~olymer Scze~ce U.S.S.R. Vol. 24, No. 7, pp. 1702-1708, 1982 0082c-8950/82107170~t-07507.

5010
~[Ilte~ in Polai~ O 1983 I'ergLmon ~ LkL

~ R M O D Y N A M I C S OF d/-LACTIDE, POLYLACTIDE AND

POLYMERIZATION OF dI.LACTIDE IN THE RANGE OF 0-430K*

T. G. KULAGINA, B . V. LEB~DEV, Y.E.O. KIPARISOVA, YE. B. LYUDVIO and

I. O. BARSKAYA
~eientifie Research Institute of Chemistry, N. I. Lobachevskii State University, Gorkii
L. Ya. Karpov Scientific Research Institute of Physleo-Chemmtry
(Received 11 March 1~81)

Adiabatic and isothermal calorimetry were used for the first time to study
thermodynamic properties of d/-laetide, polylaetide and thermodynamic .parame-
ters of polymerization Of d/-lactide. Specific heat C~ was measured with an accuracy
of ~ (~2°/o in the range of 8-330°K and 0. 7~/o in the range of 330-430°K. Functions
of H°(T)-H°(O), g°(T), G°(T)-H°(0) of the monomer and polymer.were calcu-
lated for the range of 0-430°K. Zero entropy S~(0) of the polymer was determined
in the glassy state. Combustion enthalpy values of the monomer and polymer
were measured and standard parameters of the formation of these substances
ztH~, zl~ and JG~, calculated. From results obtained thermodynamic parameters
of polymerization of lactide ztH~, ztS~ and JG~ were alculated for the range of
0-430°K; the upper maximum temperature of polymerization T~ was established.

_A~STUDY Was carried out of thermodynamic properties of d/-laetide (I), poly-

]actide (II) and thermodynamic characteristics of the process
CH:,
I
CH--C0 0 0
/ \ II II
n 0 O----[--O--EH--C--O--CH--C--]~ 7-
\ / 1 i
CO--CII CH3 Ctt.~
• CH3
I II
a n d this is of interest for the technology of synthesis and processing of I I widely
used in medicine [1].
The temperature dependence of specific heat C~ of d/-lactide and polylactide
was examined for the first time in t h i s paper in the range of 8-4300K; tempera-
tures and enthalpy values of physical transitions were determined and combustion
e n t h a l p y values o f the monomer and polymer measured. Results obtained were
used to calculate thermodynamic functions in the range of 0-430°K, standard
thermochemical l~arameters of formation of I and I I and thermodynamic criteria
o f process I-~II.

* Vysokomol. soyed. A24: N o . 7, 1496--1501, 1982.

1702
 Thel~nodynami~ of d~,lactids 1703

The monomer was synthesized b y d e h y d r o c y v l i ~ t i o n of d/-lactic acid during vacuum

distillation b y methods previously described [2]. The d/-lactide thus obtained was purified
b y fourfold r e c r y s t a l l i ~ t i o n from ethylacetate a n d dried in vacuum to constant weight.
Polymerization was carried out in m e l t at 170 ° wit~ Zn()l= initiator ( 5 × 1 0 -s mole/1.) in
vacuum. The reaction m i x t u r e obtaine d w u ! ~ I v e $ in dio~ane, the polymer precipitated
with ethanol a n d dried to constant weight in vacuum at 50 °. ~n----8•95 X 10 ~ was determined
b y gel-permeation c h r o m a t o g r a p h y using a Waters-200 device. According to our calo-
rimetric results, polylactide in the temperature range examined was in the glassy a n d high-
elastic states. I t was found t h a t for d/.lactide: C 50.19; H 5.76; O 44.05; for polylactide:
C 50-20; H 5. 60; O 44.20~/o. Calculated values for the monomer and recurrent polymer unit
were: C 5@04; H 5.59; 0.44.44.
To measure C~ in the range of 8-330°K, a n d adiabatic vacuum calorimeter [3] was
used a n d in the range of 330-430°K--an adiabatic calorimeter. The design a n d methods
of operation of the calorimeter were described previously [4, 5]. B y measuring =-Al=O8
and KC1 i t was established t h a t the device used and the methods employed enabled O~
to be o b t a i n e d for substances in the solid and liquid states with a n accuracy of 1% a t
~ 10°K, 0.5~/o--at 1 0 < T < 3 0 ° K , (~2% in the range of 30-330 K a n d ~ ~ 7 % in t h e range
of 330-550°K. I n the range of 250-500°K polylactide was examined b y D T A (PRT-1000 ]K
device). The design a n d methods of operation are desoribed in a separate s t u d y [8].

0 2OO L/O0T,K

300; I I ~ L
C _ ~_D--
}
Vii . K

T°m 80 7

I00 40 r~

.[ , l 0
3f ,
40 80
T,K
Specific' heat of e~s]]me (AK) and liquid (M-~) d~-tactide, glassy (AB) and high-
elastic (CD) polylactide. '

The variation of internal energy AU I in combustion of samples I a n d I I was measured

in a B-08 t y p e calorimeter with a static charge and isothermal layer b y methods previously
d e ~ r i b e d [7]. The energy equivalent of the calorimeter W=75980-t-(F13 J . O h m -~ was
determined experimentally b y the oombustion of standard benzoic acid (AUz-------26.435~ "
-[-5.3 j.g-1) under s t a n d a r d conditions of combustion a n d a t 298.15°K. After every oom-
bustion gaseous products of combustion were analysed using CO= a n d CO. Analytical ac-
c u r a c y for CO= was (~04%; sensitivity of analysis for CO was 6X 10 -6 g.
1704 T. G. K v ~ G m A ~ a/.

TABL~ l. T ~ O D Y I ¢ ~ C FUNOTIOI~So]r dt-y_4~tr~v~•

~,IH°(T)-H°(O),t,~°(T),I--[G°(T)-H°(O)],
T, K J/mole_l.K_l , kJ.inole_ 1 J/mole_LK_1 kJ.mole_1

C4Tstalline state
5 0.307 0. 000294 ~0659 0. 000353
10 2.420 0. 00606 (~780 0.00174
15 7.2110 0.02966 2"625 0.009714
20 13.13 (~08046 5"505 ~02964
25 19.09 (~1602 9.070 (~06584
30 25.01 (~2712 13. 07 ~1210
40 36.10 (~5783 21"83 (~2950
50 45. 47 (~9871 30.91 (~5587
60 54. 06 1.485 39"97 0. 9132
80 69.18 2.719 57. 62 1.890
100 82. 64 4. 420 74' 53 3.213
200 137.3 15.36 149.4 14.52
250 162.0 22. 84 182"7 22.83
298.15 184. 3 31.17 213.1 32. 37
310 19~8 33.39 220.4 34. 94
360 22(~5 43. 66 "251"1 46.73
397 243. 7 52. 24 273. 7 56.43
Liquid
397 297.1 76.93 33~ 9 56. 43
400 297.2 77.82 338-2 57.45
430 297.6 86.63 359-4 67. 91
* In terms of mole d/-lactide(Mffi144.12).

~q1~ecific hea~ C~ of d/-lactide was measured in the range of 8-430°K, of poly-

lactide--in the range of 8-360°K. For I in 18 series of measurements 89 experi-
mental values of C~ were obtained, for I I in 21 series--126 values were derived.
Samples I and I I examined weighed 5.7100 and 4.373 g, respectively. Their
specific heat ~ a s ~ 60~/o of the overall specific heat of.the calorimeter containing
the substance. Variation of experimental points near correstmnding averaging
curves C~=f(T) at T < 5 0 ° K was within the range of 0.5%, at T > 5 0 ° K - - i t
did not exceed 0.2~. Experimental values of C~ and curves of C~=f(T) are given
in the Figum. A comparatively marked increase in C~ of the polymer in the
range of 260-300°K is due to devitrification. I n other respects C~ of the monomer
and polymer has no special features: the specific heat of crystalline and liquid
d/-lactide, glassy and high-elastic polylactide shows a smooth increase with an
increase in temperature; I t was established b y DTA t h a t during heating high-elas-
tic polylactide phase transitions are absent and the initial temperature of decom-
povition is somewhat higher than 400°K.
Parameters of glass-t~ansition and melting. Glass-transition of the polymer
took place in the range of 260-300°K. The temperature of glass-transition T~
 Thermodynamles of d/-laetide 1705

T~us~.'~ 2. T ~ U O D Y I ¢ ~ C FUNCTIONS OF POLYLACTIDE*

T, K J/mole_L K_I kJ.mole- 1 J/mole_LK_ ~ kJ/mole_ ffi

Glassy state /
0 0 0 20 0
5 ~628 ~000821 20.5 0.102
10 4. 502 0.01213 21"9 0.204
15 699 (~04730 24-7 (~ 3232
20 1648 11)99 28.3 (~4493
25 21.17 (~2017 32"3 ~4561
30 2~ 30 6- 3207 36"7 7701
40 36-12 •• 6338 45.7 1.178
50 45.17 1.043 54"7 1.676
60 53.15 1.534 63"6 2.282
80 68. 39 2.751 81.9 3. 803
100 82e 29 4. 257 97"8 5' 490
150 112.4 9.133 136. 9 11-36
200 139.5 ' 1~44 173.0
250 167.0 23.12 207.1 19-10
277 180 27. 80 225. 6 34.61
High-elastic state
277 26~ 5 27. 80 2266 34~61 "
298.15 264, 8 33. 40 244~4 39. 39
300 265. 2 33.88 246.0 39. 92
330 273. 0 41- 96 271.7 47. 60
360 28~ 7 56- 26 296 8 56- 23

* In terms of mole l ~ a r r e n t unit (Mffi144.1~J.

T ~ I ~ 3. EXPER'rM'~.NTAL RESULTS OF A U I FOR CRYSTAT;r.T.N'E AND HIGH-ELASTIC POLYLACTIDE

Sample oxpts,
!
m, g -Q, J
1 qrz, J
t
I
q~, J

I 9 I (~5990-08677 24,536-29,196 11,707-14,189 1 --

II 6 I (~417~ ~ 7 4 21,824-24,226 t 10,707-16,264

Sample qc.t., J q~N0,, J I m(COJ: × 100% --AUx, j . g - i

I 28. 4-4~ 7 4. 6-1~ 9 99. 52-99. 74 18,838-1-12

II 25.1-33. 5 4- 6-9.8 99. 82-10~ 2 18,779 ~- 8

~Vo~. m--weight of~mple; Q-amou~at of ei~ergy l i b e r a t ~ in one exlmr~ment; ~ , q~A, ~,.t., q~oa-- c o ~ t i o ~ u for
the energy of combustion of PE, benzoic acid, cotton thread and the formstio~t of nitric acl~ sohttion, t ~ e c t i v e l y ; m(CODt
and m(CO.)c are the weight of carbon dioxide fouad ill products of combustion aud calculated from the equation of oom-
bustion; J ~ is the variation of internal energy in combustion of I and r f in a calorimetric charge.
1706. T . G . KULAGI~A e~ a/,

(277~- 1) K was determined from the curve showing the temperature dependence
of entropy S°(T)~J(T) using methods previously described [8]. An increase in
specific heat during devitrification zlC~- 80.5 J.mole-l.K -1 was derived diagram-
matically (BC segment in the Figure). According to the formula proposed pre-
viously [1O], S~-~AC~.ln (1.294-0.14) and from the value of z~C~ of polylactide
configuration entropy S~--20 J.mole-l.K -1 was determined. It was shown pre-
viously [9-11] that S~ is close to zero entropy:S~(0) of glassy polymers. This
enables absolute entropy values of amorphous PolYmers to be etablished using
calorimetric data based on the third law of thermodynamics.
Thermodynamic functions. To calculate thermodynamic functions the specific
heat of d/-lactide and polylactide was extrapolated from 8 to 0 K using the
Debye function of specific heat
G~=~D (SD/T) , (1)
where D is the symbol of I)ebye function, n and ODare parameters specially
selected; for a monomer and polymer n--5 and 3, 0~-----109.5 and 72-8, respecti-
vely. Equation (1) with the parameters indica~<l describes values of C~in the
interval of 8-15°K within the range of error of 1~. When calculating functions
it was assumed that in the interval of 0-8°K it reproduces C~ of the monomer and
polymer with the same accuracy. Calculations of H°(T)-H°(O) and S°(T) were
Carried out by numerical integration using corresponding dependences of Cp
-~f(T) and C ~ J ( ! n T) using a computer and G°(T)-H°(O) according to the
Oibbs-Helmheltz equation from values of enthalpy and entropy. Results of
calculation are given in Tables 1 and 2.
Combu~io~ enthallry valufs and thermochemical l~ararneters of formation.
dl-Lactide was burnt i n polyethylene ampoules and polylactide--in a mixture
with benzoic acid. JUI of PE and benzoic aci~l was measured previously in 10
expe~ments for each. For PE AUI------(46470±7.) j.g-1, for benzoic acid zfUi
=--26443-V4 J.g-~ at 298"15°K and p = 3 × 10a kPa. Experimental results for
zl UI of the monomer, and polymer are given in T~ble 3. Analysis of gaseous pro-
ducts of combustion of the monomer and polymer was carried out after each
experiment. Carbon monoxide has not been found in any experiment. A certain
shortage ~f CO2 in products of combustion of d/-lactide is due to the existence of
some moisture in the sample examined. When calculating standard values of
zfU~ from experimental results of zt Ui of the monomer a corresponding correction

TABLE 4.

Sample / kJ.mole-1 J. mole-I .×

1
×K-1
 Thermodynamics of d/.lactide 1707
~vas introduced; bearing this in mind AU~ corresponds to the combustion of
monomer of 100% purity. Accordi~ to results of JU~ of samples I and I I stan-
dard values of JH~ w~ro caleulated~ which c o ~ n d to equations of monomer
combustion CeHsO~(c)+e0i(g)=~s(g)+4Hs0(1) and polymer combustion
C~sOd(h.e.)+60~(g)~6CO~(g)+4H~O(1) at 298.15°K and p~101.325 kPa.
Physical states of initial substances and reaction products are shown in brackets;
e--crystalline; l--liquid; h.e.-high-elastic and g is gaseous. Table 4 indicates
enthalpy values of combustion, enhalpy, entropy and Gibbs energy values of
the formation of I and II. When calculating AH} standard enthalpy values of
formation of the liquid phase and gaseous carbon dioxide were used [13]. Entropy
of formation was calculated from our results of entropy values of I and II (Tables
1 and 2) and from results in the literatureS14] of the entropy of.gaseous hydrogen
and oxygen and carbon in the form of graphite. The Gibbs energy of formation
was calculated from values of JH~ and JS~ for the monomer and polymer.
Thermodynamic parameter8 of polymerization. Thermodynamic parameters
of polymerization are given in Table 5. The enthalpy of polymerization AH~
at 298.15°K and1~=-101.325 kPa was calculated from enthalpy values of the for-
mation of the polymer and monomer (Table 4) and for a number of other temper-
atures--usihg the Kirchhoff f o r m u ~ . Polymerization entropy AS~ was calcu-
lated from absolute entropy values of the polymer and monomer; Gibbs energy of
polymerization was determined from values of JH~ and ztS~. To calculate these
parameters at 400°K C~ values of polylactide ~ere extrapolated from 360 to 400°K
according to the equation C~--187,7~0.2583 T, describing average values of
C~ of the polymer in the interval of 310-360°K with an accuracy of 0-2%. Ana-
lysis of results indicates that polymerization of dl-lactide is resolved thermo-
dynamically in the entire studied range of temperature, since the Gibbs energy
of the process is always negative. Judging by absolute values of J(7~ the equili-
brium of I ~ I I is practically fully displaced in the direction of II. Process enthalpy
is also always negative. Entropy .of polymerization is positive for processes of
I(c)-*II(c); I(c)-*II(h.e.) and is negative for the process I(1)-*II(1). The upper
maximum temperature of polymerization I was determined by the I)aintorL
method [15] using values of AH~ and JS~ at 400°K and this results in T~ _ 2160 K
which is, of course, much higher than the initial temperature of polymer break-

TABLE 5.

Physical --JH~, AS~, --Adt~,

T, K state of kJ'mole-x J.mole-X.K-j kJ.mole -x
0 or; g 1~90 20"0 10.9
100 or; g 1(~ 88 23'3 13"2
200 cr;g 1~ 82 23"6 15.5
29& 15 or; h.e. 8"7 31"3 18.0
397 cr; h.e, 2-1 50"2 2~ 05
400 1; 1 27.0 --13"0 22-0
1708 T. G. KULAGn~A e$ a/.

d o w n ( ~ 400°K). Therefore, the s i x - m e m b e r e d cyclic m o n o m e r studied a t n o r m a l

pressure is always unstable t h e r m o d y n a m i c a l l y in respect to polymerization.
Since for t h e process o f liquid m o n o m e r - , l i q u i d p o l y m e r ztH~ depends m a i n l y
o n t h e stress e n e r g y of t h e ring~ Es, liberated during polymerization, for dl-lactide
i t m a y be assumed t h a t E I ~-27 kJ-mole -1.

TranalaSe,d by E. SEME~.

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