Alkoxylated dioxolanes as paper sizing agents

This invention concerns a new class of compositions for the sizing of paper and the method of treating paper using such compositions. Such new compositions comprise the reaction products of glyoxal and a hydrophobe which contains at least one hydroxyl group. Such compositions can be used either for internal or surface sizing.

BACKGROUND 
Paper is sized to resist the penetration of liquids. This invention is 
concerned with the sizing of paper to resist penetration by water and 
aqueous solutions. 
Paper can either be surface sized or it can be sized internally. Internal 
sizing is accomplished by the application of a sizing agent to the pulp 
slurry prior to formation of the paper sheet. Surface sizing, on the other 
hand, entails application of the sizing agent to the surface of a formed 
paper sheet. Internal and surface sizing are discussed in J. P. Casey, 
Pulp & Paper, Chemistry and Chemical Technology, Second Edition, Volume 
II, Interscience Publishers, Inc., New York, 1960. 
For well over a century, internal sizing operations have employed rosin in 
combination with alum. Various improvements in the rosin-alum treatment 
have been made. 
More recent internal sizing agents include wax emulsions, stearates, 
alkylketene dimers and alkenyl succinic anhydrides. Most of these new 
sizes are described in TAPPI Monograph Series 33, "Internal Sizing of 
Paper and Paperboard," Mack Printing Company/Easton, PA, 1971. 
Current commercial internal sizing agents have important individual 
drawbacks. For example, rosin requires alum and an acid pH in papermaking. 
Alkylketene dimers give best performance in a non-acid system. Alkenyl 
succinic anhydrides cannot be produced as stable emulsions and require 
special emulsification at the site of use. Some other sizes are less 
efficient or have other particular drawbacks. 
OBJECTS 
It is an object of this invention to provide new efficient sizing agents 
useful in both surface and internal sizing of paper. 
Another object of this invention is to provide sizing agents effective 
against acid, neutral and alkaline solutions. 
A further object is to provide sizing agents which can be used over the pH 
range normally encountered in papermaking. 
Yet another object is to provide sizing compositions in ready-to-use form. 
THE INVENTION 
The invention is a class of paper sizing compositions and the method of 
application to paper furnishes. Such compositions comprise the 
acid-catalyzed reaction product of glyoxal and a hydrophobe containing at 
least one hydroxyl group. 
We are aware of U.S. Pat. No. 2,242,051, wherein H. Beck teaches a process 
for producing water-repellent textile materials by treatment of such 
materials with the acid-catalyzed reaction product of fatty alcohols and 
glyoxal. Webster's Third International Dictionary defines "textiles" as 
"cloth, woven or knit cloth, fiber, filament or yarn used in making 
cloth." 
An earlier application, Ser. No. 893,639, since abandoned, taught the 
reaction of aqueous 40% glyoxal with hydrophobic alcohols at acid pH and 
the method of wet end and surface application to paper to provide sizing. 
Since that application was abandoned, we have now: 
(a) established predominant chemical structures of our glyoxal-hydrophobic 
alcohol sizes 
(b) shown that appreciably higher sizing performance can be realized for 
use of aqueous glyoxal of appreciably above 40% concentration 
(c) shown that for use of such higher concentration glyoxal, further 
outstanding improvement in paper sizing performance can be realized by 
increasing the ratio of glyoxal to hydroxyl hydrophobe to levels not 
taught in the earlier art. 
(d) determined that the active ingredients for optimized sizing, either 
internal or surface, are glyoxal-hydrophobe reaction products which are 
dimeric or trimeric dioxolanes. 
Gyloxal 
Although monomeric glyoxal can be produced in the laboratory, generation of 
such glyoxal is generally impractical for industrial purposes. We prefer 
to use aqueous glyoxal such as commercial 40% or 80% glyoxal or other 
concentrations as attained by stripping or adding water from or to 
commercially availably glyoxals. 
The Hydrophobe 
The hydrophobe will be chosen from the group consisting of: 
(a) linear and branched, saturated and unsaturated fatty alcohols 
containing from 10-30 carbon atoms; and 
(b) esters formed from the esterification of a polyol containing from 2-6 
hydrocarbon atoms with a fatty acid containing from 10-30 carbon atoms 
wherein the resulting esters contain at least one free hydroxyl group. 
Preferable hydrophobes include such fatty alcohols as cetyl alcohol, 
myristyl alcohol, stearyl alcohol, decanol, dodecanol and olyeyl alcohol 
and esters such as sorbitan tristerearate and pentaerythritol disterarate. 
An especially preferred hydrophobe is a commercially available blend of 
C.sub.16 -C.sub.20 linear alcohols known as Alfol 16-20 H.sup.+. 
Reactant Ratios 
In reacting the glyoxal and the hydrophobe, the ratio of glyoxal to 
hydrophobe should be from 0.1 mole to 6.0 mole of glyoxal to each hydroxyl 
group in the hydrophobe. Preferably the ratio will be from 0.2 moles to 
3.0 moles glyoxal to each hydroxyl group, and most preferably this ratio 
will be between 0.4-2.0 moles glyoxal to each hydroxyl group. 
Catalysis and Reaction Temperature 
It is preferred that acid be used to catalyze the reaction. When 
concentrated sulfuric acid is used, the amount should range from 0.1-50% 
based on the weight of the glyoxal and hydrophobe combined. Reaction times 
generally range from 5 minutes to 6 hours. 
Other acidic catalysts may be used in lieu of the sulfuric acid including 
mineral acids such as hydrochloric acid, organic acids such as p-toluene 
sulfonic acid and acid salts such as ferric chloride and zinc chloride. 
The reaction temperature should be in the range of room temperature to 
100.degree. C. Preferably, the reaction temperature will be from room 
temperature to 80.degree. C. 
Application of Glyoxal-Hydrophobe Reaction Products 
A preferable form of the internal sizing agent is as a fine particle size 
emulsion or suspensoid. The term colloid will be used herein to refer to 
both emulsions and suspensions of solids. 
The glyoxal-hydrophobe reaction product lends itself well to emulsifiction 
in water. Colloids containing up to 40% of the glyoxal-hydrophobe reaction 
product can be prepared at the site of use or they can be prepared at the 
point of manufacture and shipped as ready-to-use products. 
Those skilled in the art will recognize that certain additives such as 
protective colloids and surfactants will aid in producing stable, fine 
particle size aqueous colloids. Useful surfactants include polyethylene 
oxide adducts. Useful protective colloids include guar gum, locust bean 
gum, polyvinyl alcohol, and hydroxyethyl cellulose. 
Optimal wet-end application of the glyoxal-hydrophobe reaction product 
requires use of binding agents to attract and bind the sizing composition 
to the pulp fibers. Various binding agents can be used including cationic 
agents, anionic agents and nonionic agents. 
Useful cationic agents include cationic hydrocolloids such as cationic 
starches and cationic gums, cationic homopolymers such as diallyl dimethyl 
ammonium chloride polymer, diallyl amine polymer, ethylenimine polymer; 
cationic copolymers such as cationic acrylamide copolymers, cationic 
thermosetting resins, cationic epichlorohydrin-amine resins, cationic 
amino polyamides, ethylene dichloride-ammonia reaction products, long 
chain fatty amines and aluminum chloride. Useful anionic agents include 
anionic surfactants, anionic hydrocolloids such as anionic starches and 
carboxymethyl-cellulose and anionic polymers such as acrylamide-acrylic 
acid copolymers. Non-ionic agents include gums such as locust bean gum and 
guar gum. 
The preferred binding agents include cationic starches, cationic 
epichlorohydrin-amine resins, cationic amino polyamides, ethylene 
dichloride-ammonia reaction products and polydiallyl dimethyl ammonium 
chloride. 
When used for internal sizing, the glyoxal-hydrophobe reaction product in 
combination with a binding agent (sizing composition) is added to the 
aqueous pulp suspension at a point after refining is complete and prior to 
sheet formation. The sizing composition will generally be added to the 
pulp suspension as a dilute solution. 
The preferred ratio of binding agent to glyoxal-hydrophobe reaction product 
for purposes of internal sizing will depend upon the nature of the binding 
agent. Generally, the ratio of the binding agent to the glyoxal-hydrophobe 
reaction product will be in the range of about 1:20 to 4:1. 
We do not restrict ourselves as to manner of combination (of the size and 
binding agent). Thus, for example, they can both be incorporated in the 
colloidal sizing composition, or be added separately to the paper system 
for wet end application. 
The amount of glyoxal-hydrophobe reaction product added to the aqueous pulp 
slurry will generally be from 1 to 30 pounds per ton based on the weight 
of dry cellulose fiber (0.05-1.5%). Efficient performance of internal 
sizing agents requires that the agents be well dispersed in the pulp 
slurry prior to formation of the paper sheet. This insures that the sizing 
agent will be uniformly distributed among the cellulose fibers of the 
dried paper sheet. Following addition of the sizing composition to the 
pulp furnish, the paper sheet is formed and dried. 
The glyoxal-hydrophobe reaction product in combination with a binding agent 
as described above may be used in surface sizing as well as in internal 
sizing of paper. A cationic hydrocolloid such as a cationic starch would 
be a useful binder in such applications. The glyoxal-hydrophobe reaction 
product may also be used satisfactorily in surface sizing in the absence 
of a binding agent. 
The surface size is applied in the conventional way during paper 
manufacture by treating the partially dried cellulose fibers. After 
treatment the sheet is dried to leave a residue on the paper surface. The 
dosage of the sizing composition should be from 0.05-1.0% based on the dry 
weight of the paper being surface sized.

EXAMPLES 
Synthesis and testing work was carried out as described below to determine 
the efficacy of the invention. 
Glyoxals used included a commercial grade of glyoxal solution of 40% 
concentration, this material concentrated to 70% by vacuum distillation, 
and a commercial grade of 80% glyoxal in solid form. 
The sulfuric acid used was analytical grade concentrated sulfuric acid of 
95-98% assay. As a matter of simplicity in much of the work, a commercial 
grade of cationic starch was used. For this purpose, the starch was cooked 
in water at 200.degree. F. for 30 minutes and quenched to 3% or lower 
concentration. 
To study preparation of colloidal emulsions, a laboratory hand homogenizer 
was used. 
The examples below describe the preparation and evaluation of various 
sizing compositions falling within the teaching of the invention. 
Evaluations were carried out on paper, using handsheets prepared on a 
laboratory Noble & Wood sheet machine. A bleached softwood-hardwood blend 
of 50 seconds Williams slowness was used. The diluted size sample was 
added to the pulp slurry with mixing and a series of handsheets formed, 
pressed and dried on the drum drier. 
Portions of the finished handsheets were set aside in a constant 
temperature-humidity room to permit aging studies. Sizing performance was 
evaluated with a Hercules Sizing Tester, with use of pH 7 or pH 2 ink. 
Sizing times as given are the intervals in seconds required to reduce 
reflectance to the 80% level. 
For the surface sizing studies, a laboratory Keegan coater was used. 
As given herewith, Examples 1 to 8 primarily concern variables of size 
preparation, formulation for paper application, and evaluation in paper 
application for use of aqueous glyoxal of 40% concentration. Examples 9 to 
11 concern use of glyoxal of 40%, 70% and 80% concentration in size 
preparation and relative sizing performance of such compositions. 
EXAMPLE 1 
Sizing compositions were prepared from cetyl alcohol and glyoxal using 
variable sulfuric acid charge. 
Six 50 gram portions of cetyl alcohol (0.2 mole) were placed in 8 ounce 
bottles on a 70.degree. C. water bath equipped with mixers, melted and 
stirred continuously. 14.9 Grams of 40% glyoxal (0.1 mole) were slowly 
added to each portion. After an additional 15 minutes, increasing portions 
of sulfuric acid were added dropwise to this series. 
The samples were stirred for an additional 90 minutes, removed from the 
bath and allowed to solidify. After 3 hours, the samples were placed on 
the bath and remelted without mixing. On remelting, distinct separation of 
the water phase occurred. 
The water phase was removed and analyzed for glyoxal content. The fraction 
of the glyoxal retained in the organic phase was then calculated. The 
results are shown in Table I. 
TABLE I 
______________________________________ 
% of Glyoxal 
Sample 
H.sub.2 SO.sub.4 Charge (Grams) 
Retained in Alcohol Phase 
______________________________________ 
1(a) 0 65.9 
1(b) 1.25 79.0 
1(c) 2.5 83.5 
1(d) 5 88.0 
1(e) 7.5 96.5 
1(f) 10 98 
______________________________________ 
Two gram portions of (a), (d) and (f) were melted and blended with 100 cc 
of 2% cationic starch at 70.degree. C., pH adjusted to 4 with dilute 
caustic, homogenized and allowed to cool. These products were therewith 
tested for internal sizing performance by preparation of Noble & Wood 
handsheets as earlier described. Application as size was 5 pounds per ton 
and papermaking pH was 7.6. Hercules size tests for pH 7 ink were 
conducted. The results are shown in Table II. 
TABLE II 
______________________________________ 
Sample Seconds Sizing 
______________________________________ 
Blank (no size) 0.15 
1(a) 0.4 
1(d) 83.4 
1(f) 71.0 
______________________________________ 
Test results indicated that the H.sub.2 SO.sub.4 promoted the reaction and 
enhanced the performance. 
EXAMPLE 2 
This example involves lower sulfuric acid catalysed levels. Fifty gram 
portions of octadecanol were melted and brought to 75.degree. C. The 
samples were treated with increasing levels of concentrated sulfuric acid 
and mixed well for 5 minutes. They were then treated with 13.4 grams of 
40% glyoxal and mixed well at 75.degree. C. for 6 hours. 
1.5 Gram portions of the products were homogenized in 100 cc of 3% cationic 
starch with pH adjustment to 4.0. These samples were then evaluated for 
internal sizing with papermaking pH 7.6, at the size level of 3.5 pounds 
per ton. The results are shown in Table III of a Hercules size test, using 
pH 7 ink. 
TABLE III 
______________________________________ 
H.sub.2 SO.sub.4 Charge 
Sizing Against 
Sample (Grams) pH 7 Ink (Seconds) 
______________________________________ 
3(a) 0.10 0.3 
3(b) 0.20 3.1 
3(c) 0.42 200.4 
3(d) 0.84 200.2 
3(e) 1.68 215.4 
______________________________________ 
EXAMPLE 3 
For use of octadecanol, shorter reaction times than those of Example 2 were 
studied. Two 50 gram portions of octadecanol were each melted and brought 
to 75.degree. C. The samples were then treated with 0.418 grams of 
concentrated sulfuric acid and mixed well for 5 minutes. The 2 samples 
were then treated with 13.4 grams of 40% glyoxal and mixed well at 
75.degree. C. over periods of 2 hours and 1 hour respectively. 
1.5 Gram portions of the products were homogenized in 100 cc of 3% cationic 
starch with pH adjustment to 4.0. These samples were then evaluated for 
internal sizing with a papermaking pH at 7.6, at the size level of 3.5 
pounds per ton. The results are shown in Table IV of a Hercules size test 
using pH 7 ink. 
TABLE IV 
______________________________________ 
Reaction Time Sizing Against 
Sample Hours pH 7 Ink (Seconds) 
______________________________________ 
4(a) 1 137.4 
4(b) 2 144.2 
______________________________________ 
EXAMPLE 4 
This series of tests concerned glyoxal charge for otherwise fixed 
conditions, for use of 40% glyoxal. 
Five 50 gram portions of cetyl alcohol were melted on a 70.degree. C. water 
bath as in Example 1. Increasing charges of 40% glyoxal were added to the 
5 samples, followed by 5 grams of concentrated H.sub.2 SO.sub.4. The 
samples were mixed well for 1 hour at 70.degree. C. following H.sub.2 
SO.sub.4 addition. 
The samples were then removed from the water bath and further treated as in 
Example 1 to separate the water phase. Analysis of the water phase in each 
case for remaining glyoxal permits calculation of the amount taken up in 
the reaction into the organic phase. The results are given in Table V. 
TABLE V 
______________________________________ 
% of Glyoxal 
Sample 40% Glyoxal Charge 
Retained in Alcohol Phase 
______________________________________ 
5(a) 11.2 grams 96.8 
5(b) 14.9 grams 89.9 
5(c) 18.7 grams 85.3 
5(d) 22.4 grams 75.3 
5(e) 29.9 grams 65.3 
______________________________________ 
Samples of the glyoxal-alcohol compositions were homogenized in the cooked 
cationic starch as in Example 1. However, for this series, the ratio of 
cationic starch to size was increased to 2:1. The samples were evaluated 
for internal sizing as in Example 1, except that the level of size 
application was reduced from 5 to 3.5 pounds per ton. The results are 
given in Table VI. 
TABLE VI 
______________________________________ 
Seconds Sizing 
Sample For pH 7 Ink 
______________________________________ 
6(a) 26.9 
6(b) 92.0 
6(c) 105.0 
6(d) 109.2 
6(e) 109.2 
______________________________________ 
These results show that within limits the level of glyoxal is not extremely 
critical. 
EXAMPLE 5 
This series of tests demonstrates the effect of alcohol chain length on the 
properties of the compositions when used as internal sizes. Six 
substantially pure commercially available alcohols, and three industrial 
blends were used: 
Alcohols: octanol, decanol, dodecanol, tetradecanol, hexadecanol 
(cetylalcohol), and octadecanol. 
Blends: Alfol 14-18 DDB; a blend of C.sub.14 -C.sub.18 linear alcohols. 
Alfol 16-20H+; a blend of C.sub.16 -C.sub.20 linear alcohols. Alfol 20+; a 
blend containing about 74% of C.sub.20 -C.sub.28 alcohols. 
The blends were obtained from Conoco Chemicals Division, Continental Oil 
Company. 
The sizing compositions were prepared by bringing the alcohol to 75.degree. 
C. on a water bath, and then adding, with good mixing, 0.5 moles of 40% 
glyoxal solution per mole of alcohol. After an additional 15 minutes, 
concentrated sulphuric acid was slowly added in an amount equal to 25% by 
weight of the added glyoxal solution. The samples were maintained at 
75.degree. C. for 1 hour after completion of the acid addition, and then 
removed from the bath. Samples were then homogenized in cooked cationic 
starch, neutralized to pH 4 dilute sodium hydroxide), and allowed to cool. 
The samples were evaluated for papermaking at a pH of 7.6, by using a 
Hercules sizing test using a pH 7 ink. The results are shown in Table VII. 
TABLE VII 
______________________________________ 
Sample 
Alcohol in Application Seconds Sizing, 
No. Sizing Composition 
Rate, pounds/ton 
pH 7 Ink 
______________________________________ 
7(a) Octanol 6.0 0.35 
7(b) Decanol 6.0 52.0 
7(c) Dodecanol 6.0 127.6 
7(d) Tetradecanol 3.5 57.8 
7(e) Hexadecanol 3.5 76.2 
7(f) Octadecanol 3.5 124.3 
7(g) Alfol 14-18 DDB 
3.5 55.0 
7(h) Alfol 16-20H+ 3.5 83.0 
7(i) Alfol 20+ 3.5 10.5 
______________________________________ 
EXAMPLE 6 
This example illustrates the preparation and evaluation of a sizing 
composition using a sorbitan ester of a fatty acid. For this purpose 
sorbitan tristearate (sold commercially as Span 65, a product of ICI 
America, Inc.) was used. 
50 Grams of the sorbitan tristearate were melted on a 75.degree. C. bath. 
With good mixing, 6.45 grams of 40% glyoxal and 1.25 grams of sulfuric 
acid were added. The blend was stirred for 1 hour and removed from the 
bath. 1.5 Grams of the composition was blended with 100 cc of 3% cooked 
cationic starch at 75.degree. C., homogenized and pH adjusted to pH 4.0. 
The product was then evaluated as in earlier studies for internal sizing 
performance. At 5 pounds per ton size, sizing was 4.4 seconds against pH 7 
ink. 
EXAMPLE 7 
For wet end paper application, earlier examples have involved homogenizing 
the sizing compositions at low concentration, below 3% concentration, in 
cooked cationic starch solutions. For commercial use, preparation of the 
finished product at such low concentration is generally less attractive 
than preparation at higher colloid concentration. 
This example illustrates the preparation of a sizing composition at a 
higher concentration than practiced in earlier examples, the incorporation 
of a cationic resin instead of cationic starch, the use of surfactants to 
facilitate product preparation, and use of a protective colloid to 
stabilize the finished product. 
In a pilot plant operation, 12 pounds of Alfol 16-20H.sup.+ alcohol 
(Conoco) was melted in a kettle and heated to 80.degree. C. With moderate 
mixing, 120 grams of 96% sulfuric acid was added. Four pounds of 40% 
glyoxal was added, and the composition mixed at 73.degree.-80.degree. C. 
for 2 hours. It was allowed to cool to 70.degree. C. Meanwhile, a blend of 
18.8 pounds of distilled water, 134 grams of Igepal C0977 surfactant and 
31 grams of Igepal C0660 surfactant were heated to 70.degree. C. They were 
charged to the above melt and mixed for 10 minutes. Therewith, 6 pounds 
(active basis) of a resin solution prepared by reacting epichlorohydrin, 
dimethyl amine and ammonia in an aqueous phase, with final addition of 
hydrochloric acid (see column 5, lines 16-75 of U.S. Pat. No. 3,738,945) 
was added, with continued stirring. Temperature fell to 60.degree. C. 
Therewith, 348 grams of 50% sodium hydroxide was slowly added, to raise 
the pH to 5.0. This composition at 60.degree.-57.degree. was homogenized 
in a Manton-Gaulin homogenizer at 1500 p.s.i. pressure and run into a 0.4% 
guar gum solution at room temperature with mild stirring to provide a 
final product of 30.6% solids concentration. This colloidal concentrate 
gave good sizing in laboratory handsheet preparation and had good shelf 
life on aging. 
EXAMPLE 8 
This example illustrates use of the sizing compositions of the invention in 
surface sizing of paper. The sizing composition in Example 7 was used. 
A hydroxyethylated starch was batch cooked at 10% concentration in water 
and cooled to 140.degree. F. The starch was then split into 4 portions of 
500 cc each. Three of the portions were treated with increasing levels of 
the size concentrate. 
A commercial 45 pound offset paper grade was then treated with the above 4 
portions in a Keegan coater to simulate size press application at starch 
level of 100 pounds per ton. The treated paper was dried on a drum-drier, 
conditioned in a constant temperature-humidity room and evaluated for 
sizing against pH 7 and pH 2 inks. The results are shown in Table VIII. 
TABLE VIII 
______________________________________ 
Hercules Sizing 
Tests, Seconds 
pH 7 Ink 
pH 2 Ink 
______________________________________ 
Starch alone 24.1 10.7 
Starch + 2.5 pounds per ton size 
28.0 13.3 
Starch + 5 pounds per ton size 
58.2 38.3 
Starch + 10 pounds per ton size 
100.0 83.6 
______________________________________ 
EXAMPLE 9 
Herewith, use of glyoxal of 80% concentration is compared to use of glyoxal 
of 40% concentration. Sizing compositions were prepared with the following 
molar ratios of reagents: 
TABLE IX 
______________________________________ 
ALFOL 
GLYOXAL 16-20H+ SULFURIC 
CONCEN- GLYOXAL ALCOHOL, ACID, 
TRATION MOLES MOLES MOLES 
______________________________________ 
(a) 40% 1.0 1.6 0.096 
(b) 80% 1.0 1.6 0.096 
(c) 80% 1.0 1.0 0.096 
(d) 80% 1.0 0.5 0.096 
______________________________________ 
We note that in earlier work with 40% glyoxal (Example 4), a range of 
glyoxal levels are studied. 
In preparation of the sizing composition, the alcohol was melted, the 
sulfuric acid added, the glyoxal solution or solid added with vigorous 
stirring, and the reaction maintained at 75.degree.-85.degree. C. for 90 
minutes. 
In contrast to earlier sizing evaluations, these preparations were 
dissolved in chloroform at 1% size concentration, unsized paper was 
immersed in this solution for 30 seconds, and the paper dried on a drum 
drier, and evaluated for surface sizing, with results as follows: 
TABLE X 
______________________________________ 
MOLAR RATIO 
GLYOXAL ALCOHOL TO SIZING (SECONDS) 
USED GLYOXIAL pH 7 INK pH 2 INK 
______________________________________ 
(a) 40% 1.6:1 329 390 
(b) 80% 1.6:1 275 893 
(c) 80% 1:1 382 1038 
(d) 80% 0.5:1 352 3018 
______________________________________ 
The 80% glyoxal reaction product gave appreciably higher pH 2 ink sizing 
than did the 40% glyoxal product. In the 80% glyoxal case, pH 2 ink sizing 
increased appreciably with increasing glyoxal to alcohol ratio. 
EXAMPLE 10 
The sizing compositions from Example 9 were formulated for, and evaluated 
in wet end sizing. Preparation of the cationic colloids was generally as 
described in Example 7, but on a smaller scale, with hand-homogenizing. A 
slightly different surfactant formulation was used. Overall composition 
was as follows: 
18.8% sizing composition 
21.8% soft water 
0.24% Ethomeen 18/60 surfactant 
0.08% Igepal CO-660 surfactant 
14.7% cationic resin solution 
0.9% 50% caustic 
44.3% 0.4% guar gum solution 
Wet end sizing evaluation gave results as follows for papermaking at pH 
7.6. 
TABLE XI 
__________________________________________________________________________ 
SIZE PREATION SIZING PERFORMANCE 
SIZE APPLICATION 
GLYOXAL MOLAR RATIO 
SECONDS 
POUNDS/TON CONCENTRATION 
ALCOHOL TO GLYOXAL 
pH 7 INK 
pH 2 INK 
__________________________________________________________________________ 
6 40% 1.6:1 100 170 
6 80% 1.6:1 250 394 
6 80% 0.5:1 270 890 
8 40% 1.6:1 160 500 
8 80% 0.5:1 390 1800 
10 40% 1.6:1 270 680 
10 80% 0.5:1 480 2400 
__________________________________________________________________________ 
From this wet end sizing study, two significant points are as follows: 
(a) when glyoxal of 40% concentration was replaced by glyoxal of 80% 
concentration in the initial sizing composition, appreciably superior 
sizing performance was realized 
(b) when the ratio of 80% glyoxal to fatty alcohol was increased further, 
significant improvements in sizing were realized. 
EXAMPLE 11 
A glyoxal solution of 70% concentration was prepared by vacuum-stripping a 
40% glyoxal solution in a rotary evaporator. This glyoxal was reacted with 
Alfol 16-20 H.sup.+ alcohol and sulfuric acid at a 1.6 mole alcohol to 1.0 
mole glyoxal ratio as described in Example 9, and emulsified for wet end 
application as described in Example 10. It was applied at 6 pounds per ton 
in wet end application. pH 7 ink sizing was 180 seconds and pH 2 ink 
sizing 482 seconds, distinctly superior to that obtained for use of 
glyoxal of 40% concentration, as given in Example 10. 
Thus, Examples 10 and 11 show distinctly superior wet end sizing 
performance for use of glyoxal of 70% and 80% concentration than for use 
of glyoxal of 40% concentration in size preparation. 
Earlier, J. M. Kliegman and R. K. Barnes (J. Org. Chem., Vol. 38, p. 556, 
1973) studied reactions of relatively low molecular weight alcohols 
(methanol to 2-ethyl hexanol) with glyoxal. Herewith, compositions of our 
acid-catalyzed fatty alcohol-glyoxal reaction products is considered. We 
performed NMR analyses on the following reaction products from Example 9: 
(a) 40% glyoxal-1.6 moles Alfol, 0.096 mole H.sub.2 SO.sub.4, 1.0 mole 
glyoxal 
(b) 80% glyoxal-1.6 moles Alfol, 0.096 mole H.sub.2 SO.sub.4, 1.0 mole 
glyoxal 
(d) 80% glyoxal-0.5 mole Alfol, 0.096 mole H.sub.2 SO.sub.4, 1.0 mole 
glyoxal and on a purified tetra-alkoxy ethane. 
The following structures were confirmed: 
##STR1## 
wherein R represents a fatty alkyl group. 
From the NMR studies and from Examples 9 and 10, the following table shows 
the relations of initial size formulation, composition of the size and wet 
end sizing performance. 
TABLE XII 
__________________________________________________________________________ 
ALCOHOL AND GLYOXAL 
IN SIZE FORMULATION 
MOLAR WET END SIZING 
RATIO COMPOSITION AS 
APPLICATION 
PERFORMANCE 
GLYOXAL 
ALCOHOL- 
DETERMINED BY 
POUNDS PER 
(SECONDS) 
CONCN. GLYOXAL NMR TON pH 7 INK 
pH 2 INK 
__________________________________________________________________________ 
40% 4:1 [1] tetra-alkoxy ethane 
relatively poor performance 
40% 1.6:1 tetra-alkoxy ethane 
6 100 170 
and probably 
8 160 500 
dioxolane oligomer 
10 270 680 
80% 1.6:1 alkoxy dioxolane 
6 250 394 
dimer and trimer, 
with little monomer 
80% 0.5:1 alkoxy dioxolane 
6 270 890 
dimer and trimer 
8 390 1800 
10 480 2400 
__________________________________________________________________________ 
[1] speciallyprepared tetraalkoxy ethane. 
From the NMR and paper sizing studies, higher sizing performance 
corresponds to predominantly higher proportions of alkoxy dioxolanes and 
possibly alkoxy-hydroxy dioxolanes and lower proportions of alkoxy monomer 
and alkoxy-hydroxy monomer in the sizing composition.