вход по аккаунту


Патент USA US2407248

код для вставки
Patented Sept. 10, 1946
2,407,248 , »
‘ Joseph N. Borglin, Wilmington, Del., assignor to
Hercules Powder Company, Wilmington, Del., a
corporation of Delaware
No Drawing. Application June 26, 1942,
Serial No. 448,625
7 Claims. (01. zen-#103)
This invention relates to a method for the pro
duction of resinous materials and more particu
larly to a method for dehydrogenating polymer
ized rosins and esters thereof.
melting point of 101° C'., was heated under a ni
trogen atmosphere until a temperature of 286° C.
was attained. At this point, one and one-half
per cent of sulfur, based upon the weight of the
The polymerization of rosin and rosin esters’ 5 rosin, was added slowly, and the temperature was
with sulfuric acid, boron ?uoride, andvother polyheld constant at 280° C‘. for three hours. After
merization catalysts has been described in the art.
this, the product was cooled. By means of this
Such polymerized resins and rosin esters are
procedure, the bromine number of the polymer
highly valuable materials because they have inized rosin was reduced from 107 to 56 and the
creased melting points in comparison with ordi- 10 drop melting point was increased.
nary rosin and its esters. As a result, these polyExample 2
merized materials have found wide use in the
preparation of improved coating compositions
.A sample of the Same polymerized resin em
which dry to form much harder ?lms than those
ployed in Example 1 was heated under a carbon
obtainable» from coating compositions prepared 15 diOXide atmosphere to a temperature of 200° C-,
from ordinary rosin and esters thereof. Moreat Which point One and One-half Del‘ cent of $111
over, polymerized rosin and its esters possess a
fur, based upon the Weight Of the polymerized
lighter color and increased coltl'r. stability when
resin. was added. The temperature of the reac
subjected to the action of light, heat,.etc., than
tion mixture was held at 200° C. for three hours,
rosin and rosin esters which have not been poly- 20 after‘which the product was cooled- This DIO
merized. Further important . advantages and
cedure reduced the bromine number of the poly
uses of polymerized rosin and its esters have been,
merized rosin to 74.
disclosed in the art.
Now, in accordance with this invention, a
Emmpl? 3
method has been discovered for the further im- 25 -A Sample of the polymerlzed rosin employed in
provement of the qualities of polymerized rosin
Example 1 was heated under a carbon dioxlde
and esters of polymerized rosin to provide a maatmosphere to a temperature of 250°
and two
terial of increased stability. This novel method
Per cent of sulfllr» based upon the Welght of the
comprises contacting a polymerized rosin or a
polymerized rosin, was added. The temperature
polymerized rosin ester with from about one to 30 of the mlxtul‘e Was-held {it 250° C- fol‘ ?Ye hours
about ten per cent of sujlfur, based upon the‘
and then the reaction mixture was subJected to
weight of the polymerized rosin or polymerized
Vac1_1um to remove ‘the hem ends- A Product,
rosin ester. at a temperature between about 150°
and 350“ C. under conditions adapted to effect
'havms a drop meltme point of 110° C‘. and a
bromme number ‘of 63’ was produced
substantial dehydrogenation of the rosin or rosin _ _
ester. The new product of this invention is a 5°
Emmple 4
dehydrogenated polymerized rosin or polymerized
The glycerol. ester of a 811115111“ 9301a polynger'
rosin ester characterized by a‘ bromine number
ized msm, havmg a drf’p meltmg pomt of 110 C:
below about 75 and by an increased melting point.
was heated ,under 3‘ mtrogen atmosphere to 280
It has been determined in accordance with this
0-’ after which one and one'half per cent of Sul"
invention that by dehydrogenating 9, polymerized 40 fur was added. 0 The temperature of the mixture
rosin or polymerized rosin ester to provide a
was held at 280 C. for three hours and the prod
product with a bromine number below about 75
not was then ‘cooled- By means of this proce'
a material of substantially increased stability is
‘we’ the bmmine number 0f the ester was re
_ duced from 82130 43.
Having thus indicated in a general way the 4”
Thus’ the Improved polymenzed rosin and
*polymerized rosin esters are provided by contact
nature of this invention, the following examples
ing the polymerized rosin or polymerized rosin
are given to illustrate the method of preparing
ester with sulfur under conditions adapted to ef
the improved polymerized rosin and polymerized
fect substantial dehydrogenation of the material.
rosin esters of this invention. In the speci?ca
tion and in the claims, the parts and per cents 50 The temperature range within which the dehy
drogenation may be conducted may vary within
are by weight unless otherwise speci?ed.
wide limits. Reaction temperatures of from 200°
Example 1
to 280° C. were employed in the examples, but
A rosin, polymerized with 100% sulfuric acid
any temperature between about 150° and about
while dissolved in benzene and having a drop 55 350° 0., and preferably from about 225° to about
280° 0., will be found to be suitable. The amount
of sulfur employed may also vary within wide
limits. In the examples, the amount of ele
polymerized rosin or polymerized rosin ester and
the elemental sulfur as such. Alternatively, dehy
drogenation may be effected with the polymerized
rosin or ester thereof orthe sulfur,,or.both, dis
mental sulfur employed was one and one-half or
two percent, based: upon the weightlof- the poly
merized rosin or polymerized rosin ester. Gen
erally, from about one to about ten and prefer
ably from about one to about ?ve per cent by‘
weight of sulfur, based upon‘ the’weightv off the
solved in a suitable inert organic solvent, ,such as
the para?in hydrocarbons as hexane, V,“ M. & P.
naphtha, etc., the aromatic hydrocarbons such as
benzene, toluene, xylene, etc., the mixed aromatic
alicyclic-hydrocarbonsias tetrahydronaphthalene,
rosin or ester, is used as a dehydrogenating agent“ 10' etc;, thealicyclic hydrocarbons as cyclohexane,
The reaction time which will be found to be most
decahydronaphtha'lene, etc., Solvesso No. 1, 2, 3, 4,
suitable will vary with the particular rosin or
etc. Dependinguponlthe reaction temperature
rosin ester being dehydrogenated‘, with there
and upon_.the,vaporrpressure of the solvent em
action temperature, with the degree of‘d'ehydro
ployedgthe. dehydrogenation may be conducted
genation desired, and will also depend upon other 15 at atmospheric or superatmospheric pressure, and
obvious factors. Generally, a reaction-period of“
the’- polymerized‘ rosin or polymerized rosin ester
not more than ?ve hours is used.
maybe dehydrogenated by a batch or continuous
The polymerized rosins which may be dehydroe
process; As shown in the examples, the method
genated in accordance with this invention may
of this invention is preferably conducted under
be those derived from any of. the various grades 20 an. inert. atmosphere, such- asnitrogen . or. carbon
of " wood‘ or gum rosin.
They may be produced’
dioxide, in,of the.light_~
fromisuch" rosins ‘by polymerization according to
any-of" the known methods, such as by treating
with various‘ catalysts. as sulfuric acid, organic
substituted sulfuric acids, boron ?uoride, metallic
halides as stannic. chloride, zinc chloride, alumi_
est color. ,
AS shown in Examplev 3, the .productmayalso;
be improved by subjecting.the.polymerized rosin
to .a .partiaLvacuum vdistillation at. the, end of the
reactionperiod :in.order. to remove .thelight ends
nunr chloride, hydrogen fluoride, or by treatment
of the‘ rosins with a highvoltage, high ‘frequency
electrical discharge; or by treatment with an acid
sludge formed by treatment of the rosin with sul
furic acid, such as isrdescribed in an application,
Furtherimprovementmay also be,.re
moving. the lightends through continued :Sparging,,gas,such as carbondioxide 0r-,ni-<
trogen,. or. by‘ combinationof tlie= sparging, and.
vacuum distillation.
The polymerized. rosin , and. polymerized. rosin,
ester. prepared as: described herein are .highly use-_
Serial No. 328,864, ?ledApril 10, 1940, by Clell E.
Tyler, now U.’ S. Patent No. 2,288,659. The poly;
merizedirosins whichmay. be dehydrogenated to
ful and desirableproducts characterized.bygreat.
stability and highmelting point. Thus, these:
polymerized products ?nd importantluseincoat
ing compositions;adhesives, paper sizes,.soaps,
rubber compounds, etc., of increasedresistance to.
produce the improved products of this invention
will‘be those. having adrop melting. pointfrom
about 5° ‘to about 100° C. above the melting point
of the original jrosinused in the polymerization.
The polymerized.rosinesters which may be de
hydrogenated' willinclude. polymerized monohy- . 40
- dric alcohol esters and polymerized polyhydric al
cohol esters of rosins which have been polymerized
according to any of themethods mentioned in the
precedingparagraph. Thus, theylwill include the
methyl;,.ethyl,_propy1, butyl, ethylene glycol, pro
pylene. glycol, diethylene glycol, trimethylene gly
col, glycerol, pentaerythritol, etc., esters of such
polymerized rosins. Alternatively; the polymer
ized rosinesters maybe. prepared by-esterifying
any of the: aforementioned alcohols with any wood
or'glumrosin and then‘ polymerizing the: ester
with' any,~of" the polymerization. catalysts men
tioned in the preceding-paragraph, according to
procedures well known. in the art. The poly_
oxidation anddeterioration through other. causes...
What .I. claim. and. desirev to protect. by Letters.
Patentis: .
1. The method of stabilizing, a- material, se-k
lected. . from. the group - consisting. of. polymerized
rosin and. polymerizedrosin. esters~ whichi com.»
prises.- contacting. the. material. with - from. about.
one to , about. ten. per. cent, of. sulfur, basediupon .
the weight. of. said material,- attae. temperature.
between. about .1509 and about 350‘? C. until the»
bromine number- of the material. has. become.
reducedto. below‘ aboutz75 without a.».decr.ease-in'
its. melting. point. .
2t The. method. of. stabilizing;a.-ma-terial selected.
from: the: gl'oup- consisting. of‘. polymerized; rosin.
and; polymerized rosin. esters» which- comprises;
merized rosin esters suitable for use in this in
contacting the~ material with . from ~ about'one-toi.
vention‘ are those having a‘ drop melting point
from about 5° to about 100°C.‘ above the melting
pointfofi the original rosin ester employed in the
about?ve‘ per. cent‘. of sulfur,‘ based‘ upon‘ the;
process described in this speci?cation, the poly
merizedi rosin or polymerized r0sin'ester may be
ing point;
subjected‘ to a conventional heat treatment at a
whioh'compri‘sesi contacting'the polymerized "rosin
temperature from about 250° to about 350°C. to
effect a re?ning of the rosin ester. The methods
with from about one to about ten per cent! of?‘
‘ sulfur,‘ based‘. upon the: weightxof therosin', at
a temperature between‘ about 1150"? and'ab outf1350"?'
weight of said material, at-artemperature between:
about 225‘" and about‘ 280° C..until theibromine:
number of the. material‘hasbecomerreducedf to?
Before being subjected'to the dehydrogenation 60 below about 75 withouti-aiwdecrease in'v itsv'melte
for conducting such a heat treatmentare more
fully disclosed in an application entitled “Method
of're?ning polymerized rosin,” Serial No. 371,991,
?led December 2'7, 1940 by Raymond F.v Schlaan
stine and in an application, entitled “Method of
3.‘ Themethod of 'stabllizingrpolymerizedJrosini .
C. untilithe bromine" number ‘of ‘the polymeriz'edi
rosin has- become reduced to‘ below: about‘ '75"
without a. decrease inv its' melting: point:
4. The method" of‘ stabilizing a» polymerized‘
re?ning polymerized rosin esters,” Serial No.
378,056‘, ?led February 8, 1941 by Alfred L, Rum
rosin glycerol ester which- comprises‘ contacting’
The dehydrogenation-process may be conduct
cent of sulfur, based upon the. weightof. the
ester,.at a temperature. betweemaboutl 15.03 and.
about‘ 350°"C'. until'the bromine number of the
ed‘; as‘sh'own'in the-examples; by contacting the
the ester with from abonttone: to about ten per
polymerized rosin ester has become reduced to
below about '75 without a decrease in its melting
5. The method of stabilizing a polymerized
rosin pentaerythritol ester which comprises con
tacting the ester with from, about one to about
ten per cent of sulfur, based upon the weight
01’ the ester, at a temperature between about 150°
and about 350° C. until the bromine number of
the polymerized rosin ester has become reduced
to below about 75 without a decrease in its melt
ing point.
6. A method of stabilizing polymerized rosin
which comprises contacting the polymerized
rosin with from about one to ten per cent of sul
fur, based upon the weight of the rosin, at a
temperature between about ‘200° C. and 350° C.
7. A method of stabilizing a material selected
from the group consisting of polymerized rosin
and polymerized rosin esters which comprises
contacting the material with from about one to
ten per cent of sulfur, based upon the weight 01
said material, at a temperature between about
150° C. and 350° C.
Без категории
Размер файла
390 Кб
Пожаловаться на содержимое документа