Manufacture and use of non-ionogenic interface-active agents based on modified rosins

Compounds of the formula EQU A[(X--O).sub.n --H].sub.m wherein PA1 A is a cycloalkyl-, aralkyl- or aryl-modified rosin acid radical or a radical of an ester of a polyhydric alcohol with such an acid, PA1 X stands for the same or different group or groups of the formulae EQU --CH.sub.2 --CH.sub.2 -- and EQU --CH.sub.2 --CH(CH.sub.3)--, PA1 n is a number of 1 to 100 and PA1 m is an integer of 1 to 5 are surface- and interface-active agents, especially dispersants, emulsifiers, wetting agents and dyeing adjuvants.

The present invention relates to non-ionogenic compounds based on modified 
natural rosins, their manufacture and their use as interface-active 
agents. 
One embodiment of the invention is compounds of the general formula 
EQU A--[(X--O).sub.n --H].sub.m 
in which 
A stands for a cycloalkyl-, aralkyl- or aryl-modified rosin acid radical or 
the esterification product thereof with a polyol, 
X strands for identical or different groups of the formula 
EQU --CH.sub.2 --CH.sub.2 -- 
or 
EQU --CH.sub.2 --CH(CH.sub.3)--, 
n is a number of from 1 to 100, and 
m is an integer of from 1 to 5. 
Another embodiment of the invention is a process for the preparation of 
these compounds, which comprises reacting compounds of the general formula 
EQU A--(H).sub.m 
with n.multidot.m mols of ethylene oxide and/or propylene oxide, A, n and m 
being defined as above. 
A further embodiment of the invention is the use of these compounds as 
interface-active agents, especially as dispersing agents for the fine 
distribution and stabilization of solids, and as wetting, emulsifying, 
levelling and dyeing auxiliaries. 
The rosin acid radical A is preferably derived from the following 
compounds: 
(a) modified rosin acids and/or mixtures of the same, as they are obtained 
from commercial types of colophony or disproportionation products thereof 
by a reaction with aromatic hydroxy compounds or with cycloalkyl, 
preferably aryl or aralkyl compounds capable of splitting of halogen, 
(b) esterification products and/or mixtures thereof, as obtained by 
esterification from 1 mol of a di- to hexahydric alcohol with of 1 to 4, 
preferably from 1 to 2, mols of a rosin acid modified according to (a) 
and/or mixtures thereof. 
The starting materials are obtained by reacting natural rosin acids or the 
disproportionation products thereof with aromatic hydroxy compounds or 
with cycloalkyl, preferably aralkyl or aryl compounds capable of splitting 
off halogen, according to known processes and optionally esterifying the 
products with polyols. 
In the following, the percentages refer to the weight unless otherwise 
stated. 
Suitable modified rosins are rosin-phenol compounds, as obtained by the 
addition of phenol, o-, m- or p-cresol, o-cresol acetate, salicylic acid, 
guaiacol, bisphenol A or .alpha.- or .beta.-naphthol to natural rosin 
acids, such as abietic acid, dehydroabietic acid, dihydroabietic acid, 
tetrahydroabietic acid, levopimaric acid, dextropimaric acid and 
isodextropimaric acid, as present in commercial types of colophony, as 
well as to disproportionated, hydrogenated and dimerized rosin acids in 
the presence of strongly acid catalysts or catalysts splitting off acid, 
for example, boron trifluoride, hydrogen chloride, tin tetrachloride, 
aluminum chloride or strong mineral acids at a temperature of from 
20.degree. to 120.degree. C. in an organic medium, wherein there is 
reacted per mol of rosin acid suitably from 0.5 to 1.0, preferably from 
0.7 to 0.8, mol of the above-mentioned phenols or naphthols. 
Also suitable are modified natural rosin acids, as obtained by a reaction 
of natural rosin acids with aryl, aralkyl or cycloalkyl compounds capable 
of splitting off halogen, from example, benzyl chloride, 
bis-(chloromethyl) benzene, chloromethyl toluene, 4-chloromethyl-diphenyl 
ether, 1-(chloromethyl) naphthalene, benzal chloride, 2-, 3- or 
4-chlorophenol, 5-chloro-2-hydroxy-toluene, 2-chloro-5-hydroxy-1,3-xylene, 
4-chlorobenzyl, alcohol, 4-chlorodiphenyl, 4-chloro-diphenyl ether, 
1-chloronaphthalene, 2-chloronaphthalene, 4-chloro-1-naphthol, 
1-chloro-2-naphthol, 2-chloro-1-naphthol and cyclohexyl chloride in the 
presence of a catalyst, such as about 0.2% zinc chloride, at a temperature 
of from 100.degree. to 220.degree. C., preferably from 150.degree. to 
210.degree. C., in such process there is reacted, per mol of rosin acid, 
suitably from 0.5 to 1.0, preferably from 0.7 to 0.8, mol of the 
above-mentioned compounds capable of splitting off halogen. 
Thus, preferred modified rosins contain--optionally bound via a methylene 
group--phenyl or naphthyl radicals which may be substituted by hydroxy, 
lower alkyl, lower alkoxy, carboxy, phenyl or hydroxyalkyl groups, the 
hydroxy and carboxy groups thus introduced are also suitably alkoxylated. 
The following are examples of polyols suitable for the esterification of 
the modified rosin acids: glycol, glycerol, 1,2,4-butane triol, butane 
diol-(1,4), 1,1,1-trimethylol propane, pentaerythritol, 
2,4-dihydroxy-3-methylol pentane, hexane triol, sorbitol, anhydrosorbitol, 
hexitol and mannitol. The esterification of the modified rosin acids with 
the polyols is effected in a molar ratio of from 1:1 to 4:1, preferably 
from 1:1 to 2:1, in accordance with known esterification processes at a 
temperature of from 180.degree. to 300.degree. C., preferably from 
200.degree. to 270.degree. C., optionally while adding an entrainer, such 
as an aromatic hydrocarbon or chlorinated hydrocarbon. As catalysts there 
may be used, for example, benzene-sulfonic acid, p-toluene-sulfonic acid, 
boric acid, powdered tin or sulfuric acid. 
The reaction of the modified natural rosin acids and the esterification 
products thereof with 1,2-propylene oxide and/or, preferably, ethylene 
oxide is carried out according to known methods, preferably with alkali 
metal hydroxides or alkoxides as catalysts at 100.degree. to 200.degree. 
C., preferably at 140.degree. to 180.degree. C. 
Suitable alkali metal hydroxides are potassium hydroxide and, preferably, 
sodium hydroxide; suitable alkali metal alkoxides are sodium methylate and 
sodium ethylate. The catalyst concentration is in the range of from 0.05 
to 1.0%, calculated on the starting material. The oxalkylation may be 
carried out without pressure or in pressure vessels with propylene oxide 
or preferably ethylene oxide or mixtures of the same, the ethylene oxide 
being fed in in either a gaseous or liquid state. If pressure is applied 
for the operation, it is in the range of from 1 to 10, preferably from 2 
to 8, bars of over-pressure. 
The amount of ethylene oxide and/or propylene oxide is proportioned in a 
way that a stable emulsifiability or a complete solubility of the addition 
products in water is reached. There are advantageously added from 1 to 
100, preferably from 8 to 75, mols each of ethylene oxide and/or propylene 
oxide to each free carboxy and hydroxy group of the modified natural rosin 
acids or esterification products of these modified natural rosin acids. 
The amount of alkylene oxide added is also proportioned in accordance with 
the desired application, and thus with the degree of hydrophilic 
properties intended to be exhibited. 
The starting materials obtained by the addition of phenols to natural rosin 
acids are known and suitable for preparation of lacquers (German Pat. Nos. 
536,170; 581,956; 582,846 and 652,602), whereas the starting materials 
obtained by the reaction of natural rosin acids with aryl or aralkyl 
compounds capable of splitting off halogen and subsequent esterification 
with alcohols are described as oil-soluble synthetic resins (German Pat. 
No. 570,958). 
It has further been known to oxethylate colophony, in which process there 
are obtained detergents, emulsifying and levelling agents (Ullmanns 
Encyklopadie der technischen Chemie, 3rd edition, vol. 8, page 409). 
The oxalkylation products of the invention and/or their mixtures yield, in 
water, stable emulsions or are clearly soluble in water, they reduce the 
surface tension according to the ring method for measuring the surface 
tension (DIN 53 914) to 0.04 N/m and are almost free from foam according 
to the Ross-Miles test (DIN 53 902). They wet cotton fabric according to 
the dip-wetting method (DIN 53 901) within 70 to 180 seconds and are 
resistant to strong alkali and to strong acids under the common 
application conditions for surfactants. In an aqueous solution, the 
products show a very light color or are practically colorless. 
The compounds of the invention are excellently suitable as dispersing, 
wetting and distributing agents, for example for pigments, furthermore for 
the formulation of plant protective and pest control agents and as 
emulsifiers for the preparation of carrier emulsions and as levelling and 
dyeing auxiliaries in the dyeing and printing of natural and synthetic 
fiber material, such as cotton, wool, cellulose, spun rayon, cellulose 
acetate and triacetate, polyester, polyamides and polyacrylonitrile, or of 
fiber materials containing said substances. 
The advantages of the compounds of the invention as compared with known 
non-ionogenic compounds are to be seen in the fact that they hardly show 
any foaming tendency, but exhibit a markedly improved dispersion behavior 
in aqueous applications and, likewise, favorable wetting properties. The 
novel products are also easily biodegradable. 
The compounds of the invention may be employed by themselves, as a mixture 
or in combination with other non-ionogenic as well as anionic or cationic 
compounds, builders and other additives and auxiliaries in emulsifying and 
dispersing agent formulations.

In the following Examples the preparation of the compounds of the invention 
is described. Parts and percentages relate to the weight, and pressure 
values to overpressure unless otherwise stated. The acid numbers (AN) are 
determined according to DIN 53 185. 
EXAMPLE 1 
(a) Preparation of the rosin-phenol compound 
173.8 Parts of a 25% solution of boron trifluoride in phenol are added 
while stirring at 10.degree. C. within 4 hours to a solution of 604 parts 
of colophony in 800 parts of tetrachloromethane, and stirring is continued 
for 14 hours at 15.degree. to 18.degree. C. For the elimination of the 
catalyst, the reaction mixture is washed with water until neutral and 
dried over anhydrous sodium sulfate. Subsequently the tetrachloromethane 
is removed by distillation. There are obtained 630 parts of a clear resin 
having an AN of about 114 and a softening point of about 105.degree. C. 
(b) Preparation of the rosin oxalkylate 
After having added 1.5 parts of sodium hydroxide, 367 parts of the modified 
rosin described under (a) are oxethylated in a pressure vessel, with 
stirring and feeding in of 378.4 parts of ethylene oxide at 150.degree. to 
170.degree. C., while maintaining a pressure of from 1.5 to 2.5 bars. 
After the total amount of ethylene oxide has been introduced under 
pressure, stirring is continued for 1 hour at 150.degree. to 160.degree. 
C. There is obtained a viscous brown rosin oxethylate having an ethylene 
oxide content of 8.6 mols, the cloud point of the product being found at 
56.5.degree. C. in a 25% butyl-diglycol solution. 
EXAMPLE 2 
After the addition of 1.5 parts of sodium hydroxide, 367 parts of the rosin 
prepared according to Example 1 (a) are oxethylated in a pressure vessel, 
with stirring and feeding in of 2200 parts of ethylene oxide at 
150.degree. to 170.degree. C., while maintaining a pressure of from 1.5 to 
2.5 bars. After the total amount of ethylene oxide has been introduced 
under pressure, stirring is continued for 1 hour at 150.degree. to 
160.degree. C. The wax-like rosin oxethylate obtained is ocher-colored and 
contains 50 mols of ethylene oxide. Its cloud point in aqueous solution is 
found at about 60.degree. C. 
EXAMPLE 3 
After having added 1.5 parts of sodium hydroxide, 367 parts of the rosin 
prepared according to Example 1(a) are oxethylated in a pressure vessel, 
with stirring and feeding in of 3300 parts of ethylene oxide at 
150.degree. to 170.degree. C., while maintaining a pressure of from 1.5 to 
2.5 bars. After the total amount of ethylene oxide has been introduced 
under pressure, stirring is continued for 1 hour at 150.degree. to 
160.degree. C. The resulting rosin oxethylate contains 75 mols of ethylene 
oxide and corresponds in its appearance to the addition product of Example 
2. The cloud point in a 25% butyl-diglycol solution is found at 
101.degree. to 102.degree. C. 
EXAMPLE 4 
(a) Preparation of the rosin-guaiacol compound 
264.5 Parts of a 25% solution of boron trifluoride in guaiacol are 
introduced while stirring at 10.degree. C. within 4 hours to a solution of 
604 parts of colophony in 800 parts of tetrachloromethane, and stirring is 
continued for 14 hours at 15.degree. to 18.degree. C. After the 
working-up according to Example 1 there are obtained 630 parts of a clear 
rosin having an AN of about 101 and a softening point of about 110.degree. 
C. 
(b) Preparation of the rosin oxethylate 
After having added 1.5 parts of sodium hydroxide, 367 parts of the modified 
rosin described under (a) are oxethylated in a pressure vessel, with 
stirring and feeding in of 2200 parts of ethylene oxide at 150.degree. to 
170.degree. C., while maintaining a pressure of from 1.5 to 2.5 bars. 
After the total amount of ethylene oxide has been introduced under 
pressure, stirring is continued for 1 hour at 150.degree. to 160.degree. 
C. The brown rosin oxethylate obtained is of a wax-like consistency and 
contains 50 mols of ethylene oxide. The cloud point in aqueous solution is 
found at 97.degree. C. 
EXAMPLE 5 
After having added 1.5 parts of sodium hydroxide, 868.5 parts of the 
modified rosin prepared according to Example 4(a) are oxethylated in a 
pressure vessel, with stirring and feeding in of 3300 parts of ethylene 
oxide at 150.degree. to 170.degree. C., while maintaining a pressure of 
from 1.5 to 2.5 bars. After the total amount of ethylene oxide has been 
introduced under pressure, stirring is continued for 1 hour at 150.degree. 
to 160.degree. C. The wax-like rosin oxethylate obtained is ocher-colored 
and contains 75 mols of ethylene oxide. The cloud point in aqueous 
solution is found at 96.5.degree. C. 
EXAMPLE 6 
(a) Preparation of the rosin-salicylic acid compound 
174 Parts of boron trifluoride-ethyl ether complex are added with stirring 
at 10.degree. C. within 4 hours to a solution of 604 parts of colophony 
and 220.8 parts of salicylic acid in 600 parts ot tetrachloromethane, and 
stirring is continued for 14 hours at 15.degree. to 18.degree. C. After 
working-up according to Example 1 there are obtained 710 parts of a clear 
rosin having an AN of about 173 and a softening point of from about 
115.degree. to 120.degree. C. 
(b) Preparation of the rosin oxethylate 
After having added 1.5 parts of sodium hydroxide, 412.4 parts of the 
modified rosin described under (a) are oxethylated in a pressure vessel, 
with stirring and feeding in of 1100 parts of ethylene oxide at 
150.degree. to 170.degree. C., while maintaining a pressure of from 1.5 to 
2.5 bars. After the total amount of ethylene oxide has been introduced 
under pressure, stirring is continued for 1 hour at 150.degree. to 
160.degree. C. The wax-like brown rosin oxethylate obtained contains 25 
mols of ethylene oxide and shows a cloud point in a 10% sodium chloride 
solution of 49.5.degree. C. 
EXAMPLE 7 
(a) Preparation of the rosin-naphthol compound 
At 10.degree. C., 106 parts of boron trifluoride-ethyl ether complex are 
added while stirring within 4 hours to a solution of 604 parts of 
colophony and 203.2 parts of .beta.-naphthol in 600 parts of 
tetrachloromethane, and stirring is continued for 14 hours at 15.degree. 
to 18.degree. C. After working-up according to Example 1 there are 
obtained 726.3 parts of a clear rosin having an AN of about 145 and a 
softening point of from about 115.degree. to 120.degree. C. 
(b) Preparation of the rosin oxethylate 
After having added 3.0 parts of sodium methylate, 403.6 parts of the 
modified rosin specified under (a) are oxethylated in a pressure vessel, 
with stirring and feeding in of 2200 parts of ethylene oxide at 
160.degree. to 180.degree. C., while maintaining a pressure of from 2 to 8 
bars. Stirring is continued for 1 hour at 150.degree. to 160.degree. C. 
The wax-like yellowish brown rosin oxethylate obtained contains 50 mols of 
ethylene oxide with a cloud point in a 25% butyl diglycol solution of 
95.5.degree. C. 
EXAMPLE 8 
(a) Preparation of the rosin-phenol compound 
At 10.degree. C., 173.8 parts of a 25% solution of boron trifluoride in 
phenol are added while stirring within 4 hours to a solution of 604 parts 
of colophony in 800 parts of tetrachloromethane, and stirring is continued 
for 14 hours at 15.degree. to 18.degree. C. After working-up according to 
Example 1, there are obtained about 630 parts of a clear rosin having an 
AN of 114 and a softening point of about 105.degree. C. 
(b) Preparation of the rosin-phenol-glycerol ester 
367 Parts of the rosin-phenol compound described under (a) are esterified 
in the presence of 5 parts of powdered tin with 92 parts of glycerol in a 
stirring vessel, while eliminating the reaction water by distillation, 
within 8 to 10 hours at a temperature of from 230.degree. to 250.degree. 
C., while simultaneously passing nitrogen through the vessel, until an AN 
of about 25 has been reached. 
(c) Preparation of the rosin-phenol-glycerol ester oxethylate 
After having added 3.3 parts of sodium methylate, 438 parts of the 
rosin-phenol-glycerol ester described under (b) are oxethylated in a 
pressure vessel, with stirring and feeding in of 440 parts of ethylene 
oxide at 150.degree. to 160.degree. C., while maintaining a pressure of 
from 2 to 3 bars. After the total amount of ethylene oxide has been 
introduced under pressure, stirring is continued for 1 hour at 150.degree. 
to 160.degree. C. There is obtained a viscous brown rosin glycerol ester 
oxethylate containing 10 mols of ethylene oxide and showing a cloud point 
in a 25% butyl diglycol solution of 56.5.degree. C. 
EXAMPLE 9 
(a) Preparation of the rosin-cresol compound 
At 10.degree. C., 200 parts of a 25% solution of boron trifluoride in 
technical cresol are added while stirring within 4 hours to a solution of 
604 parts of colophony in 800 parts of tetrachloromethane, and stirring is 
continued for 14 hours at 15.degree. to 18.degree. C. After working-up 
according to Example 1, there are obtained 767 parts of a clear rosin 
having an AN of 117 and a softening point of from 105.degree. to 
110.degree. C. 
(b) Preparation of the rosin-cresol-glycerol ester 
377 Parts of the rosin-cresol compound described under (a) are esterified 
in the presence of 5 parts of powdered tin with 92 parts of glycerol in a 
stirring vessel, while eliminating the reaction water by distillation, 
within 8 to 10 hours at 230.degree. to 250.degree. C., while 
simultaneously passing nitrogen through the vessel, until an AN of about 
25 has been reached. 
(c) Preparation of the rosin-cresol-glycerol ester oxethylate 
451 Parts of the rosin-cresol-glycerol ester described under (b) are 
oxethylated with 440 parts of ethylene oxide, after 3.3 parts of sodium 
methylate have been added. The brown rosin ester addition product obtained 
is viscous and contains 10 mols of ethylene oxide. The cloud point in a 
25% butyl diglycol solution is found at 60.degree. C. 
EXAMPLE 10 
(a) Preparation of the rosin-phenol compound 
At 10.degree. C., 173.8 parts of a 25% solution of boron trifluoride in 
phenol are added within 4 hours to a solution of 604 parts of 
disproportionated colophony in 800 parts of tetrachloromethane, and 
stirring is continued for 14 hours at 15.degree. to 18.degree. C. After 
working-up according to Example 1, there are obtained 625 parts of a clear 
rosin having an AN of 111 and a softening point of from about 90.degree. 
to 100.degree. C. 
(b) Preparation of the rosin-phenol-glycerol ester 
367 Parts of the rosin-phenol compound described under (a) are esterified 
in the presence of 5 parts of powdered tin with 92 parts of glycerol in a 
stirring vessel, while eliminating the reaction water by distillation, 
within 8 to 10 hours at a temperature of from 230.degree. to 250.degree. 
C., while simultaneously passing nitrogen through the vessel, until an AN 
of about 25 has been reached. 
(c) Preparation of the rosin-phenol-glycerol ester oxethylate 
After having added 3.3 parts of sodium hydroxide, 438 parts of the 
rosin-phenol-glycerol ester described under (b) are oxethylated in a 
pressure vessel, with stirring and feeding in of 550 parts of ethylene 
oxide at 150.degree. to 170.degree. C., while maintaining a pressure of 
from 1.5 to 2.5 bars. After the total amount of ethylene oxide has been 
introduced under pressure, stirring is continued for 1 hour at 150.degree. 
to 160.degree. C. The rosin oxethylate obtained is brown and viscous and 
contains 12.5 mols of ethylene oxide. Its cloud point in a 25% butyl 
diglycol solution is found at 60.degree. C. 
EXAMPLE 11 
(a) Preparation of the rosin-naphthol compound 
At 10.degree. C., 106 parts of boron trifluoride ethyl ether complex are 
added while stirring within 4 hours to a solution of 604 parts of 
colophony and 203.2 parts of .beta.-naphthol in 600 parts of 
tetrachloromethane, and stirring is continued for 14 hours at 15.degree. 
to 18.degree. C. After working-up according to Example 1, there are 
obtained 726.3 parts of a clear rosin having an AN of 144.5 and a 
softening point of from about 115.degree. to 120.degree. C. 
(b) Preparation of the rosin-naphthol-glycerol ester 
403.6 Parts of the modified rosin described under (a) are esterified in the 
presence of 5.3 parts of powdered tin with 92 parts of glycerol in a 
stirring vessel, while eliminating the reaction water by distillation, 
within 8 to 10 hours at 230.degree. to 250.degree. C., while 
simultaneously passing nitrogen through the vessel, until an AN of about 
25 has been reached. 
(c) Preparation of the rosin-naphthol-glycerol ester oxethylate 
After having added 3.4 parts of sodium methylate, 477 parts of the 
rosin-naphthol-glycerol ester described under (b) are oxethylated in a 
pressure vessel, with stirring and feeding in of 660 parts of ethylene 
oxide at 150.degree. to 160.degree. C., while maintaining a pressure of 
from 2 to 8 bars. After the total amount of ethylene oxide has been 
introduced under pressure, stirring is continued for 1 hour at 150.degree. 
to 160.degree. C. The rosin acid-glycerol ester addition product obtained 
contains 15 mols of ethylene oxide. Said product is brown and viscous and 
shows a cloud point in a 25% butyl diglycol solution of 58.degree. C. 
EXAMPLE 12 
(a) Preparation of the rosin-guaiacol compound 
At 10.degree. C., 264.5 parts of a 25% solution of boron trifluoride in 
guaiacol are added while stirring within 4 hours to a solution of 604 
parts of colophony in 800 parts of tetrachloromethane, and stirring is 
continued for 14 hours at 15.degree. to 18.degree. C. After working-up 
according to Example 1 there are obtained 630 parts of a clear rosin 
having an AN of about 101 and a softening point of about 110.degree. C. 
(b) Preparation of the rosin acid-glycerol ester 
403.6 Parts of the modified rosin described under (a) are esterified in the 
presence of 5.3 parts of powdered tin with 92 parts of glycerol in a 
stirring vessel, while eliminating the reaction water by distillation, 
within 8 to 10 hours at 230.degree. to 250.degree. C., while 
simultaneously passing nitrogen through the vessel, until an AN of about 
25 has been reached. 
(c) Preparation of the rosin acid-glycerol ester oxethylate 
After having added 3.4 parts of sodium methylate, 477 parts of the rosin 
acid-glycerol ester described under (b) are oxalkylated in a pressure 
vessel, with stirring and feeding in of 660 parts of ethylene oxide at 
150.degree. to 160.degree. C., while maintaining a pressure of at first 
from 2 to 8 bars and subsequently from 1.3 to 3 bars. After the total 
amount of ethylene oxide has been introduced under pressure, stirring is 
continued for 1 hour at 150.degree. to 160.degree. C. The resulting rosin 
acid-glycerol ester addition product is brown and viscous and contains 15 
mols of ethylene oxide. The cloud point in a 25% butyl diglycol solution 
is found at 63.5.degree. C. 
EXAMPLE 13 
477 Parts of the rosin acid-glycerol ester prepared according to Example 
12(b) are reacted according to Example 12(c) with 3300 parts of ethylene 
oxide. The resulting yellowish brown rosin acid-monoglycerol ester 
addition product is wax-like and contains 75 mols of ethylene oxide. Its 
cloud point in a 25% butyl diglycol solution is found at 101.degree. to 
102.degree. C. 
EXAMPLE 14 
(a) Preparation of the benzyl-rosin-glycerol ester 
After having added 0.4 part of zinc chloride, 302 parts of colophony are 
slowly heated to 100.degree. C. in 126.5 parts of benzyl chloride, while 
passing nitrogen through the mixture, and said temperature is maintained 
for 2 hours. As soon as the development of hydrogen chloride slows down, 
the temperature is increased to 200.degree. C. and is maintained at 
200.degree. to 210.degree. C. for about 1 hour, until the reaction product 
is practically free from halogen. After cooling to about 100.degree. C. 
and adding 92 parts of glycerol and 130 parts of xylene, the mixture is 
heated to boiling under reflux conditions, and the reaction water is 
collected by azeotropic distillation in a water separator. After 4 hours 
the reaction is completed, and the volatile components are removed by 
vacuum distillation or at a rotation evaporator. As residue there is 
obtained a clear rosin having an AN of 30 and a softening point of from 
120.degree. to 125.degree. C. 
(b) Preparation of the rosin oxethylate 
After having added 3.4 parts of sodium methylate, 465 parts of the 
benzyl-rosin-glycerol ester described under (a) are oxethylated with 600 
parts of ethylene oxide. The viscous rosin-glycerol addition product 
obtained is brown and contains 13.6 mols of ethylene oxide. The cloud 
point in a 25% butyl diglycol solution is found at 58.5.degree. C. 
EXAMPLE 15 
After having added 3.4 parts of sodium methylate, 465 parts of the 
benzyl-rosin-glycerol ester prepared according to Example 14(b) are 
reacted with 1496 parts of ethylene oxide. The resulting rosin oxethylate 
contains 34 mols of ethylene oxide. It is of a wax-like consistency and 
brown color, and its cloud point in a 10% sodium chloride solution is 
found at 61.5.degree. C. 
EXAMPLE 16 
After having added 3.4 parts of sodium methylate, 465 parts of the 
benzyl-rosin-glycerol ester prepared according to Example 14(b) are 
reacted with 2706 parts of ethylene oxide. The rosin oxethylate obtained 
contains 61.5 mols of ethylene oxide. The appearance corresponds to that 
of the product of Example 15, and the cloud point in a 10% sodium chloride 
solution is found at 56.5.degree. C. 
EXAMPLE 17 
(a) Preparation of the rosin-phenol-glycerol ester 
After having added 0.4 part of zinc chloride, 302 parts of colophony are 
slowly heated to 100.degree. C. together with 128 parts of 4-chlorophenol, 
while passing nitrogen through the mixture, and the temperature indicated 
is maintained for 2 hours. As soon as the development of hydrogen chloride 
slows down, the temperature is increased to 200.degree. C. and is 
maintained for about 1 hour at 200.degree. to 210.degree. C., until the 
reaction product is practically free from halogen. After cooling to 
100.degree. C. and after the addition of 92 parts of glycerol and 130 
parts of xylene, the mixture is boiled at reflux, and the reaction water 
is collected by azeptropic distillation in a water separator. After about 
4 hours the reaction is completed, and the volatile components are removed 
by vacuum distillation or at a rotation evaporator. As residue there is 
obtained a clear rosin having an AN of 25 and a softening point of from 
120.degree. to 125.degree. C. 
(b) Preparation of the rosin oxethylate 
After having added 2.4 parts of sodium hydroxide, 468.5 parts of the 
rosin-phenol-glycerol ester described under (a) are oxalkylated in a 
pressure vessel, with stirring and feeding in of 616 parts of ethylene 
oxide at 140.degree. to 150.degree. C., while maintaining a pressure of 
from 2.5 to 3.5 bars. After the total amount of ethylene oxide has been 
introduced under pressure, stirring is continued for 1 hour at 140.degree. 
to 150.degree. C. The resulting viscous rosin-glycerol addition product is 
reddish brown and contains 14 mols of ethylene oxide. The cloud point in a 
25% butyl diglycol solution is found at 60.degree. C. 
EXAMPLE 18 
(a) Preparation of the rosin-phenol compound 
After having added 0.4 part of zinc chloride, 302 parts of colophony are 
slowly heated to 100.degree. C. together with 128 parts of 4-chlorophenol, 
while passing nitrogen through the mixture, and said temperature is 
maintained for 2 hours. Subsequently the temperature is increased to 
200.degree. to 210.degree. C., until after about 1 hour the reaction 
product is free from halogen. After cooling there is obtained a clear 
rosin having a softening point of about 105.degree. C. 
(b) Preparation of the rosin oxethylate 
After having added 2.1 parts of sodium hydroxide, 393.5 parts of the 
rosin-phenol compound described under (a) are oxethylated at 140.degree. 
to 150.degree. C. in accordance with Example 17(b). The resulting slightly 
viscous rosin-phenol addition product is olive green and contains 12 mols 
of ethylene oxide. The cloud point in butyl diglycol is found at 
50.5.degree. C. 
EXAMPLE 19 
(a) Preparation of the rosin-cresol-glycerol ester 
302 Parts of colophony are condensed according to Example 17(a) with 114 
parts of 5-chloro-2-hydroxytoluene in the presence of 0.4 parts of zinc 
chloride and subsequently esterified with 92 parts of glycerol. As residue 
there is obtained a clear rosin having an AN of 24 and a softening point 
of from 110.degree. to 115.degree. C. 
(b) Preparation of the rosin oxethylate 
After having added 2.5 parts of sodium hydroxide, 478 parts of the 
rosin-cresol-glycerol ester described under (a) are reacted according to 
Example 17(b) with 660 parts of ethylene oxide. The resulting viscous 
rosin-glycerol addition product contains 15 mols of ethylene oxide. The 
cloud point in a 25% butyl diglycol solution is found at 60.degree. C. 
EXAMPLE 20 
(a) Preparation of the rosin-naphthol-glycerol ester 
After having added 0.4 part of zinc chloride, 302 parts of colophony are 
condensed according to Example 17(a) with 489.4 parts of 
4-chloro-1-naphthol and are esterified with 92 parts of glycerol. After 
having removed the volatile components, there is obtained a brown rosin 
having an AN of 29 and a softening point of from 115.degree. to 
125.degree. C. 
(b) Preparation of the rosin oxethylate 
After having added 2.5 parts of sodium hydroxide, 489 parts of the 
rosin-naphthol-glycerol ester described under (a) are reacted according to 
Example 17(b) with 772 parts of ethylene oxide. The viscous rosin-glycerol 
addition product obtained is reddish brown and contains 18 mols of 
ethylene oxide. The cloud point in a 25% butyl diglycol solution is found 
at 59.degree. C. 
In the following Table the surface-active properties have been indicated 
according to the following DIN standards: 
Wetting power: DIN 53 901 
Surface tension: DIN 53 914 
Foaming power: DIN 53 902 
Iodine color number: DIN 6162 
The foaming properties were judged by the following scale: 
0 non-foaming, 
1 slightly foaming, 
2 slight to medium foaming tendency, 
3 medium foaming tendency, and 
4 strongly foaming. 
TABLE 
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Surface Iodine 
Comp. Wetting power 
Foaming tension color 
acc. to 
(sec.) power (10.sup.-3 N/m) 
number 
Example 
20.degree. C. 
70.degree. C. 
C = 2 g/l 
C = 2 g/l 
C = 2 g/l 
______________________________________ 
1 &gt;300 116 1 40.5 2 
2 &gt;300 86 1 43.5 1 
3 &gt;300 91 1 42.5 1 
4 290 77 1 41.5 1 
5 &gt;300 78 1 41.6 1 
6 &gt;300 93 1 44.4 1 
7 &gt;300 93 1 43.7 1 
8 &gt;300 93 1 43.7 2 
9 &gt;300 227 1 42.5 1 
10 188 73 1 40.0 1 
11 &gt;300 114 1 43.8 1-2 
12 142 67 1 41.4 2 
13 &gt;300 131 1 40.9 1 
14 &gt;300 143 1 43.6 1 
15 &gt;300 145 1 44.4 1 
16 &gt;300 140 1 42.3 1 
17 147 92 1 40.2 1 
18 178 78 1 39.8 1 
19 148 91 1 42.8 1 
20 300 134 1 39.3 20 
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