Unsaturated Polyesters. Polyester lll.

from MaleicAnhydride and 1,4-Butylene Glycol

V. CRSTOBAI I-AREZ and GILBERTO PERDOMOMENDOZA' A. l. U n i v e r s i d ad e L o sA n d e s , a c u l t a d e C i e n c . i aD,e r a r t a m e n do Q u i n r i r . a , a H e c : h i c e r M,e r i d a5 1 0 1 ,V e n e z u e l a d F te L a s

SYNOPSIS The polyesterification reaction of maleic anhydride and 1,4-butylene glycol was carried out, usingp-toluensulphonic acid as catalyst,. The resulting material was characterizedby IR and Ht-NMR spectroscopy,end group analysis, and gel permeation chromatography. It is shown that there is a relationship between maleate to fumarat,eisomerization and steric interaction among condensediroupson the one hand and the tendency of the reacting system to crosslink or gel.

INTRODUCTION
In spite of'all the work which has been carried out on polycondensation of maleic anhydride ( MA ) with diflerent glycols, it is not clear why the maleate to f'umarate isomerization occurs. Although it is quite certain that the glycol structure plays an imp<lrtant part in the isomerization, which is enhanced when bulky groups are clclseto the hydroxyls, there has been little work done on seriesof linear polyesters. In previous work,r'2 it has been shown experimentally that isomerization diminished in going from ethylene glycol to 1,3-propyleneglycol, from around 70 to 15%. The fct that there is one more methylene group, in the 1,3-propyleneglycol, may be indicative ofless spatial interaction between condensedgroups. Nonetheless,diflerent behavior has been exhibited by glycols with larger numbers of methylene groups, 1,G-hexamethyleneglycol and diethylene glycol,'' where the percentageisomerization is over 35 and 55Vo,respectively. These results suggestsintramolecular spatial interaction between ester groups in close proximity, and not only to steric hindrance around the hydroxyl group, or the length of the glycol chain. With 1,4-butylene glycol, once condensed,there could be some sterical interaction, since the spatial arrangement of two consecutivees-

ter functions might acquire a nonplanaro configuration, deviating from the rlanar zig-zag configuration generally accepted.s This deviation could be attributed to the attractive fbrces within the ester grclups."

EXPERIMENTAL
Reactants Maleic anhydride (MA) was recrystallized fom g c h l o r o f b r m ,m p 5 2 " C . 1 , 4 - B u t y l e n e l y c o l ( A l d r i c h ) was purified by distillation, using only the fraction distilling in the range 276-218"C, which was collected. Monohydrated p-toluenesulfbnic acid ( Sigma ) used without further purification. Synthesisof Polyester The polymerization was carried out as previously d e s c r i b e d . lT o 4 . 9 0 3 g ( 0 . 0 5 m o l ) o f M A , 4 . 9 0 m L ( 0 . 0 5 5 m o l ) o f 1 , 4 - b u t y l e n eg l y c o l a n d 0 . 0 1 1 5 g (0.71% p/p) of p-toluenesulphonicacid were added. The reaction mixture was heated at 188-190'C until the acid number reached a value of 10 mg KO}{ /S sample. Purification of Polyester

* To whom coruespondenceshould be addressed.

.Iournal of Applied Polymer Science, Vol. 43, 1605 160? (1991) (O 1991 John Wiley & Sons, Inc. CCC 0021-8995/91/091605-03$04.00

The white waxy-like material was dissolved in acetone, and the resulting solution filtered through a 1605

1606

LAP.F,ZV. AND PERDOMO MENDOZA

Table I

Data from Polyesterification Temperature Time (min)

Reactions

Table IV Proton Assignments Chemical Shift (ppm)

Magnetic

Resonance

Sample

('c)
188 188 190 190 190

Acid Number' 312.3 131.6 81.8

Assignment CH CH - CH CH -C-O-QH, - C-O-CH, fumarate form maleate form CH, CH, CH, O-CCH, CH, CH, O C-

1 2
A

60 180 360 480 540

u.5
13.6

6.85s i n g l e t 6 . 2 7s i n g l e t 4 . 2 2s i n g l e t 1.80

" mS KOH/g sample.

R E S U T TA N D D S C U S S I O N S
Table II Data from End Group Analysis of the Polyester Acid Number' Hydroxyl Number

,;
M,,
') n') 1

Isomerization

30.7
" Mg KOH/g sarnple

;19

sintered glass fnnel. The filtrate was warmed and petroleum ether added.The mixture was allowed to stand overnight and the upper layer decanted.'fhe remaining material was dried under vacuum (0.1 T o r r ) a l 6 o " C f o r J -h -

Analytical Techniques Molecular weights were determined by end group analysis and gel permeation chromatography.' Thin films were obtained by casting of chlorofbrm solut,ion on NaCl disks, and the IR spectrataken on a ['erkin Elmer 377 instrument. Proton magnetic resonance analyses were carried out in a Varian A-60 (60 MHz) spectrometer,samplesbeing dissolvedin CDC13 and TMS used as internal ref'erence.

Table I summarizes the details of the polymerization process;Table II and V refers to the characterization of reprecipitated polyester. The percentageisomerization was obtained from NMR spectra. IR and NMR spectra are shown in Figr.rres1 and 2, and the main assignmentsare given in Tables III and IV. Spectroscopicand solubility results confirm the linearity of this polyester. The two absorptions at 6.27 and 6.85 ppm indicate the isomerization of maleate to fumarate, and NMR measurements indicate that it reaches39%. End group analysis indicates a relatively high molecular weight and GPC shows two fractions (Fig. 3). The fractions could not be easily separatedby normal reprecipitation. lJnsaturation was confirmed by olefinic absorp1 ' c t i o n s a t .i 1 0 7 0 m 1 ( H g - ) a n d 1 6 4 1c m 1 C - C ppm) in the Ill spectra, and from fumarate (6.811 a n d m a l e a t e( 6 . 2 7 p p m ) s h i f t s i n t h e N M R s p e c t r a . The polyester is mainly hydroxv terminated as shown by end group.analysis and IR absorption at 3 5 5 0c m 1 . The relatively high percentage of isomerization Iies between those for the polyesters from 1,3-propylene glycol and 1,2-ethyleneglycol. Though there is one more methylene group in 1,4-butyleneglycol,

Table III Infrared Absorption Bands Absorption (cm 1) 3550 (small, broad) 3450 (small, broad) 3070 (small, broad) 2980 (medium, sharp) 1725 (strong, sharp) 1645 (medium, sharp) 1190 (strong, sharp)

Assignment

of Main

Assignment Stretching Stretching Stretching Stretching Stretching Stretching Stretching terminal hydroxy terminal carboxyl H olefinic H methylenic C O ester C C olefinic C-O-C ester OH OH CC-

gc:

160!

1-!0

''1aa {ln^''l

Figure I

Infrared spectra of the polyester.

III UNSATURATED POLYESTF]RS.

1607

Table V

Data from GPC Analysis

M"
2544

M" 4673
1.84

80

7a

6'0

50 ,'ro",,,

to

2a

10

oo

Figure 2 Proton magneticresonance spectraof the polyester.

MA, the glycol chosenas counterpart fbr the polyesterification must not endure other side reactions such as that of cis-trans isomerization, which normally proceedtogether with polymerization. So, the addition of glycol segmentsto double bonds ( mainly to fumarate ) and, fumarate-fumarate double bond reaction, is avoided. The last two reactions lead to limited polymerization.

the higher degree of isomerizat,ion,in comparison with the polyester from 1,3-propyleneglycol,2may be explained as being due to spatial interactions between ester groups in close proximity. The glycol segment, within the polymer chain, could be arin ranged in a twisted zig,-zag such a way that some sort of ringlike structure is formed nearby where those close ester grclupsmay undergo spatial repulsion, thus enhancing isomerization. There may also be a critical point at which side reactions like gelation and crosslinking become kinetically or energetically more relevant even than isomerization or esterification,since the progressof the polyesterification reaction is quite slow, as measured by acid number, without any perceptible sign of any other processthan conversion of maleate intcr fumarate fbrms. In other words, whenever it is de sired to obtain a high molecular weight polyester of'

CONCLUSIONS
'I'he spatial configuration of'polyester chains is even more important than methylene groups within the glycol chain for cis-trans isomerization to occur. When it is impossible to inhibit this isomerization, it could be harmless to polyesterification if'the critical point fbr gelation or crosslinking is restrained. We wish to thank CDCHT-tll,A fbr financial support during the course of this work. We also thank Prolessor N. (]rassie lor reading the manuscript and fbr his sugges tions and comments.

REFERENCES
1. C. ,I. LarezY. and G. A. Perdomo Mendoza, PoNm. B u L l . ,2 2 ( 5 - 6 ) , 5 1 : l ( 1 9 8 9) . 2. C. J. L,arezY. and G. A. Perdomo Mendoza, PoLvm. Bull., 23, 577 ( 1990) . ll. I. Vancz Szmercsnyi,L. K. Maros, and A. A. Zah a r a n ,J . A p p l . S c i . , 1 0 , 5 1 3 ( 1 9 6 6 ) . 4. C. S. Fuller and C. L. Erickson, J. Am. Chem. Soc., 59, i144( 1937) . 5. C. S. Fuller, C. J. Frosch, and N. R. Pape, J. Am. Chem. Soc.,64, 1.54( 1942). 'furner-Jones 6. A. and C. W. Buan, Acta Cryst., 15, 1 0 5( 1 9 6 2 ) . ReceiuedDecember 7, 1990 Accepted January 3, 1991

20
Figure 3 polyester.

2a

30
ELUIION VCLUME

Gel permeation chromatographic trace of the