Us1995970 PDF

Patented Mar.
26, 1935 1,995,970
UNITED STATES PATENT OFFICE

1,995,970
POLYMERIC LACTIDE RESIN
George Lowrance Dorough, Wilmington, Del., as
signor to E. I. du Pont de Nemours & Company,
Wilmington, Del., a corporation of Delaware
No Drawing. Application April 4, 1931,
Serial No. 527,854 '
(Cl. 260-2)
6 Claims.
This invention relates to new resins and more ular weight material, comprising chie?y lactide
particularly it relates to polymeric lactide resins (B. P. 255° C.) so that this material may be re
and compositions comprising these resins. moved as rapidly as possible and thereby prevent
While it has been proposed to manufacture decomposition of the high molecular weight ma
l resins from lactic acid, the products and resins terial. The pressure should preferably be below
produced by the prior processes for treating lac 100 mm. of mercury and the temperature pref
tic acid do not possess the physical character erably lies within the range of 250° C. to 350° C.
istics and desirable ?lm forming properties of The polymerization and distillation of mono
the resins herein disclosed. meric lactide for the production of the resin is
This invention has as an object, therefore, the conducted under substantially the same condi 10
production of new lactide resins. A further ob tions of temperature and pressure as those in
ject is the production of new compositions of mat dicated above. The following examples are illus
ter, particularly coating compositions comprising trative of the method of carrying out my in
these resins. A still further object resides in a vention:
ll new process for the manufacture of lactide resins. Example I 15
My new resins may be made either from lac
tic acid or from monomeric lactide. The prep 400 g. of puri?ed technical lactic acid 85% was
aration of these resins from lactic acid solutions vplaced in a three-neck round bottom ?ask of one
involves the concentration of the solution by dis liter capacity equipped with a mechanical stirrer
20 tilling off the water, the polymerization of the and condenser for distillation. This ?ask was 20
hydroxy acid by an intermolecular condensation, heated in a bath at 150° for thirty minutes. The
and finally the removal of the lower molecular temperature was then raised to 275~300° and the
weight compounds from the resinous mass. heating continued for forty-?ve minutes. The
When the resin is made from monomeric lactide temperature of the bath was then raised to 300°
the process involves a polymerization to a high and the pressure of the system reduced to 70 mm. 25
molecular weight mass and the removal of the These conditions were maintained for 15 minutes.
low molecular weight materials from the resin. The heating bath was removed and the pressure
The concentration of the lactic acid, in the in reduced to 20 mm. The monomeric lactide dis
itial step for producing the resin, is preferably tilled out and solidified in the receivers.
80 conducted at about 150° C., but I may use tem The residue was resinous. The yield was 165 g. 30
peratures as low as 100° C. and up to about of resin or 60% of theoretical. The monomeric
200° 0., although at the higher temperature con lactide collected weighed 51 g. The total lactide
siderable loss of lactic acid occurs. When it is de (pi?ymeric and monomeric) was 79% of theoreti
sired that the resin be highly polymerized and ca .
exhibit the most desirable properties, the poly Example II 35
merization step is preferably conducted between
273° C. and 300° C. which approaches the tem The procedure described in Example I above,
perature at which decomposition of a polymer was followed. 400 g. of puri?ed lactic acid of
ized product begins to occur. Decomposition of 80% concentration yielded 176 g. of resin and
the polymerized product is indicated by the evo 45 g. of monomeric lactide. This represents 'an 40
lution of volatile materials which are gaseous at 85% yield on the basis of monomeric and poly
the temperature at which the decomposition takes meric lactide.
place. Acetaldehyde, for example, may be Example III
trapped and identi?ed when decomposition of 100 g. of monomeric lactide was placed in a
the pohrmerized product takes place. Tempera three-neck flask of one liter capacity equipped 45
tures as low as 250° C. may, however, be used for with a mechanical stirrer and a condenser for
‘the polymerization step with results satisfactory distillation. This was placed in a bath at 275°
for some purposes. The ?nal step, which con and heated for forty-five minutes. The tem
stitutes an important part of my process, con perature was raised to 300° and the heating con
50 sists in removing the low molecular weight ma tinued for fifteen minutes. The heating bath 50
terial at low pressures and at a temperature just was removed and the pressure reduced to 10 mm.
suilicient at the particular pressure used to re The monomeric lactide distilled into the receiver
move these objectionable materials by distilla and the resin remained in the flask. The resin
tion. Low pressure is used in this step to lower obtained was '14 g. or 74%, the monomeric lactide,
the boiling point of the objectionable low molec 14 g. or 14%. The total yield of lactide (mono
2 1,995,970
meric and polymeric) represented 88% of theo made therefrom show ?lms of high durability.
retical. Suitable ratios of cellulose acetate and polylactide
'
Through the practice of the present process, resin for use in these compositions are indicated
high yields of the resin may be easily and eco in the following example:
nomically obtained from all grades and concen
trations of lactic acid. Example V 5
When the resin is made from lactic acid, the
initial heating of the dehydrated acid during the Parts cellulose Parts polylactide
acetate . resin
?rst part of the polymerization step results in the
10 formation of monomeric lactide which is poly 1 1o
merized as the heating proceeds. It will be ap 4 2
parent, therefore, that whether my new resin is 4. 4
made from lactic acid or the lactide as the initial
material, the process in either case comprises the Coating compositions which yield ?lms of good
15 polymerization of lactide and the subsequent re quality may be made from nitrocellulose and 15
moval by distillation of the low molecular weight mixtures of my new resins and those of the oil
material. ' modi?ed polyhydric alcohol-bolybasic acid type.
The removal of the monomeric lactide from the Suitable nitrocellulose compositions containing
resin by heating under reduced pressure results these resins are as follows: L
20 in a marked improvement in the durability of the
Example VI , 20
?lms from the resin. This low molecular weight
material can in turn be polymerized.
The polymeric lactide resins prepared as dis
closed herein are quite hard and brittle. Their
$853‘
N. _ _ .
sass.
.
25 color depends somewhat upon the purity of the Parts Parts Parts Parts 25
raw materials used, being almost colorless when - 4 2 (A) 2 _ 2
U. S. P. or C. P. acid is used and darker when 4 , 203) 2 2
4 2(0) 2 2
edible and technical grades of acid are used.
Samples of resins which exhibit good properties
30 in ?lms soften at temperatures around 80-100° C. The compositions of resins A, B and C, and the 30
Average molecular weight values were found to mode of their manufacture is as follows:
be about 3000-4000. - Films of this resin are quite Resin A
water resistant if all of the volatilizable low molec Per cent
ular weight lactide has been removed. The resin Glycerol---“ 24.2
35 is soluble in ethyl or methyl alcohol, acetone, ben Phthalic anhydride 54.3 35
zene, toluene and esters of all kinds. The resin Castor oil 21.5
is soluble in and compatible with softeners and Acid number, 70-75
plasticizers of the ester type (dibutyl phthalate,
etc.) . The ingredients were mixed and heated at
40 My new polylactide resins are compatible with 180-225’ C. until the resulting resinous material 40
cellulose derivatives such as nitrocellulose, cel showed an acid number of 70-75.
lulose acetate, and other esters and ethers of Resin B
cellulose. They are also compatible with various Per cent
natural resins, and when combined with cellulose Glycerol 19.87
45 derivatives are more or less compatible with syn Phthalic anhydride ____________________ __ 36.52 45
thetic resins such as those of the polyhydric al Linseed oil acids 31.15
cohol-polybasic acid type. These resins are also China wood oil acids __________________ __ 12.46
compatible with damar resin. The resins are Acid number, 40-45
particularly useful in coating compositions, im
'50 pregnating compositions, and molding composi The ingredients were mixed and heated at 60
tions containing cellulose derivatives and natural 185-220° C. until the resulting resinous material
or synthetic resins of the type mentioned. showed an acid number of 40-45.
Lacquers containing my new polylactide resins, Resin C’
nitrocellulose and dibutyl phthalate have shown ~ Per cent
55 by test to possess a better durability than control Glycerol - __ 17.11 55
lacquers formulated with damar gum. The Phthalic anhydride ____________________ __ 27.09
quality of the ?lm is considerably improved by Linseed oil acids 55.80
the addition of a suitable softener. Acid number, 20-25 _
Preparations of nitrocellulose, polylactide resin
60 and dibutyl phthalate which have been used in‘ The ingredients were mixed and heated at 60
formulating lacquers that I have tested for dura 225-250° C. until the acid number was approxi
bility are given in the following table: mately 20-25.
The value of these polylactide resins in im
Example IV pregnating compositions may be noted from the
65 fact that paper impregnated with compositions 65
Nitrocellulose Polylactide resin Dibutyl phthalate consisting of polylactide resin, nitrocellulose and
dibutyl phthalate exhibits a much higher re
Paris In; weight Parts his weight Pam bzswelaht sistance to tear after impregnation. These
4 2 l o polylactide resins may also be of use as adhesives
70 4 1 2 for glass and wood as well as coating and im- 70~
4 2 2
4 4 pregnating agents for fabrics. Various other uses
2
1 4 2
will present themselves to those skilled in the
art.
The polylactide resins are also compatible with As many apparently widely di?‘erent embodi
75 cellulose acetate and the coating compositions ments of this invention may be made without
1,995,070 3
departing from the spirit and scope thereof, it perature within the range of about 250° C. to
is to be understood that I do not limit myself to about 300° C. until polymerization occurs, and
the speciiic embodiments thereof except as de distilling oi! the lactide by heating the polymer
fined in the following claims. ized product within said temperature range and
I claim: at a pressure below 100 mm. of mercury.
1. A process for making a resin which com 5. A process for making a resin which com
prises polymerizing lactide by heating it within prises concentrating aqueous lactic acid at about
the range of 250° C. to about a temperature ap 150° C., heating the concentrated acid at a tem
proaching that at which decomposition of the perature within the range of about 273° C. to
10 polymerized product begins to occur, and‘further about 300° C. for approximately 45 minutes, con 10
heating the polymerized product within said tem tinuing the heating approximately 15 minutes
perature range and at a pressure below 100 mm. at about 300° C. under a pressure of about '70
of mercury. mm. of mercury, and continuing the heating at
2. A process for making a resin which com a pressure not greater than about 20 mm. of
prises heating lactide within the range of about mercury.
273° C. to 300° C. until polymerization occurs, 0. Aresinhaving ameltingpointof80° C.to
and further heating the polymerized product 100° C. which comprises polymerized lactide sub
within said temperature range and at a pressure stantially free from unpolymerized lactide, said
below 100 mm. of mercury. resin being obtainable by polymerizing lactide
20 3. A process for making a resin which com by heating it within the range of about 250° C.
prises heating lactide at a temperature within to a temperature approaching that at which de 20
the range of about 273° C. to 300° C. for about composition of the polymerized product begins to
60 minutes, and continuing the heating at a pres occur, and further heating the polymerized prod
sure not greater than about 20 mm. of mercury. uct within said temperature range and at a pres
4. A process for making a resin which com sure below 100 mm. of mercury.
prises concentrating aqueous lactic acid above
100° C., heating the concentrated acid at a tem GEORGE LOWRANCI DOROUGH.

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Patented Mar.

26, 1935 1,995,970

UNITED STATES PATENT OFFICE

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