXY + D3VZY)[(1/2) 6235 DE = 40*DE 6237 NEXT (17) 6238 LPRINT "
"; LPRINT " " 62440 LPRINT " THE VALUE FOR THE COLOR DIFFERENCE IS
"; DE; LPRINT " " 6250 PRINT " TO CONTINUE ITERATION , `ENTER` 1.
": PRINT " " 6260 PRINT " TO DISCONTINUE ITERATION, `ENTER` 2. ":
PRINT " " 6270 INPUT ZZ 6280 ON ZZ GOTO 10000, 6300 6300 END 10000
OPEN "I",1,1 "VALUES" 10010 INPUT#1, X, Y, Z 10020 CLOSE 1 10030
OPEN "I",1, "TRISTIM" 10040 INPUT#1, TM(1,1), TM(2,1), TM(3,1)
10050 CLOSE 1 10060 DT(1,1) = X - TM(1,1) 10070 DT(2,1) = Y -
TM(2,1) 10080 DT(3,1) = Z - TM(3,1) 10090 OPEN "I",1, "INVERSE
10100 FOR I = 1 TO 3 10110 INPUT#1, A(I1,). A(I2,), A(I3) 10120
NEXT 10130 CLOSE 1 10140 FOR I = 1 TO 3 10150 DC(I,1) = 0 10160 FOR
K = 1 TO 3 10170 DC(I,1) = DC(I,1) + A(I,K)*DT(K,I) 10180 NEXT K
10190 NEXT I 10200 OPEN "I",1, "CONCN" 10210 INPUT#1, V(1,1),
V(2,1), V(3,1) 10220 CLOSE 1 10230 V(1,1) = V(1,1) + DC(1,1) 10240
V(2,1) = V(2,1) + DC(2,1) 10250 V(3,1) = V(3,1) + DC(3,1) 10260
LPRINT " "; LPRINT " " 10270 LPRINT " C1 = ";V(1,1) : LPRINT " "
10280 LPRINT " C2 = ";V(2,1) : LPRINT " " 10290 LPRINT " C3 =
";V(3,1) : LPRINT " " 10300 OPEN "O",1, "CONCN" 10310 PRINT#1,
V(1,1), V(2,1), V(3,1) 10320 CLOSE 1 10330 RUN "FORMULA3" 10340
END
[0034]
9TABLE 11 Color of Standard Soybean Cosmetic Formulations - NUMBER
Y R B 1 1.9 3.7 0 2 3.6 4 0 3 1.3 1.2 0
[0035]
10TABLE 12 Skin Color of Females- NUM COLOR RANGE HUE VALUE CHR
X-BAR Y-BAR Z-BAR Y DE 12 1 1 7.53 4.86 4.03 0.4034 0.3733 0.2234
19 1-4 YR 29 2 2 6.79 4.43 3.54 0.4 0.3619 0.2388 15 4-7 YR 13 3 2
6.63 6 3.5 0.3761 0.3563 0.2677 30 11-12 YR 12 4 4 5.29 3.59 2.99
0.3964 0.356 0.2546 10 7-9 YR 15 5 4 5YR 5.34 3.75 0.3848 0.3562
0.259 23 9-10 22 6 5 4.27 4.68 3.01 0.3777 0.3509 0.2717 17 12-13
YR 5 7 6 3.06 5.73 4.62 0.3968 0.3528 0.2504 27 10-11 YR 10 8 6
3.26 4 2.19 0.3668 0.3403 0.2929 12 17-18 YR 44 9 7 2.5 4 2.86
0.3832 0.344 0.2727 12 14-15 YR 36 10 7 2.47 4.68 3.36 0.3818
0.3464 0.2718 17 13-14 YR 19 11 8 10R 4.68 3.71 0.388 0.3417 0.2708
17 15-16 17 12 8 10R 6 5.38 0.3633 0.3478 0.2889 30 16-17
[0036]
11 Preparation of Triacylglycerol Oligomers Cosmetics 1. Cold Cream
Soybean Z - 6 40.1% Lecithin Sludge 8.1% Water 51.8% 2. Lotion
Soybean Z - 3 30.1% Lecithin Sludge 8.1% Water 60.8% 3. Foundation
Soybean Z - 8 25.0% Lecithin Sludge 8.0% Water 57.0% Pigment 10.0%
4. Lipstick Soybean Z - 10 40.0% Lecithin 8.0% Water 42.0% Pigment
10.0% 5. Pucker Paint Soybean Z - 5 37.3% Lecithin Sludge 8.0%
Water 44.7% Pigment 10.0% 6. Blusher Soybean Z - 6 37.9% Lecithin
Sludge 8.0% Water 44.1% Pigment 10.0% 7. Mascara Soybean Z - 9
48.0% Lecithin Sludge 8.0% Water 34.0% Carbon Black 10.0%
[0037] Color has three qualities which are hue, value and chroma or
intensity. Hue is the quality which distinguishes one color from
another, for example red or blue. It is the name of the color
family. The lightness or darkness of a color is called value. We
can visualize how light or how dark a color is by comparing it with
a value scale showing black at the bottom and white at the top. The
third dimension of color is chroma or intensity. It is often
thought of as the strength or weakness of a color. We can think of
intensity as the degree to which a color departs from a neutral
gray of the same value.
[0038] A pleasing combination of colors is known as a color
harmony. One of the greatest teachers of color harmony is nature.
This phenomenon is apparent in everything that grows. Nature
presents a protusion of colors, beautifully arranged and spaced is
as to present a pleasing spectacle to the eye. Flowers of strong
and weak colors are striking against their background. Trees in the
fall of the year are never more harmonious than in their bright
color schemes of red, orange, yellow, and purple against the
background of clear blue sky with fading green grass and brown
earth in the foreground. These colors brings a change of hues,
values, and chroma, and presents a beautiful color scheme. There
are four general ways to combine colors; contrast in hue, value,
chroma and area. The Munsell color theory suggests three paths for
color harmony: The first path is vertical with rapid changing
value. We refer to this color harmony as SOPHISTICATED. The second
path is lateral. This is a rapid change of hues adjacent on the
color wheel. We refer to this color harmony as EXOTIC. The third
path is inward. The inward path leads to the neutral center and
onto the opposite on the Munsell color wheel. We refer to this
color harmony as PROVACATIVE.
[0039] Using the color of the skin, the color of the eyes, the
color of the hair and a related red a computer program was
developed to produce sophisticated, exotic, and provocative color
harmony schemes for skin colors shown in Table 13.
12TABLE 13 Listing for Cosmetic Wardrobe Computer Program
[0040]
13TABLE 14 Color Harmony Data for Color No. 35 C LOR HUE VALUE CHR
MA HAIR 4.5 R 2.3 4.5 EYES 6.7 B 3.4 1.2 SKIN 3.5 yr 4.4 3.3
RELATED RED 4.4 r 2.3 1.4
[0041]
14TABLE 15 Color Harmony Data for Color No. 45 COLOR HUE VALUE
CHROMA HAIR 4.5 4.5 4.5 EYES 6.7 6.7 6.7 SKIN 8.9 8.9 8.9 RELATED
RED 6.7 6.7 6.7
[0042]
15TABLE 16 Cosmetic Wardrobe Listing for Color No. 35 COSMETIC CODE
COLOR DIFFERENCE 1.98 FOUNDATION DEEP COCOA #11 BLUSHER TITIAN
LIPSTICK #11 DAZZLE DUST VIOLET PUCKER PAINT CURRANT
[0043]
16TABLE 17 Cosmetic Wardrobe for Color No. 45 COSMETIC CODE COLOR
DIFFERENCE 0.456 FOUNDATION DEEP COCOA #11 BLUSHER BURGUNDY LIQUID
LINER BROWN MASCARA BLACK LIPSTICK 4 LIPGLOSS 4 DAZZLE DUST BRONZE
FROST PUCKER PAIN AMETHYST
[0044] Heat-set web offset ink was introduced in the 1950's as a
printing process and is used for the production of magazines,
catalogues and brochures. All heat-set inks are expected to fulfill
exacting criteria, in addition to properties of cold-set ink, such
as high gloss and dry quickly in an oven. Heat-set ink are dried by
passing the printed web of paper through an oven using high
velocity hot air; sufficient to raise the temperature of the to
100-140 C. TAGOS ink has been formulated which meet the criteria of
heat-set web offset ink and does not need to be passed through an
oven for drying. This is accomplished by formulating printing ink
using TAGOS of viscosity above 300 poises to obtain high gloss and
rub-off resistance. Quick drying is accomplished by using a drying
agent.
17TABLE 18 Soybean Oligomer Printing Ink - Formula I SUBSTANCE
PERCENT CARBON BLACK 20 SOYBEAN OLIGOMER Z - 6 71 CLAYTONE HY 9
[0045]
18TABLE 19 Soybean Oligomer Printing Ink - Formula II SUBSTANCE
PERCENT CARBON BLACK 20 SOYBEAN OLIGOMER Z - 6 70 CLAYTONE HY 9
COBALT ACETATE 1
[0046]
19TABLE 20 Soybean Oligomer Printing Ink - Formula III SUBSTANCE
PERCENT CARBON BLACK 15 SOYBEAN OLIGOMER Z - 10 30 SOYBEAN OLIGOMER
Z - 3 40 CLAYTONE HY 9 COBALT ACETATE 1
[0047]
20TABLE 21 Soybean Oligomer Printing Ink - Formula IV SUBSTANCE
PERCENT CARBON BLACK 20 SOYBEAN OLIGOMER Z - 6 61 CLAYTONE HY 9
POLYOL 10
[0048]
21TABLE 22 Cottonseed Oligomer Printing Ink - Formula V SUBSTANCE
PERCENT CARBON BLACK 20 COTTONSEED OLIGOMER 71 CLAYTONE HY 9 COBALT
ACETATE 1
[0049]
22TABLE 23 Sunflowerseed Oligomer Printing Ink - VI SUBSTANCE
PERCENT CARBON BLACK 20 SUNFLOWERSEED OLIGOMER 71 CLAYTONE HY 9
COBALT ACETATE 1
[0050]
23TABLE 24 Corn Oligomer Printing Ink - VII SUBSTANCE PERCENT
CARBON BLACK 20 CORN OLIGOMER 71 CLAYTONE HY 9 COBALT ACETATE 1
[0051]
24TABLE 25 N,N'-di-n-butyl-N.sub.a-lauroyl Glutamide(BLG) Soybean
Oligomer Printing Ink - VIII SUBSTANCE PERCENT CARBON BLACK 20
BLG-SOYBEAN OLIGOMER* 71 CLAYTONE - HY 9 *Preparation given in
Section VI
[0052]
25TABLE 26 Thermosetting Epoxy Printing Ink SUBSTANCE PERCENT
EPOXY(I) SOYBEAN* 70 PHTHALO BLUE PIGMENT 15 SOLVENT 5 HyTONE 5
*See Section IX
[0053]
26TABLE 27 Fountain Solution SUBSTANCE PERCENT A B DICK UNIVERSAL
95 T-BUTYL HYDROPEROXIDE 5
[0054] In screen printing the ink is forced through the open areas
of a stencil supported on a mesh of synthetic fabric stretched
across a frame. The ink is mechanically forced through the mesh
onto the substrate underneath by drawing a squeegee across the
stencil. These inks are high viscosity, low tack, short cure times,
and good color retention after several wash cycles. TAGOS were
formulated to meet these criteria.
27TABLE 30 Screen Printing Ink - Formula I SUBSTANCE PERCENTAGE CI
PIGMENT RED 49 20 SUNFLOWERSEED OLIGOMER 30 SOYBEAN OLIGOMER Z - 6
50
[0055]
28TABLE 31 Screen Printing Ink - Formula II SUBSTANCE PERCENTAGE CI
PIGMENT RED 49 20 SUNFLOWERSEED OLIGOMER 30 SOYBEAN OLIGOMER X - Y
50
[0056]
29TABLE 32 Screen Printing Ink - Formula III SUBSTANCE PERCENT CI
PIGMENT RED 49 20 SUNFLOWERSEED OLIGOMER Z-6 30 SOYBEAN OLIGOMER
Z-6 25 SOYBEAN OLIGOMER X-Y 25
[0057]
30TABLE 33 Screen Printing Ink - Formula IV SUBSTANCE PERCENT BLUE
DYE 10 SOYBEAN OLIGOMER Z - 6 25 WATER 74.98 THICKNER 0.1 COBALT
ACETATE 0.1
[0058]
31TABLE 34 Screen Printing Ink - Formula V SUBSTANCE PERCENT BLUE
DYE 10 COTTONSEED OLIGOMER 25 WATER 74.98 THICKNER 0.1 COBALT
ACETATE 0.1
[0059]
32TABLE 35 Screen Printing Ink - Formula VI SUBSTANCE PERCENT BLUE
DYE 10 SUNFLOWERSEED OLIGOMER 25 WATER 74.98 THICKNER 0.1 COBALT
ACETATE 0.1
[0060]
33TABLE 36 Screen Printing Ink - Formula VII SUBSTANCE PERCENT BLUE
DYE 10 CORN OLIGOMER 25 WATER 74.98 THICKNER 0.1 CORN 0.1
[0061] The inks were printed on cotton and coated cotton fabrics
and allowed to dry. The printed fabrics were then washed and dried.
The color was measured before and after each wash cycle to
determine color fastness.
34TABLE 37 Color Fastness of Screen Printed Uncoated Cotton Fabrics
Gray INK Change- FORMULA L* a* b* L* a* b* Difference I 36.31 43.35
12.60 37.59 38.00 9.97 3.00 6.10 II III IV 38.99 -14.21 -39.57
40.96 -12.85 -35.00 3.00 5.16 V VI VII
[0062]
35TABLE 38 Color Fastness of Screen Printed Coated Cotton Fabrics
Gray COLOR BEFORE COLOR AFTER Change- INK FORMULA L* a* b* L* a* b*
Difference I 37.63 47.09 12.42 39.55 44.52 9.44 3.00 4.37 II III IV
38.99 -14.21 -39.57 40.96 -12.85 -35.00 3.00 5.16 I
[0063] Although many valuable products are fabricated each day from
fibers, these items could never exist unless a finish had been
applied to the fibers during the extrusion or spinning process.
Fabric finishing is intended to provide a special performance
characteristics or properties to a textile fabric. This can be the
development of dimensional control or resistance to wrinkling
during use. The characteristics may be the provision of permanent
crease and smooth drying performance or the requirement for the
fabric to withstand subsequent processing steps. There may be the
need for a finish to impart resistance to end use exposure, i.e.,
water or oil repellency or resistance to crocking or bleeding. Of
equal importance is the need to provide the finished fabric with
improved or changed aesthetic properties. TAGOS were developed for
applications in sizing and finishing.
[0064] Solutions to size fabrics were made according to the formula
given in Table 39. TAGOS were soybean, cottonseed, sunflowerseed,
and corn. Strips of gauzy cotton fabric (5.times.30 cm were padded
twice at 25 C. to ca. 110% wet pick-up, followed by drying at 120
C. for 3 minutes and conditioning for 48 hours at 65% relative
humidity and at room temperature.
[0065] Textile finishers were made using soybean, cottonseed,
sunflowerseed, and corn oligomers according to the formula given in
Table 40. Poplin cotton fabric pieces (30.times.45 cm) were padded
twice at room temperature in the finish solution to ca. 80% wet
pick-up, followed by drying (100 C./3 min.) and curing (160 C./3
min.). The cured samples were then given an after wash in a bath
containing g/il sodium carbonate along with 1 g/I on triton X-100
at 55 C. for 15 minutes./rinsed, and air dried, and
conditioned.
36TABLE 39 Formula for Textile Sizers SUBSTANCE PERCENTAGE TAGO 12
TRITON X - 100 5 WATER 83
[0066]
37TABLE 40 Formula for Textile Finishers SUBSTANCE PERCENTAGE TAGO
25 WATER 65 MAGNESIUM CHLORIDE HEXAHYDRATE 5 TRITON X-100 5
[0067] Historically, reactions on polymers have been of major
importance, as they have made possible the applications of
cellulose as textile fibers, plastics, coatings, and even
explosives. Reactions of polymers can occur with oxygen,
irradiation, heat, moisture, and bacterial attack which induces the
problem of "aging" of polymeric materials. The most important of
them are atmospheric oxygen and irradiation, since they are most
likely to induce chain scission. Polymers can undergo chemical
reactions by chemical modification of the functional groups of the
polymers. As discussed earlier a Diels-Alder diene synthesis was
used as a basis for explaining the polymerization of TAGOS which is
most often referred to in the literature. Most investigators agree
with the formation and presence of hydroxyl groups, carboxylic acid
groups, cyclic compounds, and double bonds during thermal
polymerization. These functional groups along with the ester group
provide the basis for producing polymers from TAGOS.
[0068] An equivalency based on hydroxyl number of the glycol and
assumed hydroxyl number of TAGOS per molecule was calculated. The
hydroxyl number for glycol was two and the hydroxyl number for TAGO
varied for each experiment. The equivalency mass for glycol was the
molecular weight divided by two. The equivalency mass for TAGOS was
obtained by dividing the apparent molecular weight by the hydroxyl
number for each experiment. Apparent molecular weights were
determined by gel permeation chromatography. An illustrative
example was the formation of complexes between soybean oligomer
(SBO) and ethylene and propylene glycol. The apparent molecular
weight of SBO was 10,000.
[0069] A series of experiments were conducted using N,N'- di
n-butyl-N.sub.a-lauroyl glutamide (BLG) to crosslink TAGOS. One
gram of BLG was dissolved in 99 grams of TAGOS and heated to
150.degree. C. The solution viscosity increased depending on the
amount of BLG added.
38TABLE 43 Triacylglycerol Oligomer Complexes with Ethylene and
Propylene Glycol TAGOS VISCOSITY HYDROXYL* MOL. WT. GLYCOL RATIO
VISCOSITY SOYBEAN 22683cp 10 10000 ETHYLENE 1::1 17733cp SOYBEAN
22683cp 10 140000 PROPYLENE 1:01 17983cp
[0070] When ethylene glycol, 10 grams, was mixed with SBO, 300
grams, the solution thickened and became very turbid. The mixture
was heated up to a temperatures of 120.degree. C. and a white vapor
was given off. The mixture was removed from the hot plate for
thirty minutes after which time the mixture was replaced on the hot
plate and heating continued. No vapors were given off after heating
for 3.75 hours. After heating for more than six hours the mixture
became completely clear with the appearance of small crystal like
substances at the bottom if the flask. After more than nine hours
of heating, the mixture was removed from the heat and allowed to
cool. As it cooled down to room temperature it became a turbid
viscous mixture.
[0071] SBO, 306 grams, was mixed with propylene glycol, 10 grams,
in an Erlenmeyer flask. The mixture remained clear after mixing.
The mixture was heated to a temperature of 120.degree. C. The
mixture was heated to a temperature of 115.degree. at which time
white vapors were given off. However, the mixture remained clear.
After more than eight hours of heating, the mixture was removed
from the hot plate and cooled to room temperature. At room
temperature, the mixture became very turbid and viscous.
[0072] Emulsion polymerization of linseed and safflower acrylates
and methacrylactes were prepared by Joshi (1978). The alcohol were
first prepared by Rheberg's (1946) procedure involving the
alcoholysis of methyl acrylate or methyl methacrylate in the
presence of an acid catalyst and a polymerization inhibitor. In a
one liter two-necked round-bottomed flask are placed 200 grams of
soybean resin and 50 grams of methyl acrylate, 2 grams of
hydroquinone, and 500 milligrams of p-toluenesulfonic acid. The
flask is attached to an all-glass fractionating column without
packing and the solution is heated to a temperature of 100.degree.
C. using a heating mantle and stirred with a magnetic stirrer. The
column is operated under total reflux until the temperature of the
vapors at the still head falls to 62-63.degree. C. which is the
boiling point of the methanol-methyl acrylate azeotrope. This
azeotrope then distilled as rapidly as it is formed, the
temperature at the still head not being allowed to exceed
65.degree. C. When the production of methanol has become very low
(6-10 hours), the excess methyl acrylate is distilled. The soybean
resin methacrylate mixture is extracted with suitable solvent(s) to
remove the hydroquinone and p-toluenesulfonic acid. The soybean
resin methacrylate is characterized by IR spectroscopy. All
polymerization reactions were carried out in emulsion using the
standard procedure of Fisher and Mast (1940) suitably modified to
meet our requirements. The exact procedure followed is described
below. A 250 ml capacity ground-glass joint Erlenmeyer flask,
carrying a Teflon-enclosed magnetized stirring bar and fitted with
a reflux condenser, is charged with 40 ml of deionized water, 200
mg of Triton X-100, 200 mg of SLS-Liquid, and 1-2 mg of ammonium
persulfate. The solution is stirred slowly on a hot plate with
magnetic stirring, and 50 grams of soybean resin methyacrylate is
added into it. Heat is initially applied to induce polymerization
and thereafter continued at a rate just sufficient to cause gentle
refluxing. The polymerization is considered to be completed when
the emulsion becomes very viscous. The viscous material is then
shaken shaken with warm water and the suspension centrifuged. The
process is repeated two or three times to remove the surfactant
completely. The mass is then dried in a vacuum and films cast on
tin plates (1 mil, dry).
[0073] Vinyl and allyl ester of soybean resin were prepared using
the method of Swern and Jordan (1948). In a 500-ml round bottom
three-necked flask provided with a thermometer, a reflux condenser,
and a gas inlet tube through which steam or nitrogen is passed are
placed 100 grams of freshly of freshly distilled vinyl acetate and
grams of 200 grams of soybean resin viscosity Z-6. and 1.6 grams of
mercuric acetate is added. The mixture is shaken by hand for about
30 minutes, and 0.15 ml of 100% sulfuric acid is added dropwise.
The solution is heated under reflux for 3 hours, then 0.83 grams of
sodium acetate trihydrate is added to neutralize the acid. The
excess vinyl acetate is recovered by distillation at atmospheric
pressure (vapor temperature about 70-80.degree. C.) until the
solution temperature reaches 125.degree. c. The distillation is
completed at 10 mm of Hg or lower.
[0074] Polymerization is carried out in one ounce screw cap bottles
equipped with oil resistant gaskets and perforated caps so that
small samples could be removed with a hypodermic syringe without
opening the bottles. The bottles were charged with soybean resin
vinyl ester and 3% d-t-butyl peroxide. The bottles were heated by
suspending them in an oil-bath maintained at the desired
temperature. The polymers are isolated by stripping the monomers in
vacuo (0.1 mm) at a maximum temperature of 200.degree. C., and
extracting the residue repeatedly with methanol.
[0075] Soybean X-Y, TAGO 310 grams, is added into a closed reactor
and purged with nitrogen for a few minutes. The oligomer is heated
to about 260.degree. C. with constant stirring. The stirring is
continued throughout the reaction. Dicyclopentadiene, 104 ml, is
added at a slow addition rate of 0.4 to 0.6 ml/min at the bottom of
the vessel under the hot TAGO. After the addition of
dicyclopentadiene is complete, the reaction mixture is kept at
260.degree. C. for 3.5 hours with stirring. Then the mixture is
stripped at 1 mm Hg for 30 minutes and removed from the reaction
vessel. The product is cooled to room temperature.
[0076] Soybean oligomer Z-6(TAGO), 500 grams, is heated to
145.degree. C. and 1000 g of myrcene and 10 grams of di-tert-bu
peroxide is added. The reaction is continued for 6 hours at
140-150.degree. C. The modified TAGO is treated with 0.05% Co and
heated in a dryer.
[0077] Vegetables oils as an alternative diesel and fossil fuel is
limited by their high viscosity. Several routes have been tried for
reducing this viscosity and most recently has been the direct
catalytic upgrading of the vegetable oils to produce liquid fuels.
The catalytic cracking of vegetable oils, which is nothing more
than reduction of the molecular weight and viscosity, gives several
types of products, either gaseous, solid, or liquid. Numerous
reports are given in the literature for the catalytic cracking of
soybean oil and other vegetable oils. Most investigations have
shown that the products obtained from the cracking process are
comparable to diesel fuel but not to fossil fuel. The physical
properties and chemical compositions of bio and fossil fuels were
determined by Pioch (1993). The results showed that the aromatic
content of fossil fuel is higher than the aromatic content of
biofuels. The olefin content is in the same range as well as the
saturated branched chain hydrocarbons. The octane number for fossil
fuel was reported as 90 and that of catalytically cracked copra and
palm stearine were 91 and 86 respectively. Concerning the diesel
fractions, the chemical compositions are close to the fossil fuels
The biodiesel fuel had a high content of normal paraffin, no
olefins and no heavy hydrocarbons and similar aromatic content as
the fossil diesel fuel. Kobayashi (1921) distilled soybean and
coconut oil mixed with kaolin at approximately 700.degree. C.
decomposed to give " vegetable petroleum" or biofuel. During world
war II, Chang (1947) reported that large scale decomposition of
tung oil and soybean oil was carried out in large scale batch
reactors in China, with the use of acid(AlCl.sub.3) or basic (MgO,
CaO, NaOH) catalysts.
[0078] Attempts to produce fuel that could be gasoline substitute,
i.e. contain a significant fraction of aromatics are reported in
the literature. Novella (1984) applying ZSM-5 type zeolites in acid
form transformed various kinds of vegetable oils to hydrocarbon
fuel. The use of soybean oligomer as a feed stock for catalytic
cracking to increase the aromatic content of biofuels is evident
from the proposed chemical structure of the repeating unit. As
described in the introduction the Diels-Alder diene synthesis has
received the most support from data collected for the
polymerization mechanism of TAGS. This mechanism, wherein a diene
and a dienophile combine to form a cyclohexene structure is
supported by data showing the presence of cyclic structures in
polymerized oils. It is therefore proposed to investigate the
formation of biofuels with high aromatic content by reductive
catalytic hydrocracking of TAGOS of differing viscosity. Filho
(1993) reported a production yield (weight % of feed) using soybean
oil of 66.6% alkanes, 11.9% cycloalkanes, 4.3% alkylbenzenes. The
authors concluded that depending upon the multifunctionality of the
catalyst, isomerization, cyclization, and aromatization processes
can occur during hydrocarbon fuel production from vegetable oils.
Using a similar approach with the resin, it is the expectation to
obtain a biofuel that is high in aromatic content comparable to
fossil fuel due to existence gcyclic structures in TAGOS.
[0079] Reductive catalytic hydrocracking will be with either a two
gallon or a 50cm.sup.3 (Autoclave Engineering) stainless steel
batch reactor equipped with a stirrer, and the temperature and
pressure limits being 450.degree. C. and 25 MPa respectively. The
feedstock consists of soybean resin with viscosity of 500 poises
and 1000 poises using catalysts precursors of NiMo/-Al.sub.2O.sub.3
and Ni/SiO.sub.2 (2 wt % based on resin) and elemental sulfur (1.75
wt % based on resin). The procedure of Filho (1993) was
followed.
[0080] Maplewood shavings, 16.1 grams, and soybean oligomerZ- 6,
53.5 grams, were mixed together until all shavings of maplewood
were covered with the oligomer. The mixture was placed in a 8-1/2
cm daimeter.times.7 mm thick brass dish. Hot air was blown over the
mixture for one hour. The mixture was placed in a convection oven
at 75.degree. C. for 26 hours. The board was removed and allowed to
cool to room temperature and examined. The board was spongy.
[0081] Addition of sodium hydroxide to soybean Z-6 on standing
formed a solid polymer film.
[0082] Addition of sodium hydroxide to soybean X-Y on standing
formed a turbid solution and a lot of foam when shaken.
[0083] Lawn grass with long stems and long blade-like leaves was
cut into small pieces and dried. The grass sample was then placed
into a mill and reduced to small fragments. A small mesh screen was
used to separate the smallest pieces from the larger pieces. The
smaller pieces were used for the preparation. Grass, 2.0 grams, was
mixed with SBO, 200 grams, in an Erlenmeyer flask. The mixture was
stirred and placed on a hot plate. After approximately one hour of
heating the mixture turned a very dark green. The mixture was
heated for a total of twenty one hours, removed from the hot plate
and allowed to cool to room temperature. The viscosity of the
mixture was determined.
39TABLE 44 Viscosity Data for Complex Between Triacylglycerol
Oligomers and Gramineae (Grass) TAGOS TAGO VISCOSITY COMPLEX
VISCOSITY SOYBEAN 22,683 cp 33,367 cp COTTONSEED SUNFLOWERSEED
CORN
[0084] Johnson's pure cotton balls, made from 100% pure,
non-chlorine bleached cotton, was purchased from a local drug
store. One cotton, which weighed 0.3 grams, was pulled into small
pieces and added one at a time to an Erlenmeyer flask containing
203 grams of SB(Z-6) which had been heated to 100.degree. C. The
mixture was stirred and placed on a hot plate. After heating for
approximately seven hours at 110.degree. C. the cotton started to
form gelatinous mass. It was not observable whether the liquid
portion of the mixture was also becoming more gelatinous. Continued
heating of the mixture resulted in the cotton becoming almost
completely gelatinous. The mixture was removed from the hot plate
after 40 hours of heating. The viscosity of the liquid portion was
measured.
40TABLE 45 Data for Complex Between Triacylglycerol Oligomers and
Cotton TRIACYLGLYCEROL OLIGOMER COMPLEX VISCOSITY, P SOYBEAN (Z-6)
>8,000,000 cp COTTONSEED SUNFLOWERSEED CORN
[0085] Removal of ink from paper substrate is done commercially
using ink removal solutions containing hazardous materials. It has
been previously shown that TAGOS can be emulsified using water and
a surfactant. Paper printed with TAGOS inks are easily dissolved in
a solvent system using non- hazardous water-based cleaning
solutions which emulsifies the ink and can be reused several times
before it has to be replaced. The ink solution is filtered to
remove the deinked paper slurry which can then be further processed
to produce recycled paper.
41TABLE 28 Formulation of Ink Removal Solution #1 CONSTITUENT
PERCENT PART A* 89.07 WATER 85.07 SWS 0.1122 DYE 1.68 MONOETHA
NOLAMINE 2.25 NA4EDTA 2.81 DIPROPYLENEGL; YCOLMETHYLETHER 3.37
WITCONATE 90 K 4.27 PART B* 10.93 TRITON X-100 64.04 HYAMINE 8.51
SCENT 27.45
[0086]
42TABLE 29 Formulation of Ink Removal Solution #2 CONSTIUENT
PERCENT TRITON X-100 1 POTASSIUM HYDROXIDE (37.4%) 13.37 WATER
85.63
[0087] Approximately three drops of red ink was placed on a
5".times.8" piece of white papter and drawn down with a putty knife
making an ink strip approximately 3" in width. A length of
approximately 2" was cut and used for the test.
[0088] In one Erlenmeyer flask was placed 100 ml of formula #1
cleaning solution along with the test specimen. In another
Erlenmeyer flask was placed 100 ml of formula #2 cleaning solution
along with the test specimen. Both solution were shaken and allowed
to stand. Periodically on several occasions they were shaken again.
Ink began to be removed immediately with formulation #1 as evidence
by the solution forming a reddish color. With formulation #2 color
was being removed as evidence by the fading of the test
specimen.
[0089] The mixture obtained from printed paper is filtered and the
solution decanted. The paper slurry remaining is mixed with and
emulsion prepared using soybean oligomer Z-6(25%), triton
X-100(5%), and water (70%). The mixture is filtered and then dried
by passing through pads heated to 75.degree. C. A sheet of recycled
paper is formed.
[0090] TAGOS interaction with metals and water were examined. The
examination was to determine differences in the interaction between
metal-TAGO complex and water-TAGO complex. Soybean oligomer Z-6 and
X-Y, 5 grams each, were placed in separate containers of 95 grams
of distilled water. The mixtures were stirred and allowed to stand
at room temperature. The same procedure was repeated with 0.2 m
potassium hydroxide solution.
[0091] Both soybean oligomers X-Y and Z-6 had formed two layers.
The aqeuous layer was slightly turbid and a white oily layer. Upon
standing at room temperature for a long period of time, soybean
oligomer Z-6 formed a rubbery, spongy mass. This mass is probably
due to the interaction of air, water and the oligomer.
[0092] Water was added to a beaker which contained soybean oligomer
crosslinked with BLG. The mixture was heated to boiling. The sides
of the beaker were scraped with a spatula. Upon cooling, polymer
particles were floating in the water. The particles were removed
from the water and allowed to dry. Upon drying, the small particles
formed clear plastic pieces. The plastic pieces were very elastic
and stretched when pulled. The plastic pieces were soft and
spongy.
[0093] Upon addition of 0.2 m KOH to soybean oligmer X-Y, the
solution turned milky white with no formation of oil droplets. A
foamy layer was on top. Upon addition of 0.2 m KOH to soybean
oligmer X-6 it also formed a milky/cloudy solution with a foamy
layer on top. However, upon standing for a long period of time,
soybean oligomer X-Y produces large amount of foam when shaken with
no visible large particles present. The solution, however, is still
turbid. In the case of soybean oligomer Z-6, the mixture does not
produce a lot of foam when shaken, and it contained solid
particles.
[0094] Thus, in accordance with the present invention, there has
been provided triacylglycerol oligomers and methods for making and
using same that fully satisfies the objectives and advantages set
forth above. Although the invention has been described in
conjunction with the specific drawings and language set forth
above, it is evident that many alternatives, modifications, and
variations will be apparent to those skilled in the art.
Accordingly, it is intended to embrace all such alternatives,
modifications and variations that fall within the spirit and broad
scope of the invention.
* * * * *