VNU. JOURNAL OF SCIENCE, Nat.. S cL & Tech., T .x x , N03, 2004
S Y N T H E S I S A N D C H A R A C T E R IZ A T I O N OF S E G M E N T E D P O L Y U R E T H A N E S B A S E D ON P O L Y E T H Y L E N E A N D
P O L Y T E T R A M E T H Y L E N E GLYC OLS
PART 2: THERMO-MECHANICAL AND SWELING PROPERTIES
P h a m N goc LanPolym er Research Cen ter, Hanoi University o f Technology N g u y e n Thu H ang
College o f Science, Vietnam N ational University, Hanoi
1. I n tr o d u c tio n
In the previous paper [1] we presented our study on the synthesis and characterization of some SPUs based on polyethylene and polytetram ethylene glycols.
Segmented polyurethanes (SPUs) are multiblock copolymers. Due to th eir specific phase separation characteristics caused by incompatibility between the h a rd and soft segments, they have quite good biocompatibility [2].
In this paper we present the second p art of our study on the therm o-m echanicahand swelling properties of the SPUs based on polyethylene and polytetram ethylene glycols. The effects of the macrodiols on the properties of the SPUs obtained were discussed.
2. E x p e r im e n ta l 2.1. M a teria ls
Polyethylene and polyteramethylene glycols selected for preparation of the polyurethanes are listed in the table 1. Before use they were carefully dried by azeotropic distillation of the toluene solution and subsequent removal of the solvent.
Table 1: Polydiols for preparation of SPUs
Polyol M n “ Mn <b)
Tm,°c
Tg,°c
PE G -1000 1207 1100 40 -70 (very weak)
PEG-2000 2341 2070 55 -70 (very weak)
PEG-4000 4280 4109 62 -
PTMO-2000 2186 1950 25 -30
(a): Determined via GPC; (b): Determined via chemical titration
The hydroxyl num ber of the polyetherdiols for calculation of the molecular weights was determ ined bv esterification of the polyetherdiols with acetic anhydride and subsequent titrim etric analysis of the carboxylic acid groups according to the standard procedure [3].
19
Pham N u o c L an, N m iy c n T ill! Hang
The molecular weights of the polydiols were also verified by m eans of gel permeation chromatography (PL columns, 103A°, 7mm i. d., 60 cm length, Polym er Laboratories Ltd, Shropshire, UK. Eluent: chloroform, Differential reflectometric detection (Model W aters 4 0 1, Millipore, MA, USA). Data analysis occurred on a w aters d a ta module model M730.
Calibration was based on a peak position calibration curve estab lish ed using polystyrene standards (Millipore, Millford, MA, USA).
Diisocyanate (MDCI) (Aldrich Bornem, Belgium) was vacuum distilled and stored under dried conditions in a refrigerator prior to use.
1,4-butane diol (Aldrich, Bornem, Belgium) was dried over calcium hydride for 2 days, distilled and stored under nitrogen.
Dibutyl tin diacetate was obtained from Aldrich (Bornem, Belgium) and used without further purification.
Dimethyl formamide (DMF) (Aldrich Bornem, Belgium) was dried over calcium hydride for 2 days and then vacuum distilled.
2.2. Characterization methods
DSC therm ogram s were recorded on a P erk in -E lm er DSC u n d e r nitrogen purging (seating rate 10°c.min \ from -100°c to 100°C). The u n it was equipped with a data processing module th at allows substraction of the background an d norm alization for sample veight.
Uniaxial stress-strain experiments were carried out on a Hounsfield Test Equipment ỊÍ10-KM at 25° c (film samples 20mm in length, 5m m wide, thickness: 0.12 - 0.15 mm, crosshead: 5mm.min l). The swelling test was carried out in distilled w a te r and phosphate buffer solution (pH = 7.4) at different tem peratures.
2.3. Polymer pr ep ar a ti o n
The SPUs preparation was made according to th e procedure described in th e previous paper [1]. Briefly, the reaction for m aking the SPU s was carried out by two-stage procedure. In the first stage, the macrodiol (MD) in DMF reacts with diisocyanate (DI) with tie molar ratio MD/DI : 1/2, at 90°c for 2 hours. Dibutyl tin diacetate was used as catalyst.
rjhe reaction mixture was then cooled down to th e room te m p e ra tu re . A fterw ard 1,4-butane (iol as a chain extender was added and th e chain extension reaction was carried out at
<0°c for 2 hours. The end copolymer product was precipitated in w ater. After drying it was
^dissolved in TH F and reprecipitated in th e solvent m ixture hex an e-eth er (1/1). The copolymer product was dried under vacuum a t 60°c a t least for 2 days.
V N U . J o u rn a l o f Science, N a t.. Sci.. & Tech.. I XX, N J . 2004
Synthesis and ch aracterizatio n o f
3. R esu lts and d i s c u s s i o n
3.1. NMR sp ectra a n d IR analysis
The stru ctu re of th e SPU s obtained was confirmed by proton NMR and IR spectra.
The NMR and IR absorption b a n d s of th e SPU s were shown in the previous paper [1].
3.2. DSC a na lys is o f SPUs
The soft segm ent glass tran sitio n te m p e ra tu re (Tg) and the melting tem p e ra tu re (Tin) of the SPUs obtained from the DSC d a ta are summ arized in the table 2.
Table 2: DSC data of SPUs
Code Polyol ratio
Tg, °c
Tm, "CPƯ-1 P E G -1000 + PTMO-2000 (1/1) - -121.5
PƯ-2 PEG-2000 + PTMO-2000 (1/1) -55 35.5 / 20
PU-3 PEG-4000 + PTMO-2000 (1/1) -60 4 8 / 18
PU-4 PEG-2000 + PTMO-2000 (1/2) -60 34/18
PƯ-2 PEG-2000 + PTMO-2000 (1/1) -55 35.5 / 20
PU-Õ PEG-2000 + PTMO-2000 (2/1) -60 4 0 / 2 7
The polymers show the m elting te m p e ra tu re (Tm) which increases with increasing the molecular weight of th e polyethylene glycols. Possibly, this is due to an increase in the size of the soft seg m e nt crystallinity. The increasing of the crystalline domain probably restricts the solubilization of th e h a rd segm ents into the soft segments and consequently makes the system more incompatible. This implies t h a t the m aterial becomes more phafce separated. Following from PU-4 to PU-2 an d to PU-5 we can see t h a t the Tm increases with increasing the PEG-2000/PTMO-2000 ratio. The increase in ratio between PEG-2000 and PTMO-2000 means th e increase in crystalline domain. This causes again the enhancement of the phase separation. This re su lt is in ag reem en t with t h a t of other authors [2,4,5].
3.3. Tensile p r o p e r ti e s
The tensile properties of the SPU s are shown in the table 3.
Table 3: Tensile properties of the SPUs
Code Polydiol ratio Tensile
at break, MPa
U ltim ate Tensile,
MPa
Elongation at break,
%
PU-1 P E G -1000 + PTMO-2000 (1/1) 7.0 8.5 650.0
PU-2 PEG-2000 + PTMO-2000 (1/1) 12.1 12.6 570.2
PU-3 PEG-4000 + PTMO-2000 (1/1) 15.2 15.7 480.0
PU-4 PEG-2000 + PTMO-2000 (1/2) 9.0 10.6 600.4
PU-2 PEG-2000 + PTMO-2000 (1/1) 12.1 12.3 555.2
PU-5 PEG-2000 + PTMO-2000 (2/1) 13.8 14.0 490.0
V N U . Jo u rn al o f Science. N a t.. Sci.. & Tech., T XX, N lt3. 2004
Pham N eoc L an , N mi ven Thu Han Li
When comparing PU-1 with PU-2 and PU-3 we can see the increase in tensile strength upon increasing the molecular weights of the polyethylene glycols. DSC d ata have shown th a t the phase separation was increasing from PU-1 to PƯ-3. On the other hand, the crystalline domain of the soft segments in the SPUs is increasing from PU-1 to PU-3 too.
Thus, larger crystalline domain in the soft segments could be the cause for th e better tensile properties of the resulted SPUs. The same law can be observed when comparing PU- 4 with PU-2 and PƯ-5. An increase in ratio of PEG-2000 to PTMO-2000 m eans the increase in crystalline domain of the soft segments and would be the reason for improving the tensile strength of the SPUs.
3.4. Swelling study
The swelling study was carried out in distilled w ater a t different tem pertures, the results are shown in figure 1:
For the all SPUs samples, the swelling decreases with rising tem peratures. When comparing PU-1 with PU-2 we see the swelling of PU-2 is much higher th a n th a t of PU-1.
This is due to lareger crystalline domain of the soft segments in PƯ-2 compared to th a t in PU-1.
If we compare PU-4 with PU-2 and PU-5, we can see also the increase in swelling from PU-4 to PU-2 and to PU-5. Here again, the reason would be the same: the increase in swelling is due to enhancem ent of the crystallinities from PU-4 to PU-2 and to PU-5.
Figure 1: The swelling curves of the SPƯS in water at different temperatures
V N U . Journal o f Science. N a t., Sci.. ổi Tech.. ỉ '.XX. N J . 2004
Synthesis and charactcrization of. 23
The same swelling behaviour of the SPUs in buffer solution can be observed in Figure 2.
Comparing P U l with PU2 and PƯ3 we can see th a t when molecaular weight of the soft segments of SPUs is increasing from P U l to PU2 and PU3, the swelling is also increasing from P U l to PU2 and PU3. The swelling is increasing from PU4 to PU2 and PU5 when the ratio PEO-2000: PTMO 2000 in the soft segments is increasing. It can be therefore concluded th a t the swelling behavior of the selected SPUs for study is strongly dependent on the PEO am ount and PEO molecular weight.
700 600 500 Ị 400 1 300 cn
200
100 0
5 10 15 20 25 30 37.5 Temperature, °c
4. C o n clu sio n
The data obtained show th a t the increase in PEO am ount as well in PEO molecular weight of the macroether diols in the SPUs soft segments results in enhancem ent of their crystalline domain making the SPUs more phase separated. The mechanical and swelling properties of the SPUs are increasing upon increasing the crystalline domain of the soft segments in the SPUs as well.
REFERENCE
1. Pham Ngoe Lan, Schacht E., J. o f Science, Natural Sciences and Technology, T. 19, No 6 (2003), 21-28.
2. P.N. Lân, Corneillie s., Schacht E., Davies M. and Shard A., Biomaterials, 17 (1996), 2273- 2280.
3. Sorenson WR., Campbell TW., Preparative Methods o f Polymer Chemistry. New York:
Interscience, (1961).
-B— PU-1 -*•— PU-2
■*” PU-3 -*-P U -4
PU-5
V N U . Journal o f Science. N a t.. Sci.. á Tech.. T. XX. A y . 2004
2 4 Pham N ỉio c L an , N g u yen T h u H ang
4. Li I., Ren z., Zhao M., Yang H., Chu B. Multiphase structure of segmented polyurethanes:
Effect of hard segment flexibility, Macromolecules, 26, (1993), 612-622.
5. Aitken R. R., Jeffs G. M. F., Thermoplastic Polyurethane elastomers based on aliphatic diisocyanates: Thermal Transitions, Polymer,
18,
(1977) 197-198.TẠP CHÍ KHOA HỌC ĐHQGHN, KHTN & CN, T.xx, SÒ 3, 2004
TỔNG HỢP
v à k h ả o s á t t í n h c h a t c ủ a c á c p o l y u r e t a n p h â nĐOẠN (PU) TRÊN c ơ s ở POLYETYLEN GLYCOL VÀ POLYTETRAMETYLEN GLYCOL
(PHẦN II: NGHIÊN
c ứ u
TÍNH CHAT c ơ LÝ VÀ ĐỘ TRƯƠNG) P h ạm N gọc LânTrung tăm N ghiên cứu Vật liệu Plyme, Đại học Bách khoa Hà Nội
N g u y ễ n Thu Hằng
Trường Đại học Khoa học T ự nhiên, Đ H Q G H N
Trong bài báo trước (1) đã nghiên cứu phương pháp tổng hợp, đặc trưng cấu trúc và hình thái học của một sô polyuretan (PU) trên cơ sở polyetylen glycol và polytetram etylen glycol. Bài báo này đê cập vê nghiên cứu tính chất cơ lý và độ trương cúa các loại PU trên trong nước và dung dịch đệm. Đã thảo luận về ảnh hưởng của th à n h phần và cấu trúc của monome ban đầu lên tính ch ất cơ lý và độ trương của PU sản phẩm.
Từ khóa: Polyuretan p h â n đoạn, tách p h a, tính chất cơ lý, độ trương.
V N U . Journal o f Science, N at., S ri.. & Tech., T. XX. N J . 2004
