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atentedii
0V» 5, rest
'
.
'
2,410,418
MODH‘ICATION 0F ALKYD RESINS
Laszlo Amer, South Orange, N. .i.
No Drawing. Application Dctober 12, 1942,
Serial No. 461,799
3 Claims.
(Cl. 260-22)
i
‘
Z
and tough coatings and are important ingre
Gamer. FIELD or INVENTION AND STATEMENT or ‘ ‘
dients of various coating compositions.
Owners
This invention relates to the treatment of alkyd
resins with modifying agents, whereby to alter
the properties and characteristics of such resins.
The present application is a continuation-in-part
'
In considering the nature of the alkyds to
which the present invention is applicable, it
might further be mentioned that various alkyd
resins are sometimes classified according to their
drying'characteristics. Thus, some alkyds are
of my copending applications Serial No. 318,650,
non-drying,_some are semi-drying and baking
filed February 12, 1940, now Patent 2,298,270,
alkyds, and some are air drying alkyds. ‘Usual
issued October 13, 1942, and Serial No. 386,371, 10 ly fatty acids of non-drying oils, such as fatty
?led April 1, 1941, now Patent 2,311,200,- issued
acids of castor‘ oil, coconut oil and babassu oil,
yield non-drying alkyds. On the other hand,
February 16, 1943.
,
.
Alkyd resins are of many types, all being esters,
‘when employing fatty acids of semi-drying oils, .
most commonly esters of polyhydric alcohols,
suchas sun?ower oil and soya bean oil, the
such as glycerine, with mixtures of monobasic 15 alkyds secured are semi-drying alkyds, useful
for baking finishes and other purposes. Em
and polybasic acids,
_
Other polyhydric alcohols may also be used in
the preparation of the alkyds, such as glycols,
ployment of fatty acids of drying oils, such as
those of tu'ng 'oil, linseed oil and dehydrated
castor oil, yield alkyds having air drying prop
pentaerythritol, mannitol, sorbitol, etc.
Most usually, the polybasic acids are phthalic 20 erties.
acid and maleic acid, commonly used in the
‘Although various procedures have been em
form of their anhydrides. However, other poly
ployed in the production of alkyds, and although
basic acids and anhydrides are also sometimes
many different catalysts have been employed in
used in alkyd resin manufacture.
alkyd resin manufacture, I have found that the
The monobasic acids usually employed in alkyd
resin manufacture are the high molecular fatty
acids and/or natural resin acids, such as rosin.
The alkyd resins may be classi?ed in various
different ways depending upon their constituents
25
preformed alkyds-may be treated according to‘
the p'resent'invention, thereby modifying the
,physical and/or other characteristics of the
alkyds. For instance, the physical consistency
may be changed appreciably, as may also the acid
and properties and for some purposes certain 30 value and other properties.
characteristics are important, while for other
In referring to changes in characteristics and
purposes, other characteristics are important. v
properties, and in making comparisons of the
For instance, the esters of maleic acid and
modi?ed alkyd resins with resins not treated with
phthalic acid with glycerine are infusible and
modifying agents as used in the present process,
insoluble in organic solvents, after they have
it is to be understood that the statement regard
been heated for some time at elevated tempera 35 ing changes and comparisons are always made on
tures. Such esters yield only brittle films, in
the basis of a relation between the product treat
view of which for some purposes, it is of impor=
ed with a modifying agent and a product treated /
tance to employ combined esters of polybasic
in exactly the same manner, heating, etc., but
acids and monobasic acids, in preparing alkyd
without a modifying agent. The latter is often
resins. The monobaslc acids employed, for in
herein referred» to as a “blank” or “control” ex
stance, fatty acid and/or resin acid, impart im
periment.
\
proved solubility characteristics to the alkyds so
As is mentioned in my copending applications
that ‘they may readily be dissolved in organic
above referred to and also in others referred to
solvents, and thereafter used to advantage in
hereinafter, I believe alkyd resins to be organic
the coating arts.
~
,
isocolloids, i. e., colloidal systems in which the
Alkyds containing relatively high percentages
dispersed phase and the dispersion medium are
of phthalic anhydride or other polybasic acids are
both of the same chemical composition though
harder and less soluble in organic solvents than
present in different physical states.
alkyds containing a larger proportion of fatty
At least most of the alkyds containing-fatty
acid and/or resin acid. The type otalkyd con 50 acids behave similarly under treatment accord
taining larger proportions of polybasic acid are
commonly referred to as 7“short oil” alkyds, the
other type usually being identi?ed as "long oil”
ing to the present invention, ‘as do fatty oils,
many examples of fatty oil treatment with modie
fying agents being disclosed in copending appli
alkyds.
The medium or long oil alkyds yield elastic 55 cations. elsewhere referred to herein.
2,410,418
.
4
3
By the modi?cation process of the present in
vention, I believe the relative proportions oi’ dis
persed phase and dispersion medium are altered,
thereby altering the properties, and notably the
Typical examples of certain of the foregoing
classi?cations are given Just below:
' Metal salts of memento acids
(Formed by various combinations oi’ the fol
6 lowing:)
physical consistency of the modi?ed alkyd prod
uct.
'
‘Other properties of the alkyds which may be
Cations
Anions
altered and improved according to the present
Ammonium
- Chloride
invention, are solubility characteristics, drying
Lithium
Bromide
properties, and bodying time (of the alkyd).
Sodium _
Iodide '
Moreover, treatment with various of the modify
Barium
Carbonate-Bicarbonate
ing agents also yields alkyds having improved
Calcium
Sulphate
weather, water and alkali resistance, these prop
Zinc
Bisulphate
erties being of especial importance in coating
Iron '
Sulphite
compositions such as paints and the like.
15 Cobalt
Bisulphite
The nature of the modifying agents employed
Lead
Nitrate
Manganese
Nitrite
according to the invention is considered Just be
Copper
Borate
low but it is here ?rst pointed out brie?y that
the process involves dispersion oi’ the modifying
'
‘
Phosphate
agent in the alkyd resin and heating the mixture 20'
Metal salts of organic acids
for a time su?icient to alter the properties, as will
further appear.
(Formed by various combinations of the fol
lowing:)
Tm: Moon'rmo Adm
,
Anions
. Cations
As is mentioned in my copending applications
above identi?ed, I believe that the colloidal sys
tem of organic isocolloids may be modi?ed by
means of modifying agents. According to the
invention. such modiivlng agents are polar com
pounds in general. By polar compounds I mean
25 Ammonium
Formate
Lithium
Sodium
Barium
Calcium
Acetate
Oxalate
Salicylate
30 Zinc
Phthalate
Maleate
Iron
Cobalt
compounds having polarityiin the molecule, thus
including electrolytes. Examples are given below.
-
Citrate
Naphthol-sulphonates
Lead '
Polar compounds are of many different classes, ‘
Manganese
many of which are defined in my copending ap 35 Copper
Salts of organic amines
plications. The type 01' modi?cation secured by
Diphenylamine
trichloracetate
various groups of modifying agents and even by
Diphenylamine hydrochloride
Diphenylamine hydrobromlde
individual agents, may‘ be quite different, many’
agents and groups producing'results which are
quite distinctive, although as before mentioned, I
40
believe the polar compounds are: all capable of in
?uencing the colloidal system of alkyd resins in
‘Dlaminodiphenyl sulphate
various of the ‘respects already mentioned, and
also-in others.
>
‘
~
Aniline sulphate
’
One particular general classi?cation of polar 45
compounds is as follows:
Metal salts of inorganic acids
Metal salts of organic acids
Inorganic acids
60
'
Metal alcoholates
Aryl-metal compounds
Organic esters oi inorganic acids
Aniline hydrochloride
Inorganic acids
Carbonic acid
Sulphuric acid '
55
Inorganic salts of organic bases
.
Amines also constitute a useful class, particu 60
larly the poly-amines, for instance, diamines.
Examples of amines are benzidine, diphenylamine
and alpha-naphthyl-amine.
Many oi’ the compounds falling in certain
classes mentioned above are also of the type 65
which I have termed “two-radical” compounds,
1. e., compounds having within the molecule an
_ acidic inorganic residue and an organic residue.
'By an acidic inorganic residue I‘ mean a residue
capable of yielding an inorganic acid upon the 70
addition of one or more hydrogen atoms, OH
groups, or water molecules, or upon the applica
tion of heat.
e24’ diamino-diphenyl sulphide
Hydrobromic acid
Hydriodic acid
Metallo-organic compounds
-
Amlno-azo-benzene sulphate
Hydrochloric acid '
Organic acids
Organic esters
m-Nitroaniline hydrochloride
Trichioroaniline hydrochloride
Diphenyl amine sulphate
'
Such two radical type compounds may desir
ably contain a sulpho-, halo- or nitro- group.
Sulphurous acid
Hydrosulphurous acid
Hydrosulphuric acid
Thiosulphuric acid
Nitric acid
Nitrous acid
_
Boric acid
Phosphoric acid
Hydrocyanic
Thiocyanic
i
Chlorsulphonic ‘
Organic acids
Tartaric acid
Maleic acid
Acetic acid
Oxalic acid
Salicylic acid .
Phthalic acid
Citric acid
Trichloracetic acid
Naphthenic acids
-'
aeiaeie
7
d
d
Metal alcoholates
, Organic esters of inorganic acids
Triphenyl phosphate ‘
‘Sodium amylate '
phenyl phosphates
Two-radical compounds
Nitrobenzene
o-Nitrophenol
p-Nitrophenol
B
Dinit'robenzene
NitroI-chloro-benzene
I have found certain groups of modifying
Dinltroaniline
p-Nitro-acetanilide
agents to be particularly effective in the treat- '
15 merit of alkyd resins—for instance, the organic
Nitrocresol carbonate
m-Nitroaniline hydrochloride
Ethyl thioether of z-nitrobenzene
halo-compounds.
Hereinafter examples are given of the treat
ment of alkyd resins ‘with modifying agents se
Ethyl thioether of 2:4 dinitrobenzene
lected from various of the groups which are use-.
Ethyl thioether of nitro-aminobenzene
2:4-dinltrobenzene
'
20 full in accordancev with the present invention, but
before introducing speci?c examples, reference
-
Nitro-aminobenzene
is now made to the treatment conditions em
ployed.
B. Containing sulpho- group
Benzene sulphonic acid
25
p-Toluene sulphonic acid
2:5 dlchlorobenzen sulphonic acid
Although the treatment conditions may be
such as the particular alkyd being treated, the
p-Toluidine-m-sulphonic acid
Naphthalene 2:6 sulphonic acid
treating agent selected and the characteristics
30 desired, in general, the treatment conditions
should conform with the following:
-
Beta-naphthol 1:5 sulphonic acid
Beta-naphthol 3 : 6 : 8 sulphonic acid
With respect to temperature it is ?rst noted
that while some modi?cation may be brought
Beta-naphthylamine 3 : 6 : 8 trisulphonic
acid
about by dispersing the modifying agent in the
'
35 resin at normal room, temperature, in general,
2:11 naphthylamine sulphonic acid
2:6 naphthylamine sulphonic acid
the treatment temperature should be consider- v '
2-phenylamine~8-naphthol-6-sulphonic
acid
' ably above roomv temperature, and usually from
about 200° C. up to about the-boiling point or '
.
,
decomposition point ,of the alkyd resin. In most
Methyl-p-toluene sulphonate
.Ethyl chlorosulphonate
‘Benzene sulphonyl' chloride
40 cases the temperature should not be above about
300° C., and for many purposes treatment be
tween about 270° C. and 290° C., has been found
p-Toluene sulphonyl chloride
effective.
Naphthalene-l-sulphonyl chloride
-
Increase in temperature is usually accompan
Dimethyl sulphate
Diaminodihydroxy anthraquinone disul- _
phonic acid
' ied by more rapid and/or more extensive modi
?cationalthough as just noted, the temperature
is desirably kept below the point at which any
decomposition occurs.
C. Containing halo- group
o-Dichlorobenzene
_
The duration of the heating will again depend
somewhat on the materials used and the results
desired. Usually‘ the heating should be contin
p-Dichlorobenzene
Trichlorobenzene
ued at least until thorough dispersion of the
Naphthalene tetrachloride
Naphthalene trichloride
Naphthalene hexachlor-ide
Naphthalene monochloride
Nltro-chlorobenzenes, ortho, meta and
para
treating agent is obtained. Ordinarily it is found
that treatment for a period of at least thirty
- minutes is required for this purpose and fre
quently the treatment should be. continued for
' several hours, for instance, up to about three or
?ve hours.
Nitroedichlorobenzenes
Chloro-dinitrobenzenes
Monochlorobenzene
Chlorinated diphenyl
Pinene hydrochloride
The quantity of m0dlfying agent employed Wm..."
60 also depend somewhat on the alkyd being treat
ed, on the modifying agent selected and on the
particular characteristics desired. For various
purposes a relatively wide range is usable, for
4-chloro-o-anisidine
instance, from a trace such as .01% or .5% upto
p-Nitro-chloro-benzene
Triphenyl-chloro-methane
65 about 30%. Ordinarily, however, a range of from
about 1 or 2% up to 10% will be found to be ef
Benzyl chloride
fective.
Benzoyl chloride -.
Acetyl chloride
7,0 which occurs.
Phthaloyl chloride
_
For certain purposes, such as a
light colored product, it may be desirable to ex
clude‘air from the reaction mass, in which event
Trichloroacetic acid
Monochloroacetic acid
vacuum may be ‘applied.
Chloral hydrate
_
‘
The nature of the atmosphere in contact with
the reaction mass will in?uence the modi?cation
4 Acetyl bromide
Iodoform
TREATMENT Connrrrons
varied in accordance with a number of factors‘
m-Xylidine sulphonic acid -
.
'
Benzoyl ‘ peroxide
Dinitro-chlorobenzene
‘
‘
‘Nitrocresyl carbonate
Ethyl chlorosulphonate
Dimethyl sulphate
Peroxides
Barium peroxide
Magnesium peroxide
A. Containing nitro-group
'
‘
Tricresyl - phosphate and other. alkyl
Introduction of certain .
gases into the reaction vessel, blanketingthe sur
'
"
75 face of the batch may also serve to exclude air. .
4 2,410,418
-
8
Gases suitable for this purposes are nitrogen,
reached and the product formed a clear heavy
C01, 502, Has, amongst others. On the other
bodied oilyv material when cooled, dissolving easily
in mineral spirits.
'
*"
hand, gases released from the reaction mass may
Each of the examples employed the foregoing"
serve to exclude air, particularly where the reac
long oil alkyd as starting material. The exam
tion takes place in a closed vessel.
ples were all carried out under similar conditions,
‘The reaction‘ may also be carried out in the
there being certain variations as is indicated in
presence of air, for instance, in an open kettle,
the table of comparative experiments below.
and if desired, super-atmospheric pressure may
In all cases the resin and modifying agent were
be employed for some purposes.
10 heated in a ?ask and CO: was introduced into the
Exsmrms
?ask to form a blanket at the surface of the ’
A number of examples of the modification of
batch.
Table of comparative experiments
11%’;-
Agent
1 ..... __
p-Tclusnesulphonicacid...-
t
2 ----- --
p-Tolumsulphoshloride--_
5
3 ----- “36mm” ----------------- ~
5
4 _____ __
Percent Hedwig“ “'1
Tri-chloro-acctic acid ...... -.
5
Chloralhydrate ______ _
s
-
g
8 ..... ..
Tetra-ch oro-resorcino ---- --
9 ,,,,, __
Di henyl-amine .......... ._
l0___-_.- p-
itrophenol ............ -.
Color (Hellige)
Viscosity (Gardner)
Acid No.
zhmtzsog ..... --
Blaukl ................. -.
Paste ................... .-
Not taken,
??i?agfggoa ---- --
____d0 _____________
vmy viscous ____________ __
Do_
iéggggiggij; 'I‘urbidbrowngranuleri. Paste.-.‘................ ..
Do,
hr£¢8‘¢;7°°-5-----
clears __________________ __
H ______________________ __
9_5_
hrlemmIIIII
Clesrll ................. ._
z-1 _____________________ __
7,1,
2111'. at 280° ..... ..
Brown turbid4 ......... ..
Paste ................... --
Not taken.
2
2hr.
5
__--;do .................. __
at
'
1'68
en
D0,
2-5 ..................... ..
20.8
5
311m:
Z-ltoZ-2 ............... __
7,3,
6
2hr.
Very viscous ............ -.
Nottakan,
A ____ -. (AtlkyglmF9581 without any ---------------------------- -n ____ _.
.
Moderately viscous 011.-.. 8,0,
l
(Heated without agent) ............. __ {};;',-,:f;,’g;,._____
z-2 ..................... -_
5.4.
The products of all of the foregoing examples
alkyds are given herebelow, all of these examples 7
having been carried out with the same alkyd
were mixed with mineral spirits to yield 50%
resin, so as to give comparative results. The 35 non-volatile compounds. These mixtures were
alkyd resin was prepared in accordance with the
then analyzed and compared in connection with
following.
fertain properties thereof, the results being as fol
.
First, a resin of medium oil length was pre
' pared in accordance with the following formu
lation:
ows.
Although the materials containing the resin
products of Examples 1, 2, 3, 6, 7 and 10 were not
'
fully compatible with mineral spirits, the others
Gm.
formed satisfactory solutions- The products of
Examples 4, 5, 8, and 9 were [very good with re-‘
spect to clarity and color.
Phthalic anhydride ............ ___ ______ __ 1,560
Linseed ‘oil fatty acids _____________ __....__ 1,008
Soya bean oil fatty acids ____ ___ _________ __
672
Glycerine
912
____________________________ __
45 _
Subsequent agitation of the materials contain
ing the products of Examples 1 and 10 yielded
4,152
satisfactory solutions.
.
..
The products of Examples 3, 6 and '7 formed
Container: ‘Closed aluminum kettle with agitator.
soap-like compounds, which compounds may have
been salts of phthalic acid, having reduced solu
bility both in mineral spirits and also in that
portion of alkyd resin which is still in ester form.
heat.
The treatment with tetra-chloro-resorcinol
'C02 bubbled through vigorously during last
half hour at heat to remove some excess 55 (Example 8) indicated considerable acceleration
of bodying time in the preparation of the modi
,phthalic anhydridc.
?ed resin.
,
Reaction temperature: 240-245” C.
A test for solubility was also made on the prod
Time at heat: 2V2 hours.
ucts of Examples 1 and 10 in Solvesso No. 2, and
“"‘Prodnct: Fairly light and is plastic.
Gas used:
'
CO2 blanket throughout..
CO2 bubbled through after first half hour at
Acid No.2 15.84 (phthalic anhydride not all re
moved).
50
these displayed satisfactory solubility character
istics in Solvesso No. 2. ,
Still further, the mineral spirits solutions with
In the above formula 1.75 mols (260 parts by
the products of Examples 4, 5, 8 and 9 were tested
weight) of phthalic anhydride was used for 1.00
for drying properties after adding 0.03% cobalt,
mol .(280 parts by weight) of fatty acids. of which
60% was linseed oil fatty acids and 40% soya bean 85 0.3% lead‘ and 0.02% manganese drier. These
tests showed that the solutions containing the
oil fatty acids. 1.65 mols (152 parts by weight) of
products of Examples 4, 5 and 8 were appreciably
giycerine was used.
superior to a similar test which was made on the
The foregoing medium oil alkyd was then di
product of Example B above, the solution contain
luted with linseed oil to yield along all alkyd, the
following procedure being- employed for that pur-' 70 ing the product of Example 5 being the best of the
group.
pose.
The drying test on the solution containing the
1800 gms. of the above medium oil length alkyd
product of Example 9 indicated that the modify
Iresin and 1800 gins. of alkali re?ned linseed oil
ingagent, (diphenyl-amine) retarded drying, as
were heated together in an aluminum kettle to
170° 0., where a complete mixture of both was 75 compared with the Blank 3
2,410,418
10
In the art of alkyd resin manufacture it is a
known fact that 1 mol glycerine is never able to
VARIABLE AND SUPPLEMENTAL TREATMENT
CONDITIONS
’
esterify with the theoretical quantity of 11/2 mols
of phthalic anhydride. Instead the quantity of
phthalic anhydride is usually in the range of 1.1
to 1.3 mols of phthalic anhydride for‘each mol of
glycerine. The phthalic anhydride is completely
esteri?ed under such circumstances, as the acid
through the reaction mass or may be employed
value of the resin is low, but the glycerine mole
as a blanket upon the surface of the reaction 10 cules have some free hydroxyl groups left. On
mixture, and may be used for their supplemental
the other hand 1 mol of glycerine esteri?eswith
effect upon the primary treatment taking place.
the theoretical quantity of 3 mols of fatty acids.
The modifying agent may, if desired, be pro
Therefore when theoretical yields of alkyd resins
duced in situ, by introducing materials which will
are ?gured, it is customary to assume, that each
react under the conditions of treatment to pro 15 mol of phthalic anhydride will liberate 1 mol of
duce the modifying agent desired. Various of the
water and that excess OH-groups of the addi
agents may also be used incombinations, or se
tional glycerine present remain unchanged. 1
quentially.
mol of glycerine and 3 mols of fatty acids will
‘It is further to be noted that in general in
liberate 3 mols of water of esteri?cation.
, \
In addition to treatment at various different
pressures, as above noted, the process of modi?ca
tion may be carried out in the presence of various
gases, such for instance, as CO2, S02, H28 and
nitrogen. Such gases may either be bubbled
creasing any one or all of the variables: namely, 20
temperature, time of treatment and percentage
of modifying agent, increases the extent of modi
?cation. It will be understood that the foregoing
is a general rule normally applicable within the
Based on these well known facts, the constitu
tion of the resin used in the examples of this
speci?cation is as follows:
'
In the "first step” resin of the examples 1680
grams of fatty acids are used, being equivalent
ranges of'operation above indicated, although, as 25 with about 6 mols of fatty acids (molecular weight
to at least some variables, there may be limits
of fatty acids being about 280). These fatty acids
beyond which the general rule does not apply.
combine with 2 mols of glycerine, i.,e., 184 grams,
For instance, excessive increase in temperature
yielding 1756 grams of glyceride and 108 grams
may substantially alter the character of the
of water of esteri?cation. The phthalic'anhy
dride combines with the rest of the glycerine,
The modi?ed product of this invention may if
forms 186.3 grams of 'water of esteri?cation and
yields 2101.7 grams of glycerol phthalate. The
desired, be subject to other treatment, depending '
upon the use for which it is intended. Thus, for
theoretical yield of resin is 3,857.7 grams and the
_ example, the modi?ed products may be vulcanized
fatty acid glyceride in same is 45.50%. This resin
process.
'
.
I
with sulphur.
is extended with equal weight'of oil, so that the
long oil- alkyd, forming the starting point of they
examples has approximately 27.25% glycerol
phthalate and 72.75% fatty acid glyceride.
Light treatment and wave treatment of various
types also influence the reaction, for instance,
' treatment with visible light, ultra violet light or
with electrical potential differences. Irradiation
with oscillating energy of various wave lengths, 40
X-ray, etc., may also be used.
_
,
Iclaim:
1. A process in accordance with claim 3 in
which the heating is effected under vacuum.
Various of the foregoing and other variations
2. A process in accordance with claim 3 in
in treatment may be employed, as is mentioned
which the temperature of treatment is between
in my copendlng applications above identi?ed.
about 270° C. and 290° C.
v
3. A process for altering the properties of long ,
Such- supplemental matters need not be consid
oil alkyd resins which comprise about 73% fatty
ered in detail herein, since reference may be made
oil acid glycerides and about 27 % glycerol phthal
for that purpose to said copendlng applications,
ate, which process comprises the incorporation in
and also to certain other prior applications men-4
the long oil alkyd resin of from about 0.5 ‘7., to
tioned herebelow, all of which disclose certain
features in common with the present applica 50 about 10% of p-toluene sulpho chloride and heat
ing the mixture to a temperature between about
tion-to wit: Serial No. 359,425 (now Patent No.
260° C. and the boiling or decomposition point of
2,213,944); Serial No. 446,172 (now 'Patent No.
the mixture, whichever is lower, until a material
2,213,943); Serial No. 446,170 (now Patent No.
is produced which manifests a substantial increase
2,234,949); Serial No. 370,733 (now Patent No.
2,083,550); and Serial No. 143,786 (now Patent ., in viscosity, as compared to the same long oil alkyd
resin heated in the same way but without the in
No. 2,189,772).
corporation of the p-toluene sulpho chloride.
Some of the modifying agents may act as dis~
solution promoting agents, as described in vari
ous of my prior applications and also in my issued
LASZLO AUER.
Patent No. 2,293,038.
60
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