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Патент USA US2404213

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2,404,213
UNITED STATE 5 PATEN r OFFICE
Patented July 16, 1946
2,404,213
.ROSIN CARBONATES
Joseph N. Borglin, Wilmington, Del., assignor to
Hercules Powder Company,‘ Wilmington, Del.,
a corporation of Delaware
'
No Drawing. Application December‘9, 1942,
Serial No. 468,427
-'
5 Claims. (01’. 260—100)
1
This invention relates to a new composition
of matter and to the processior obtaining it and
and wherein a halo formyl alkyl ester is caused
to be reacted with an alkali metal rosin alco
particularly to a rosin carbonate.’
holate or a rosin alcohol.
‘
In accordance with: the present ‘invention
rosin’ alcohols and their alcoholates and esters
may be reacted with a derivative of carbonic
acid; to produce‘rosin esters‘ of‘carbonic acid.
The rosin’ carbonates may contain two rosin
groups‘ and may be referred to as neutral rosin
In general, the rosin alcohols and their esters
‘ and alcoholates that may be used in accordance
with this invention may be derived from ordinary
rosinw and‘ the speci?c rosin acid components
thereof as, for example, abi'etic' acid, sapinic
acid,‘ d-pimaric‘ acid; l-pimaric. acid-,etcq' also
carbonates. The rosin carbonates may contain 10. they: may be: derived‘ from-"chemically modi?ed
rosin as, for example, polymerized Wood, hy
drogenated rosin, dehydrogenated rosin, rosin
one rosin group and vone alkyl, aryl', or aralkyl
group and may be‘ referred to as mixed neutral
rosin carbonates. Again the rosin carbonates
which has been subjected to a heat treatment
at about 250° C. to about 350°C’. and rosin which
may contain one rosin group and; one halo group
and maybe. referred‘ to as halo rosin carbonates. 15 has been subjected to a .heat treatment at about
The neutral‘ andvmixed‘ neutral rosin carbon
100° C. to about 300°C. in the presence of a suit- ‘ '
ates may be preparediin general by means of an
ester interchange wherein an ester of a rosin
The methodv in accordance with this inven
alcohol and a. dialkyl carbonate are caused’ tobe
tion is'illustrated by the following speci?crex
reacted together with or without'the presence 20 amples; all parts and percentages being by weight
of an alkalim'etal alcoholate. Further, the neu
unless otherwise speci?ed;
tral and mixed neutral rosin carbonates may be
preparedv by means of’ an alcohol interchange
’
Example 1‘
_
‘
wherein a rosin alcohol and ‘a dialkyl carbonate
Fifty grams of ~ hydrogenated abietyl' alcohol
are caused to be reacted together in" the presence
were dissolved in 50 grams of xylene.v Twenty '
of an effective, amount of an alkali metal alco
grams of phosgene were passed through the solu
holate as a catalyst; ‘Again, vthese ‘neutral and
tion for two hours ‘at, room temperature. An
nriiin-Id'v neutral" rosin‘ ‘carbonates. may‘ be prepared‘
exothermic reaction took, place resulting in the
by means of.’v an, acid halide] reaction wherein ‘an;
acid halidejas‘; Ior‘exampl‘e, ‘a’ halo formyl‘ halide‘ ' evolution of a relativelysmall amount of heat.
able
catalyst.
-
r
y
,
r
w
al'co‘h‘ol'ate or a rosinalc'oh'ol‘ or'wherein a halo
forinyl'falkyl ester is caused to .be reacted‘ with
The xylene was removed by means of vacuum
distillation carried out at a maximum distilla
tion temperature‘ of’ 160° C‘. ' Fortye?ve grams: of
an alkali metal’ rosin al'coholate or a ‘rosin
. a brown semi-viscous, saponi?ab‘le l-iquid- were
is caused to be reacted with an alkali metalv rosin
alcohol‘
7
‘
'
"
'
_ "I'ne'halb rosin; carbonates maybe prepared,
obtained. The liquid contained about. 6mm
chlorohydroabietyl carbonate and about 37% by.
in gerieralfbyfrheans of an acid halide reaction
wherein. an acidhalide; as, forv example,' a halo
dro‘abietyl carbonate.
form‘ylhalide‘jis caused to ‘bereacted with an
out in a manner substantially, as described with
'
'
Each of the following“ examples ‘was carried
alkall‘nietal‘rosin alcoholate or a‘rosin alcohol‘, 49 reference to Example 1:‘
2,404,213
.
3
,
. 4'
The mixed neutral and the neutral rosin car
.
Carbonic acid derivatives operable in accord
'ance with the present invention
having the general formula
bonates may be prepared by means ‘of an ester
are the esters -
interchange wherein an’ ester of arosin alcohol
and an ester having the general formula
'
o=o
"
/O—R
'
0-R
0:0
/
05R’ '
'7 ‘ wherein R, and R" are alkyl, aryl, or aralkyl rad
wherein R and R’ are alkyli'aryl, or aralkyl rad-Q l0 icals, are caused to be‘reacted together with or
icals as, for example, methyl, ethyl, propyl, iso _ _ Without the presence of an alkali metal alcoholate.
amyl, isobutyl, etc., and speci?callydiethyl .car-" .The ester interchange reaction may be carried
bonate, diisoamyl carbonate, diisobutyl carbonate, ’
dimethyl carbonate, diphenyl carbonate, ' ethyl -
out by heating a rosin alcohol ester as, .for ex
ample, rosin, alcohol acetate with a dialkyl car
methyl carbonate, dibenzyl carbonate, etc; halo 15 bonate as, for examplegfdiethyl carbonate in a
formyl halides having the general formula
suitable solvent, as for example, benzenepxyl'ene,
etc. The proportions of neutral and mixed neu
tral rosincarbonates formed depend in part upon.
thelreaction time and-‘temperature. ‘Ordinarily,
20. when the reaction is carriedout at room temper-V
ature, a mixture of-vryneutralv and“. mixed neutral;
rosin carbonates are formed with the mixed neu
wherein X and X’ 'are’halogen radicals as,- for
tral rosin carbonates predominating._ The Iquan»
example, chloro, bromo, etc., and speci?cally‘
tity of neutral rosin carbonates increases with
phosgene, bromo ‘formyl bromide, chloro forrnyl,
increased reaction time and increased. temper.-,
bromide,'bromo formyl chloride, etc.;"halo alkyl‘
Generally, the 7reaction time-may. vary,
ature.
' esters having the general formula
'
'
from about 1 hour to aboutlZ-hours- and will
usually reach equilibrium in from about 5 hours
to about 10 hours.’ The temperature-may vary.
30 from about 100? C. and about 250° C..and usually
isbetween about 150$> ‘C. andabout 200‘? C‘. The
concentration of the ro'sin- alcoholesterin bene,
zene or any other suitable solvent may vary
' wherein X is a‘halogen radical as, for.‘ example,
from about 10% to about 60% andpreferably‘
chloro, bromo, etc., and-R is- an alkyl radical as,‘
‘ vfor example, methyl, ethyl, propyl, isoamyl, etc., 35 may
Thebeneutral
between
andabout
mixed15%
neutral
androsin
about
carbonates
30%.
and speci?cally chloro‘ ethyl carbonate, chloro.‘
may be prepared by meanslof an~alcfohol inter
methyl carbonate, bromo ethyl carbonate, bromo
change wherein a rosin alcoholand an"esterjjcarév
methyl carbonate, chloro propyl carbonate, chloro‘
isopropyl carbonate, chloro isoamyl carbonate,‘
etc.; and alkali metal salts?represented by the
general formula‘
'
‘
'
.'
'
.
"
>
-
bonate of the type hereinbefore referred. toare;
40 caused to be reacted together in the presence'jof
an effective amount of an alkali metal alcoholate
‘
as the catalyst. , 'Where ,dimethyl. carbonate is 1
the ester carbonate 'usecl incarryingout .the al-.
cohol» reaction with a rosin alcohol, ,methylalm
45
cohol will-distillout of the reaction mixture. as the
reaction progresses, under. the. in?uence - of heat
when .using‘ sodium/methylate as, the, catalyst.
The reaction may be carried out atja temperature.
between about 60‘? .c. and about 250° C..but is-prer.
ample,‘ sodium,‘ potassium, lithium,v etc., and
wherein R represents an alkyl, aryl,’ or aralkyl 50, erably carried out at a temperature between about
wherein M represents an alkali metal asyfor ex
radical.‘
;
f
'1
"'
'
-
'
The rosin alcohols and their ester, and alco
holate derivatives operable-in-accordance with
this invention'may be ‘prepared from any of the
natural and chemically modi?edrosins by any;
100° C. and about 200° C. , Generally, the reaction
time may vary, from about 1 hountor'about‘fll ’
hours and will, usually reach'equilibrium' in from.
about 5 hours to about 10 hours. Gvenerall?whe'nx
the reaction is carried out at the iowergtemperae
tures‘and fora shorter period of time,'a greater I
~-=percentage of the mixed neutralrosin carbonates"
.is. formed. When the reaction is carried out at.
the higher temperaturesand for a greater period
in the art to produce the rosin alcoholsand their:
,00 of time, a greater percentage ofneutral rosin car
ester and-alcoholate derivatives.- 7 ~
,g
-'_.‘
Chemically zmodi?ed rosins which may be"E bonates'is formed._ In either case, a' mixture of
treated in'accordance with procedure well known l the neutral‘ and the mixed neutral rosinjcar
in the art to form the chemically modi?ed rosin
bonates is produced when a rosin alcohol ‘and ‘a
of the methods well known in the art. Any one
‘ ' may-be
of the more
treated
than
according
50 di?‘erent
to methods
isomeric wellknown
rosin acidsp"~
alcohols?and their ester, and alcoholate' 'derivar-q '
carbonic acid derivative are caused to be reacted
rosins, the dehydrogenated rosinls, the polymer
10% to about 60% and preferably-,emayrbelbh
tives may be any rosin which has been treated 05 iri'accorda'noe with the present invention. The r
to’ modify its ‘chemical structure; Rosins whichi ' :rconcentration, of the rosin‘ alcohol in benzene or
fall within this general class are the hydrogenated ' “any other suitable solvent-may vary from: about
ized rosins,- those rosins'which have been heat‘ ' tween about :15 %_ and about 30%‘.
treated. at about 250° C. to about 350° C., those 70 The neutral rosin carbonates,,the' mixed neu-r
'traTrosin carbonatesyan’d the halo rosin car
rosins'which have been heat treated at about 100°‘
C. to about 300° C. in. the presence ,of a suitable
bonates maybe preparedby means [of 'an' acid
catalyst, polymerized ‘crystallized vrosins, hydro;
" halide‘reaction wherein'jan acidjhalideas, for ex;-~
genated crystallized resins, and heat treated crys-'. ‘
ample, a halo formyl‘ halide may be‘ caused to
tallized rosins. ->
be reacted Withatosin- alcohol; > The acid halide '
Q
5
2,404,213
reaction may be carried out by causing a rosin
alcohol or an ester or alcoholic derivative thereof
to be reacted with a halo iormyl alkyl, aryl, or
aralkyl ester. It is preferred to use the rosin al
coholate when carrying out the reaction. A suit
able halo formyl ester may be the chloroethyl
ester of carbonic acid. It is preferred to use an
excess of the chlorocarbonic acid‘ ester, for ex
through a suitable solvent solution of a rosin al
coho1 causes the formation of the various rosin
carbonates. ‘Ordinarily, when the reaction is car
ried out at room temperature, a mixture of neu- I
tral and halo rosin carbonates is formed wherein '
the halo rosin carbonates predominate. A greater
percentage of the neutral rosin carbonates is .
formed when the halo formyl halide-rosin alcohol
ample, about 25% excess which is slowly added to ‘ reaction is carried out at the increased reaction
the rosin alcohol during mild stirring of the-mix 10 temperatures and reaction time. Generally, the
ture. An exothermic reaction takes place-with
time required to carry out the halo-formyl ester
the evolution of a relatively large amount of heat.
rosin alcohol and the halo-formyl halide rosin
The resulting solution may be vacuum ?ltered to
alcoho1 reaction may vary between about 1/2 hour
remove the sodium chloride precipitate.- Excess . and about 10 hours but, in general, equilibrium is
chlorocarbonic acid. ester and solvent may be re 15 reached in from about 1 to about 2 hours. The
moved by means of distillation. The time of the
temperature for thesetwo types of reactions may
reaction may vary from about 3 minutes to about
vary from about 10° C. to about 100° C. but the
1 hour but, in general, the reactionwill take place
reaction usually takes place at about 20° C- to
in about 10 to about 20 minutes. The reaction
about 40° C.
‘
~
temperature may vary from about 10° C. to about 20
The rosin carbonates are useful in the manu
100° C. The proportion of neutral rosin car
facture of adhesive compositions; 7
bonates and halo rosin carbonates in the reaction
“What I claim and desire to protect by Letters
mixture will depend in part upon the conditions
Patent is:
of reaction including temperature, time, and re
l. A mixed ester of carbonic acid and a hy
action components. Generally, the lower tem 25 drogenated rosin alcohol and an alkyl alcohol.
peratures and relatively shorter periods of re
2. A mixed ester of carbonic acid and a hy
action time are more conducive to the formation
drogenated rosin alcohol and methyl alcohol.
of the halo rosin carbonates than to the forma
3. A method of producing a rosinyl carbonate
tion of the mixed and neutral rosin carbonates.
which comprises reacting a haloformyl halide with
The concentration of the rosin alcohol in benzene
a rosin compound selected from a group consist
' or any other suitable solvent may vary from about
ing of a rosin alcohol, its acetate and its al
10% to about 60% and preferably, may be be
coholate.
tween about 15% and about 30%.
4. A mixed ester of carbonic acid and a poly
When the acid halide reaction is carried out
merized rosin alcohol and an alkyl alcohol.
using a halo formyl halide and a rosin alcohol, a 35
5. A mixed ester of carbonic, acid’and an alkyl
mixture of halo rosin carbonates, neutral car
alcohol and a rosin alcohol selected from the
bonates and mixed neutral carbonates result
group consisting of a hydrogenated rosin alcohol,
wherein the neutral rosin carbonates predominate.
A preferred halo formyl halide in this reaction
polymerized rosin alcohol, dehydrogenated rosin
alcohol and heat-treated rosin alcohol.
is, for example, phosgene, which, when passed 40
JOSEPH N. BORGLIN.
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