вход по аккаунту


Патент USA US2406338

код для вставки
- Patented Aug. ‘27', 1946 '
Laszlo Auer, South Orange, N. 'J._
No Drawing. Application October 2'7, 1943,
Serial No. 507,895
3 Claims. (Cl. 260-106)
used with the modi?ed products.
This invention relates to treatment of rosin,
and especially to treatment with certain modify
ln-part of my copending application Serial No.‘
semi-drying oils in paints and other coating and
~ plastic compositions.
tures of rosin acids, known today as abietic acid, 10
others. Such rosins commonly have an acid value
of from about 145 to 185, usually from about 160
- to about 168, and in their ‘natural state they-are
ordinarily hard, brittle materials, of melting
point from about 70° C. to about 85° C.
' Rosin is a valuable raw material for a number
i?ed rosin products, such products may be em
ployed as a replacement ingredient, in substan
tial proportions, for linseed or other drying or
rosin. The present application is a continuation~
pyro-abietic _ acid and d-pirnaric acid amongst
Because of the improved properties of the mod-7
ing agents promoting softening or liquefaction of
461,795, ?led October 12, 1942.
As is known, gum or wood rosins contain mix
varnishes and the like. Usually, however, at least
some drying or semi-drying oil is advantageously
' For certain special purposes in .the soap and
paper sizing industries, the modi?ed rosin prod
acts of the invention may also be of advantage,
notwithstanding the'fact that the modi?ed prod
ucts have a reduced acid value.
One of the most important modi?cations
brought about by the process of the invention is
the softening Or liquefying of the rosin. i.»e.. at
least some reduction of’ brittleness or in melting
point, or both. In addition, the process of the *
and plastics industries. There‘ are, in fact, 2. 20 invention is notable in its e?'ect on the acid value,
the invention providing for appreciable reduction
number of examples in the art of use of various 1
in acid value, as will further appear. In referring
rosin derivatives for purposes such as those men
to changes of this type and in making compari
tioned, Some of the most important and common
sons of the modi?ed products with products not
examples occur in the coatings industry, 1. e., use
:11; rosin derivatives in paints, varnishes and the 25 treated with modifying agents, it is to be under
of commercial purposes, such as in paper sizing,
soap manufacture, and especially in the coatings
stood that the statements regarding changes and
comparisons are always made on the basis of a In its natural state, however, rosin is not well
suited to many commercial purposes for which ‘ relation between the producttreated with a mod
ifying agent and a product treated in exactly the
it is potentially a valuable raw material.
30 same manner (heating, etc.) but/without a modi
The primaryobiect of the present invention
fying agent.
is to modify various physical properties of rosin,
According to the invention, by appropriate con
whereby to produce modi?ed rosin products
trol of treatment conditions, and by appropriate
which are better adapted to many uses for which
selection of materials, the degree of softening or
rosin or rosin derivatives are now employed. In
addition, the modi?cations, brought about in ac 35 liquefaction and also of acid value may be regu
lated to meet various different requirements,
cordance with the present invention make it pos
For instance, according to the invention, it is pos
sible and advantageous to use the modi?ed rosin
sible-to very extensively soften the rosin, or to
products for many purposes for which rosin in
very extensively lower the acid value, or both.
its natural state and also various derivatives
Although the invention is not limited thereto,
thereof are not well suited.
it is‘of especial importance and advantage in ac
To illustrate, reference is made to coating com
cordance with the invention to subject the rosin'
positions, such as varnishes.- In its natural state,
to treatment for a time and under conditions
rosin is a brittle material and therefore yields a
brittle ?lm when employed alone .as varnish 45 such as to change the physical character of the
rosin ‘from its natural hard and brittle condition
_ solids. Thus, rosin in its natural state does not
to a consistency approximating the so-called
have ?lm forming characteristics such that it
"cold ?ow,” i. e., a consistency according to which
\ may satisfactorily be employed alone as vehicle
solids ‘in a. coating composition. ' According to
. the material will gradually ?ow at normal room
this invention, modi?cations’ are brought about 50 temperatures, so that if ‘a blob of .the modi?ed
rosin is, placed on a ?at surface, it will more or
in the rosin so as to secure a rosin product having
?atten out, often at a rate which
drying or ?lm forming characteristics which are
withthe eye. For many pur
well suited to the coating composition industry,
poses a liquefaction at least to this degree is de
thereby even making possible employment of the
modi?ed rosin products alone as vehicle solids in
For certain purposes it is- advantageous that '
' 3
the rosin be lique?ed even to the extent of be
coming a mobile‘ liquid, similar, for instance. to
' the consistency of certain oils. such as bodied
linseed oil.
even more, although usually not more than about
10% .will be absorbed by the reaction mass.
The percentage of other modifying agents pres
ent during treatment with sulfurdioxide, such
as the decarboxylation promoting agents above
My preferred range of liquefaction extends
' referred to, may be anywhere from a trace, for
from about the consistency of a viscous oil to
instance, from .0l% or .5% up to about 10% by‘
about the cold flow consistency above mentioned.
weight of ‘the rosin being treated, and I have
although it is to be understood that a greater or
found a particularly advantageous range to be
a lessor degree of liquefaction is also contem 10 from about 1%. or 2% up to about 5%.
The effects of certain variations in tempera
The modi?cation process
ture, percentage of modifying agent and time
will be pointed out more fully hereinafter.
The process of the invention involves heating
Thorough dispersion of the modifying agent in
the rosin in the presence of sulfur dioxide,~the
‘the rosin is of importance and appropriate con
duration of heating, temperature and other treat
trol of temperature and ,time both contribute
ment conditions,‘ being such as to vefl’ect. decar
to bringing about such thorough dispersion. Ag
boxylation or softening of the rosin, and being
controlled in accordance with the extent and type
itation may be employed as an aid to securing
- thorough dispersion. Usually not more than a
of modification desired.
In addition to sulfur dioxide other modifying 20 few hours treatment on temperature will be found
suiilcient, for instance, from about one hour to
about five hours, although in some cases, the re
action proceeds very rapidly, requiring not more
agents may be present, ‘such for example as the
following inorganic acids which promote decar
than about one-half hour.
Sulphurous (H2803)
Hydrosulphuric (HzS)
fying agent servejto exclude the air.
tact of .air may be brought about by blanketing
the surface of. the reaction mixture with some
1 inert gas, such as CO2, or nitrogen. Where vacu
um is-used, a pressure, for instance, of about 100
Moreover, any one of many other decarboxyla
tion promoting agents may be present, such as
organic acids, metal salts, and other groups and
mms. Hg to about 45.0 mms. Hg will be found ef
fective, although higheror lower pressure may
be used, under various circumstances.
.classes of ‘ agents as disclosed in various of my
Some. more or less general considerations re
prior patents including those patents mentioned
Vacuum is also effective for the purpose of‘
excluding air and, in addition, reduction‘ in con
elsewhere herein,
- ‘
Another important consideration is that the ‘
reaction is preferably carried out in the absence
of air, or out of contact with any substantial
quantity of air. For this purpose the reaction
may be carried out in a closed vessel, though not
necessarily at a positive pressure, so that the gases
or fumes of theréaction released from the modi-'
garding the process should be noted, as follows:
Although the complete mechanism of modi?
cation may not be fully understood, it may be
mentioned that rosin ‘is an organic isocolloid, i. e..
a colloidal system in which the dispersed phase
and the dispersion medium are both of the same
example Patent No.
The treatment in the presence of sulfur dioxide
is desirably carried out either under positive pres
sure or by bubbling the gas through the reaction
mixture. The bubbling may be employed under
chemical composition, though present in different
By selection of modifying agents, and by ‘ap 50
propriate variations in treatment procedure,
time, temperature, etc.,. I am enabled to pro
duce modi?ed rosin products having quite a wide
range‘ of properties. In fact, according to the
invention, it is possible to secure a modi?ed prod 55
physical states.
or relative proportions of the dispersed Phase and
dispersion medium may be altered. Moreover, the‘ '
modi?cation process apparently also involves de
carboxylation, the extent of which is usually in- '
I uct in which either the- acid value or melting
By modification I believe that the relationship
Possibly also non-‘volatile aggregates or poly
point is very extensively lowered, or in which
both of these properties are simultaneously
lowered to a great extent. Various of the decor
mers are formed.
Some of the foregoing effects or reactions (par
boxylation promoting agents ‘are notable in mak-v 60 ticularly with respect to the physical consistency
of the modi?ed product) may work in one direc- ing possible extensive lowering of meltingpoint,
and others in the opposite direction.
so that in many instances liquid products are ob
In considering the nature of the modi?cations,
it is to be noted that, While some small loss inv
In carrying out the procesathe rosin i's-heat
ed in the presence of the sulfur dioxide at tem
- perature between about 100° c. and about 350°
0., depending upon the materials used and the
degree of modification desired. Usually the tem
weight may occur by volatilization (usually not
more than about 15-20%), no appreciable frac
tional or destructive distillation takes place.’
With appropriate precautions to avoid distillation
the process can usually be carried out without
perature should be at least 250° C. and most fre
quently above 270° C. in order to secure appreci 70 loss or .more than 5% or 10%, such small loss as
does occur usually comprising‘ water, CO2, etc.,
able modi?cation of the properties of the rosin.
at least in major. part. Asa precaution, the tem
Throughout the heating period the percentage ' perature
should be kept below the boiling or dis
of sulfur dioxide bubbled through or otherwise
tillation point of the main reaction product, under
brought in contact with the rosin may be any
by weight of the rosin or 75 the applied reaction conditions of the process.
where up to about 30%
By this precaution, destructive distillation or
cracking is positively avoided.
ployed may be such that gases evolved from the
reaction will serve to effectively exclude air, with
out applying vacuum. Furthermore, certain
The modi?ed rosin product is quite'unique, since
the rosin molecule retains almost as many carbon
gases, such as CO2, or nitrogen can be either
bubbled through the reaction mass or employed
_ atoms as are present in the initial basic con
stituents of the rosin, the number of carbon atoms
as a blanket on the surface of the batch'under
being reduced ‘only by, that number involved in
the decarboxylation. Still further, the types of
going ‘treatment; vExpedients of this type not
onlyserve to exclude the air from the reaction
but may also be utilized, for their supplemental
constituents of the modi?ed rosin are very few in
number, probably not more than two or three, and 10 effect on the material being treated,‘ this subject
these constituents are characterized by boiling
being more fully considered in my copending ap
points all lying within a narrow and relatively
plication Serial No. 318,650, ?led February 12,
high temperature range, as can be demonstrated
1940 (now Patent 2,298,270) , ‘of which the present
by subsequent distillation of the modi?ed prod
application is a continuation-in-part. It is here
ucts. The modi?ed products, for practical pur- ' 'further notedlthat certain features herein dis
poses, are non-volatile when exposed to the air.
closedare also disclosed in my‘ prior U. 5. ap
It is of importance in securing various of the
plication Serial No. 359,425 (now Patent 2,213,
' foregoing characteristics that the reaction take
944); and Serial No. 143,786 ‘(now Patent No.
place without any appreciable concurrent distilla
2,189,772) .l
tion. In addition, the absence of air and/ or con 20
trol of temperature are important in avoiding de
applications, still other variations in process may
structive distillation.
be employed for a number of diiferent purposes, _ ‘I
Whatever the exact nature of the chemical col
but it is not throught necessary to discuss these
loidal and/or physical changes which are brought
fully herein, since reference may be made to the
about, in general the treatment provided in ac
copending applications for that purpose. In
cordance with the present invention reduces the
passing, however, it is noted that additional treat
acid value of the modi?ed product and also sof
ment agents, of a supplemental character, may
, tens or lique?es the material. These changes,
also be present during the reaction, among which
together with others which usually take place,
might be mentioned dissolution promoting agents
such-as imparting drying characteristics to the 30 of the type disclosed in my issued Patent No.
rosin, and improving ?lm forming properties of
2,293,038. Various combinations vof modifying
the modi?ed products as compared with untreated
agents may also be used for different purposes,
rosin in the absence of other vehicle solids, for
including combinations of the modifying agents
instance, make possible or'practicable use of my
above disclosed, as well as combinations of the
modi?ed rosin products for many purposes for 35 modifying
agents herein disclosed with agents‘;
which rosin in its natural state is not suited, or at
disclosed in other of my applications mentioned
least not well adaptable, and for which many
above as well as hereinafter.
known rosin derivatives are likewisenot satis
It is further to be noted that in general increas
_ factory.
any one or all of the variables: namely, tem
By appropriate selection of modifying agent
perature, time of treatment and percentage of
and treatment conditions, such as temperature,
modifying agent, increases the extent of modi
time, vacuum, vetc., I am enabled to control various
fication. It will be understood that the foregoing
physical properties of the modi?ed products, and
is a general rule normally applicable within the
notably the acid value, saponi?cation value and
of operation above indicated, although, as
physical consistency. In general, the most valu- ,
to at least some variables, there may be limits '
able modi?ed products have, for instance, a sa
beyond which the general rule does not apply.
poni?cation value not exceeding about 120.~ ' . For instance, excessive increase in temperature
' may substantially alter the character of the proo- -
Example 1
heated in a one-liter distilling ?ask for 5 hours
at a temperature of 290-295’ C. and under a pres
sure of 400 mm. Hz. 80: ass was bubbled through '
the molten rosin during the 5-hour treatment
periodat a rate ‘of 17 grams per hour, 1. e., 3.4%
per hour based on the weight of rosin treated.
The acid number of the rosin at the end of the
treatment was 131.
Example 2
In this‘ example a batch of 300 grams of ww
,wood rosin was heated in a one-liter ?ask imder
the same conditions as in Example 1. In this
example, however, 80: was bubbled through the
batchduring the 5-hour treatment period at a
rate of 25gramsperhour. Thisisequivalentto
a rate a little above 8% per hour.
ess. On the other hand, in instances where a
50 soap forming metal is present in the modifying
agent, excessive increase in percentage of modi
fyin's asent'may not yield as soft a product as a
lower percentage of the modifying agent.
In considering the starting material on which
the process may be employed, it is ?rst noted
that the process brings about changes both of a
colloidal and also of a chemical nature.
It is ,
important, however, to bear in mind that the
process essentially involves a' reaction with the
rosin molecule. that is, with the type of molecules
of which the basic constituents'oi natural rosin
are composed. Therefore, while rosin itself, such
mas‘ gum or wood resins, represents perhaps the
most important starting material towhich the
process isadaptable, it is noted that the process
-may be employed on rosin which has been pre
treated in various ways, or- on mixed or chemicals
1y condensed materials incorporating rosin, since
The acid value of the final product was 114.5.
the reaction will take place wherever the rosin
Certain variations in procedure may be 70 molecule is present, provided, of course, that the
physical or chemical state or “environment” of
For example, vinstead of using vacuum during
the rodn- molecule 3 not such as to prevent the "
the treatment period,‘ other procedure may be I reaction from taking place.
adopted with a view to excluding air from the
It may also be mentioned that there are other
reaction. The form of the reaction vessel cm 75 natural resins, such as copnls, which act simi
I larly to rosin by treatment in accordance with
this invention. In fact, the reaction may be
carried out on any of the natural resins con
stances where the vulcanization is carried out in
a varnish solution, the sulphur chloride treat
ment is especially practical.
“iused" before becoming soluble in organic sol
vents and miscible with iatty oil. When oopals
are used in'the present process. they should ‘be
employed in the fused state.
. _
the modi?ed rosin - roducts maybe subject to
- erin or other polrhydric alcohols, such as glycols,
The modi?ed products 0! this invention may,
pentaerythritohmannitol. sorbitol, etc.
The vulcanized. lique?ed resin products made
in accordance with the invention have valuable
properties for a number of purposes including the
marina of protective coatincs, some or these vul
15 caniaed products beina useful as plasticizers ior
ing upon the use for which it is intended. Thus,
eoetins compositions and plastics.
ior'example, the modi?ed products may be vul-‘
I claim:
canized with sulphur. The modi?ed resin prod
l. Aprocess for treating rosin, which process
ucts secured in-accordance with the foregoing,
consists in heatinlr the main to a temperature of
may be vulcanized as such, or in solutions, such
at least 250° C. but not above about 350° 10.:
as varnish solutions, (in the latter case with sul
under conditions promoting decarboxylation, and
circulating sulphur dioxide gas into. through, and
phur chloride).
Further, they may be converted into emulsions
out or the reaction vessel dunnr said heating. I _
and used for various purposes in that form.
' ii'desired, be'subject
> v
still other supplemental treatments, such- for in
stance, as esterincation, as by treating with glyc
Copals are iossil gums which have to be
As is mentioned in my application Serial No.
386,371, ?ied April 1, 1941 (new Patent 2.311.200) ,
taining high molecular resin acids; Therefore,
wherever any such other natural resin behaves
similarly to rosin, it is. herein considered as an
to other treatment, depend
' In the event sulphur or other sulphur-like vul
canizing agents are used, vulcanization, for cer 25
tain purposes, is desirably carried out at tem
peratures between about 120° C. and 200° C. For
other purposes where vulcanization is to be ei
rected at lower temperatures, for instance, at
room temperature. sulphur chloride or similarly 30
acting vulcanizing agents should be used. In in
2. A process in accordance with claim 1 vin
which the treatment temperature is‘ about
290-395’ C.
8. A process in accordance with claim 1 in
is bubbled through
Без категории
Размер файла
583 Кб
Пожаловаться на содержимое документа