synthesis and characterization of constitutional isomeric poly(amide-ester)s from adipoyl chloride...

Macromol. Chem. Phys. 2001, 202, 1531–1538 1531

Synthesis and Characterization of ConstitutionalIsomeric Poly(amide-ester)s from Adipoyl Chloride and4-(2-Aminoethyl)phenol

Li Li,1 Koichiro Yonetake,1 Mitsuru Ueda* 2

1 Department of Human Sensing and Functional Sensor Engineering, Graduate School of Engineering, Yamagata University,Yonezawa, 992-8510, Japan

2 Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo 152-8552, JapanFax: +81-3-5734-2127; E-mail: [email protected]

IntroductionIf the polycondensation is carried out from a nonsym-metric monomer (XabX) and a symmetric monomer(YccY), three general cases can be deduced. That is, ahead-to-head or tail-to-tail (H-H or T-T) ordered poly-mer, a head-to-tail (H-T) ordered polymer, and a randompolymer, are formed. The three kinds of polymers are dif-ferent in their sequences, which are called as constitu-tional isomeric polymers.

We are interested in the study on constitutional isomer-ism of polymers, and want to make clear the structure-property relationships between those isomeric polymers.Several papers have been published on the synthesis ofstructural isomeric polyamides taking advantage of theirdifferent reactivity of amino groups.[1] However, no cleardifferences in physical properties among them have beenobserved due to strong interactions between polymerchains, which were thought that the strong interchainamide NH...OC hydrogen bonds may mask the subtle dif-ference of isomers.[2]

Thus, a polymer with weak interactions should beselected as a suitable candidate to study on the structure-property relationships among constitutional isomericpolymers. In our previous paper, we described the syn-thesis and characterization of ordered and random poly-(amide-ester)s from isophthaloyl chloride and 4-(2-ami-noethyl)phenol,[3] and the three isomeric polymersshowed different solubility, thermal properties, and crys-tallinity. The DSC traces of the first-heating process forthe ordered poly(amide-ester)s showed clear endothermicpeaks, but no such peaks were observed in the second-heating process, which means no crystalline could beformed on the cooling process. The chain mobilityseemed to be restricted by hydrogen bonds between therigid aromatic amide groups. We selected adipoyl chlor-ide (1) in place of aromatic dichloride to improve thechain mobility and to increase the crystallization rate ofpoly(amide-ester).

In this paper, we report the synthesis and characteriza-tion of constitutional isomeric poly(amide-ester)s by

Full Paper: Ordered [head-to-head (H-H) or tail-to-tail(T-T)] poly(amide-ester) (6a) was prepared by polycon-densation from adipoyl chloride (1) and N,N 9-bis(4-hydroxy phenethyl)adipamide (5), which was preparedfrom the selective acylation of 4-(2-aminoethyl)phenol (2)with N,N 9-adipoylbis[benzoxazoline-2-thione] (4). AndH-T ordered poly(amide-ester) (6b) was prepared by self-polycondensation of 4-carboxy-N-(4-hydroxyphenethyl)-adipamide (7) in the presence of DBOP. Random poly(a-mide-ester) (6c) was synthesized by polymerization of 1with 2. The microstructure of the polymers obtained wasinvestigated by 1H and 13CNMR spectroscopy, and it wasfound that the polymers obtained had the expectedordered structure. Furthermore, DSC and WAXD resultsdemonstrated that the constitutional regularity of poly-mers influenced their thermal properties and crystallinity.

Macromol. Chem. Phys. 2001, 202, No. 9 i WILEY-VCH Verlag GmbH, D-69451 Weinheim 2001 1022-1352/2001/0906–1531$17.50+.50/0

1532 L. Li, K.Yonetake, M. Ueda

polycondensation of adipoyl chloride with 4-(2-ami-noethyl)phenol (2).

Experimental Part

Materials

N-Methyl-2-pyrrolidinone (NMP) and nitrobenzene werepurified by vacuum distillation and stored over 4 � molecu-lar sieves. Adipoyl chloride (1) was purified by vacuum dis-tillation (908C/6 mmHg). 4-(2-Aminoethyl)phenol (2) waspurified by recrystallization from ethanol. Triethylamine(TEA), acetone and tetrahydrofuran (THF) were purified byusual methods. Other reagents and solvents were obtainedcommercially and used as received.

The condensing agent diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl)phosphonate (DBOP) was prepared accordingto the reported procedure.[4]

N-(3-Phenylpropionyl)benzoxazoline-2-thione (3)

To a solution of 2-mercaptobenzoxazole (MB) (0.756 g,5.0 mmol) and TEA (0.77 mL, 5.5 mmol) in acetone(15 mL) at 08C was added dropwise 3-phenylpropionylchloride (0.75 mL, 5.0 mmol). After stirring for 1 h, the reac-tion mixture was poured into water. The precipitate was col-lected by filtration and dried in vacuo; yield 1.350 g (96%).Recrystallization from ethanol gave yellow needles withyield of 75%. m.p.: 97–988C.

IR (KBr): 1728 (C2O), 1335 cm–1 (C2S).1H NMR (DMSO-d6 , 308C): d = 7.30–8.03 (m, phenyl,

9H), 3.78 (t, J = 7.8 Hz, 2H, Ar1CH21CH21C2O),3.04 ppm (t, J = 7.4 Hz, 2H, Ar1CH21CH21C2O).

C16H13NO2S (283.35) Calc. C 67.82 H 4.62 N 4.94Found C 67.66 H 4.74 N 5.09

Competitive Reaction of Phenethylamine and Phenol with 3

Phenethylamine (0.13 mL, 1.0 mmol) and phenol (0.094 g,1.0 mmol) were dissolved in NMP (2 mL) at 08C. To thissolution was added active amide 3 (0.283 g, 1.0 mmol).After stirring for 5 min, the product-ratio was determined byHPLC (acetanilide as the internal standard). This reactionyielded a single product, N-phenethyl-3-phenylpropanamide.The yield was 100%. m.p.: 98–1018C.

IR (KBr): 3302 (NH), 1635 cm–1 (C2O).1H NMR (DMSO-d6 , 30 8C): d = 7.92 ppm (t, J = 11.1 Hz,

2H, NH).

C17H19NO (253.35) Calc. C 80.60 H 7.56 N 5.53Found C 80.48 H 7.49 N 5.64

N,N 9-Adipoylbis[benzoxazoline-2-thione] (4)

Compound 4 was prepared from adipoyl chloride and MB aspreviously described.[5] The yield was 85%. It was recrystal-lized from toluene to give white leaflets with yield of 82%.m.p.: 242–2448C.

IR (KBr): 1725 (C2O), 1340 cm–1 (C2S).

C24H16N2O4S2 (460.53) Calc. C 58.24 H 3.91 N 6.79Found C 58.41 H 4.09 N 6.66

N,N 9-Bis(4-hydroxyphenethyl)adipamide (5)

Compound 2 (0.274 g, 2.0 mmol) was dissolved in NMP(5 mL) at 08C, to which was added 4 (0.413 g, 1.0 mmol) inone portion. The solution was stirred for 2 h and poured into1% aqueous sodium hydrogen carbonate. The precipitateformed was collected by filtration and dried. The yield was0.350 g (92%). Recrystallization from EtOH/water affordedneedle crystal with yield of 79%. m.p.: 191–1938C.

IR (KBr): 3309 (NH), 1635 cm–1 (C2O).1H NMR (DMSO-d6 , 1008C): d = 9.09 (s, OH, 2H),

7.72 ppm (t, J = 10.3 Hz, 2H, NH).C22H28N2O4 (384.48) Calc. C 68.73 H 7.34 N 7.29

Found C 68.54 H 7.20 N 7.49

Ordered H-H or T-T Poly(amide-ester) 6a

To a solution of 5 (0.384 g, 1.0 mmol) in nitrobenzene (2 mL)was added 1 (0.15 mL, 1.05 mmol) under N2 atmosphere atroom temperature. This reaction solution was heated to1408C very slowly. After 8 h of stirring at the above tempera-ture in N2 , the solvent was removed under reduced pressure atabout 1408C. The residue was thoroughly washed withmethanol and dried in vacuo to give polymer 0.480 g (97%).The inherent viscosity of polymer in NMP was 0.31 dL/g,measured at a concentration of 0.5 g/dL at 308C.

IR (KBr): 3302 (NH), 1747 (C2O, ester), 1639 cm–1

(C2O, amide).13C NMR (DMSO-d6 , 1008C): d = 171.38 (C2O, amide),

170.70 ppm (C2O, ester).

(C28H34N2O6)n (494.59)n Calc. C 68.00 H 6.93 N 5.66Found C 68.30 H 7.06 N 5.48

4-Carboxy-N-(4-hydroxy phenethyl)adipamide (7)

The condensing agent DBOP (0.422 g, 1.1 mmol) was addedto a solution of adipic acid monoethyl ester (0.174 g,1.0 mmol) and TEA (0.14 mL, 1.0 mmol) in NMP (1 mL).After stirring for 30 min at room temperature, 2 (0.137 g,1.0 mmol) was added. The solution was stirred for 2 h andpoured into 1% aqueous sodium hydrogen carbonate, andthen extracted with AcOEt. The organic layer was evapo-rated and dissolved in ethanol (10 mL). To this solutionpotassium hydroxide (0.171 g, 3.0 mmol) was added and stir-red at 808C for 2 h. Then the solvent was removed underreduced pressure, and the residue was dissolved in water.This solution was made to pH4 with aqueous HCl solution.The precipitate was filtered off, washed with water, anddried. The yield was 0.220 g (83%). m.p.: 152–1538C(recrystallization from EtOH/water with yield of 74%).

IR (KBr): 3363 (NH), 1682 (C2O, acid), 1597 cm–1

(C2O, amide).1H NMR (DMSO-d6 , 1008C): d = 12.00 (broad, COOH,

1H), 9.20 (s, OH, 1H), 7.86 ppm (t, J = 10.2 Hz, 1H, NH).

C14H19NO4 (265.31) Calc. C 63.38 H 7.22 N 5.28Found C 63.23 H 7.09 N 5.36

Synthesis and Characterization of Constitutional Isomeric Poly(amide-ester)s from Adipoyl ... 1533

Ordered H-T Poly(amide-ester) 6b

Compound 7 (0.265 g, 1.0 mmol), DBOP (0.422 g,1.1 mmol) and TEA (0.30 mL, 2.2 mmol) were dissolved inNMP (1 mL). This solution was stirred for 8 h at room tem-perature and then for 8 h at 808C in air. The resulting poly-mer was isolated by pouring the resulting solution intomethanol and dried. Yield 0.238 g (97%). The inherent vis-cosity of polymer in NMP was 0.32 dL/g, measured at a con-centration of 0.5 g/dL at 308C.


(C2O, amide).13C NMR (DMSO-d6 , 1008C): d = 171.20 (C2O, amide),

170.77 ppm (C2O, ester).

(C14H17NO3)n (247.30)n Calc. C 68.00 H 6.93 N 5.66Found C 67.87 H 6.81 N 5.54

Random Poly(amide-ester) 6c

Polymer 6c was prepared from 1 and 2 as previouslydescribed in the synthesis of polymer 6a. Yield 98%. Theinherent viscosity of polymer in NMP was 0.35 dL/g, meas-ured at a concentration of 0.5 g/dL at 308C.


(C2O, amide).13C NMR (DMSO-d6 , 1008C): d = 171.38, 171.20, 170.77,

170.70 ppm (C2O, amide and ester).

(C14H17NO3)n(247.30)n Calc. C 68.00 H 6.93 N 5.66Found C 67.81 H 7.01 N 5.38

Model Compounds

The following model compounds were prepared from thecorresponding acyl chloride and amine or phenol to verifythe microstructure of isomeric polymer chain.

N,N-Di(2-phenylethyl)adipamide (8)

Compound 8 was prepared from phenethylamine and 1 in thepresence of TEA in THF. The yield was 100%. m.p.: 188–1908C (recrystallization from ethanol with yield of 91%).

13C NMR (DMSO-d6 , 1008C): d = 171.20 ppm (C2O).

C22H28N2O2 (352.48) Calc. C 74.97 H 8.01 N 7.95Found C 74.88 H 7.92 N 7.85

Diphenyl Adipate (9)

Compound 9 was prepared from phenol and 1 in the presenceof TEA in THF. The yield was 88%. m.p.: 105–1068C(recrystallization from methanol with yield of 86%).

13C NMR (DMSO-d6 , 1008C): d = 170.62 ppm (C2O).

C18H18O4 (298.34) Calc. C 72.47 H 6.08Found C 72.40 H 5.98

Instruments and Measurements

The infrared spectra were recorded on a Hitachi I-5020-FTIR spectrophotometer and the NMR spectra on a JEOLEX270 (270 MHz) spectrometer. Viscosity measurements

were carried out at a concentration of 0.5 g/dL in NMP at30 8C by using an Ostwald viscometer. Thermal analyseswere performed on a Seiko SSS 5200 TG/DTA 220 thermalanalyzer at a heating rate of 108C min–1 and a SSS 5200DSC 220 at a heating rate of 20 8C min–1 for differentialscanning calorimetry (DSC) under nitrogen.

X-ray diffraction experiments were carried out by a RAD-rA diffractometer (Rigaku Denki Co. Ltd.). Nickel-filteredCu Ka radiation was employed. The wide angle X-ray dif-fraction (WAXD) traces were recorded by a scintillationcounter system with a 1.0 mm diameter pin-hole collimatorand 1618 receiving slit. The diffractometry was performedin transmission. WAXD traces were obtained by a step-scan-ning method: the step width and fixed time were pro-grammed for steps of 0.05 deg every 4 s. Optical textures ofthe samples were examined using the polarizing opticalmicroscope (POM) equipped with a hot stage (Linkam Co.,TH-600RMS) under nitrogen. Melt-crystallization of thepolymers were carried out using the hot stage. The opticaltextures were recorded by a VCR system.

Results and Discussion

Polymer Synthesis

Synthesis of H-H or T-T Ordered Poly(amide-ester) 6a

A multiple step method was applied for synthesis of theH-H or T-T ordered polymer 6a from 1 and 2. N,N 9-bis(4-hydroxyphenethyl)adipamide (5) was necessary forthe synthesis of polymer 6a. Thus, the following compe-titive reactions were carried out to determine which inter-mediate was suitable to obtain 5.

First, competitive reaction of 3-phenylpropionyl chlor-ide with phenethylamine and phenol was carried out inNMP at 08C for 5 min (Equation (1)).

Two products, N-phenethyl-3-phenylpropanamide andphenyl propionate, were obtained in the mole-ratio of0.75/0.25.

Then, competitive reaction of N-(3-Phenylpropionyl)-benzoxazoline-2-thione (3), which has a high selectivityto nucleophiles, with phenethylamine and phenol wascarried out in NMP at 08C for 5 min (Equation (2)). The


desired product, N-phenethyl-3-phenylpropanamide, wasobtained in quantitative yield.

Based on these results, compound 5 was prepared fromN,N 9-adipoylbis[benzoxazoline-2-thione] (4) and 2. Poly-mer 6a was prepared by condensation of 1 with 5. Thepolycondensation proceeded in nitrobenzene at 1408C,[6]

giving polymer 6a with an inherent viscosity of 0.31 dL/g(Equation (3)).

Synthesis of H-T Ordered Poly(amide-ester) 6b

The H-T ordered poly(amide-ester) (6b) was prepared asshown in Equation (4). The condensation of adipic acidmonoethyl ester with 2 in the presence of DBOP gave 4-ethoxycarboxy-N-(4-hydroxyphenethyl)adipamide, whichwas treated with an alkaline solution to afford 4-carboxy-N-(4-hydroxyphenethyl)adipamide (7). The self-polycon-densation of monomer 7 was carried out in NMP withDBOP at room temperature l808C and produced H-Tordered poly(amide-ester) 6b in quantitative yield withan inherent viscosity of 0.32 dL/g.

Synthesis of Random Poly(amide-ester) 6c

If monomer XabX is mixed with monomer YccYdirectly, only a random polymer could be prepared.[7] Therandom poly(amide-ester) 6c was obtained from 1 and 2by mixing two monomers together at once (Equation (5)),with an inherent viscosity of 0.35 dL/g.

Polymer Characterization

The IR spectra of all poly(amide-ester)s prepared showedcharacteristic bands in the range of 3302–3309 (NH),1747–1751 (C2O, ester), 1639–1643 cm–1 (C2O,amide), respectively. Elemental analyses also supportedthe formation of expected polymers.

The microstructure of the polymers was determined by1H and 13C NMR, taken in DMSO-d6 at 1008C usingTMS as internal reference. The 1H NMR chemical shiftsof proton nuclei on methylene groups for model com-pounds and monomers prepared are as shown in Equation(6).

Figure 1 shows the expanded 1H NMR spectra in thealiphatic proton region and the assignment of polymers.There are six signals of methylene protons for the H-H orT-T poly(amide-ester) 6a observed at 3.30 ppm (peak a),2.74 ppm (b), 2.60 ppm (f), 2.06 ppm (c), 1.78 ppm (e),and 1.49 ppm (d). These shifts are assigned as shown inScheme 1. One the other hand, the H-T polymer 6bshows five signals of methylene protons at 3.30 ppm(peak a), 2.74 ppm (b), 2.53 ppm (g), 2.12 ppm (h), and1.64 ppm (i and j). Compared with the two spectra ofpolymer 6a and 6b, it can be found that the signals ofproton nuclei on the methylene groups derived from adi-poyl derivatives provide sensitive probes for differentsubstitution patterns. For H-H or T-T segment, it showsfour signals; and for H-T, it shows three. However, nogreat difference are observed for those two methylenederived from 4-(2-aminoethyl)phenol (peak a and b). Forrandom polymer 6c, nine signals would be expected fromits random structure. In fact, nine signals appear. Anotherconclusive spectral evidence for the microstructure ofpolymers is provided by 13C NMR spectroscopy. The

Scheme 1.


13C NMR chemical shifts of amide or ester carbonyl car-bons for model compounds and monomers prepared areas shown in Equation (7), together with their shifts of car-bon nuclei on methylene groups.

The expanded 13C NMR spectra of polymers in the car-bonyl region and in the aliphatic carbon region are pre-sented in Figure 2. The signals of carbon nuclei in amideand ester carbonyl groups appear at 171.38 (peak 1) and170.70 ppm (2) for H-H or T-T ordered polymer 6a,respectively. On the other hand, for H-T ordered polymer6b, they are observed at 171.20 (3) and 170.77 ppm (4).

In contrast, four peaks of carbon nuclei for polymer 6cappear just as expected from its random structure (detailin Scheme 2).

Similar with the differences of their 1H NMR spectra, itcan be observed that the 13C NMR signals of carbon nucleion the methylene groups derived from adipoyl derivativespresent sensitively different probes for different substitu-tion patterns. For H-H or T-T ordered polymer 6a, theyshow four signals at 34.37 (g), 32.33 (e), 23.95 (a), and22.82 ppm (b); and for H-T ordered polymer 6b, theyshow another four signals at 34.09 (i), 32.44 (f), 23.59 (c),and 23.07 ppm (d). However, no great difference isobserved for two methylene peaks of the polymers, onesignal appear at 33.60 ppm despite different chain regular-

Figure 1. 1H NMR spectra of polymers, 6a, 6b, and 6c inDMSO-d6 measured at 100 8C (see Scheme 1).

Figure 2. 13C NMR spectra of polymers, 6a, 6b, and 6c inDMSO-d6 measured at 100 8C (see Scheme 2).


ity (peak h), and another one is overlapped with the signalsof the solvent DMSO-d6. For random polymer 6c, nine sig-nals appear in aliphatic carbon as expected.

The poly(amide-ester)s were white powders, soluble insulfuric acid, NMP and DMSO, partly soluble in DMFand completely insoluble in other solvents, such asmethanol, THF and water.

Thermal Properties and Morphologies of Polymer 6a,6b, and 6c

The thermal properties of polymers were examined bythermogravimetry (TG) and differential scanning calori-metry (DSC). The rapid weight loss of all polymersstarted at about 2908C, and 10% weight loss temperaturewas measured at approximately 3608C. Their thermaldegradation behaviors were almost same regardless ofdifferent sequence.

The DSC traces of the first and second heating pro-cesses for polymers 6 are illustrated in Figure 3 and 4,respectively. It was noted that the second-heating tracesalso show endothermic peaks as shown in Figure 4. Theprofiles of the third traces were the same as those of thesecond ones, though they were not shown. These findingsrevealed that the crystallites could be formed on coolingfrom the melts, i.e., the crystallization of polymers 6were reversible. On the other hand, aromatic poly(amide-ester) were not crystallized during the cooling processonce the polymers were melted, as reported in our pre-vious paper.[3] It was conceivable that the chain mobilitywas restricted by hydrogen bonds between the intermole-cular- or intramolecular- NH1C2O bonds.

An introduction of the aliphatic chain into the back-bone diluted the concentration of the amide bond in thechain, and enhanced the chain flexibility. Thus, the influ-ence of hydrogen bonds on the chain mobility decreasedin polymers 6, and regular chain conformations could beformed on cooling from the melt.

A monomodal endothermic peak was clearly observedat 2258C in the first trace of H-H or T-T ordered polymer6a. The first trace of H-T ordered polymer 6b showed abimodal endothermic peak appeared at 203 and 2488C.On the other hand, a broad and small endothermic peakexisted around 1848C in first and second traces of ran-dom polymer 6c. Thus, they were expected to have dif-ferent crystalline nature due to their different chain regu-larities. Sequential polymers (6a and 6b) exhibitedhigher crystallinity and melting temperatures. In the caseof 6c, however, it was hard to crystallize because of therandom chain sequence.

As demonstrated in Figure 4, the lower endothermicpeak shifted to higher temperature in the second-heatingDSC traces of polymer 6b. When as-synthesized polymer6b was annealed for 2 h at 2108C and 2308C, respec-tively, the DSC traces changed as shown in Figure 5.After annealing at 2108C, the side-peak shifted to themain peak. Moreover, after annealing at 2308C the sam-ple exhibited a monomodal trace, and the endothermic

Scheme 2. Figure 3. DSC traces of the first-heating process for polymers6a, 6b, and 6c.

Figure 4. DSC traces of the second-heating process for poly-mers 6a, 6b, and 6c.


peak became comparatively sharp. It suggested that therecrystallization took place during the annealing process.Thus, the lower endothermic peak could be assigned tosub-melting due to the thin and thermodynamicallyunstable crystallites.

WAXD curves of annealed polymers 6 are illustratedin Figure 6. Polymer 6a, 6b, and 6c were annealed for2 h at 2008C, 2308C, and 1508C, respectively. The

WAXD curves of all samples show crystalline profiles.The reflection peaks of polymer 6c are broad as com-pared with ordered polymers. Polymer 6c has a lowercrystallinity. Thus, the chain sequence of polymer 6c wasnot considered to be fully random. It seems to be com-posed of partially blocky sequence. The crystals in poly-mer 6c seem to be similar to those in ordered polymers.Figure 7 show the WAXD curves of as-made andannealed polymers 6b. Annealing treatment increased theintensities of the reflections. It was another evidence forrecrystallization. These results agreed with those of DSC.

The spherulitic texture grew up in each sample on cool-ing from the melt. The spherulites observed under thepolarized optical microscope are shown in Figure 8. Thespherulitic morphologies of polymer 6 are different fromeach other. Polymer 6b exhibits a dendritic spherulitewhich is optically negative under the crossed polarizerwith a sensitive color plate (k = 530 nm). These crystalswere developed at 2008C. The spherulites formed at1858C in polymer 6a are also dendritic. However, theydo not resemble those of polymer 6b, as shown in Fig-ure 8. It was attributable to the difference of their chainsequence. In polymer 6c, the glomerate textures grew at1508C indicating complicated fine textures. The spheruli-tic morphology of polymer 6c are quite different fromthose of ordered polymers. Thus, it can be concluded thatthe chain sequences of polymers 6 have an effect on theirmorphologies.

Figure 5. DSC traces of the first-heating process for polymers6b after annealing treatment.

Figure 6. X-ray diffraction patterns of annealed samples: poly-mer 6a, 6b, and 6c annealed at 2008C, 230 8C, and 150 8C for2 h, respectively.

Figure 7. X-ray diffraction traces of as-made and annealedsamples for polymer 6b. The sample was annealed at 230 8C for2 h.


ConclusionIn summary, we have demonstrated the synthesis of threekinds of structural isomeric poly(amide-ester)s. Amongthem, H-H or T-T and H-T ordered polymers can beachieved from 1 and 2 via a multi-step process; By mix-ing 1 and 2 directly together, a random polymer can be

obtained. The structure of polymers was characterized by1H and 13C NMR spectra, which agreed well with theirdifferent sequence. The constitutional regularity of poly-mers also strongly influenced their thermal property andcrystallinity. The ordered polymers exhibited higher crys-tallinity and melting points than those of the randompolymer. Moreover, the different chain sequences havean effect on their morphologies. In H-T ordered polymer,well-defined spherulites developed on cooling from themelt. HH-TT polymer exhibited other spherulitic texture,however, the spherulitic morphology of random polymerwas quite different from those of the ordered polymers.

Acknowledgement: We thank Sadao Kato for his assistanceand Takeyoshi Takahashi for performing the elemental analyses.We wish to also acknowledge financial support from the NewEnergy and Industrial Technology Development Organization(NEDO) for the project on Technology for Novel High-Func-tional Materials and Agency of Industrial Science and Technol-ogy (AIST). We also thank the Japan Chemical InnovationInstitute (JCII) for financial support.

Received: September 20, 2000Revised: November 27, 2000

[1] [1a] M. Ueda, T. Morosumi, M. Kakuta, R. Sato, Polym. J.(Tokyo) 1990, 22, 733; [1b] M. Ueda, M. Kakuta, T. Moro-sumi, R. Sato, Polym. J. (Tokyo) 1991, 23, 167; [1c] M.Ueda, T. Morosumi, M. Kakuta, Polym. J. (Tokyo) 1991,23, 1511; [1d] M. Ueda, M. Morishima, M. Kakuta, J.Sugiyama, Macromolecules 1992, 25, 6580; [1e] M. Ueda,H. Sugiyama, Macromolecules 1994, 27, 240.

[2] G. Xie, P. Pino, G. P. Lorenzi, Macromolecules 1990, 23,2583.

[3] L. Li, H. Seino, K. Yonetake, M. Ueda, Macromolecules1999, 32, 3851.

[4] M. Ueda, M. Kameyama, K. Hashimoto, Macromolecules1988, 21, 19.

[5] M. Ueda, K. Seki, Y. Imai, Macromolecules 1982, 15, 17.[6] K. Yamaguchi, M. Takayanagi, S. Kuriyama, Kougyouka-

gakuzasshi 1975, 58, 358.[7] [7a] P. Pino, G. P. Lorenzi, U. W. Suter, P. G. Casartelli,

A. Steinmann, F. J. Bonner, J. A. Quiroga, Macromolecules1978, 11, 624; [7b] U. W. Suter, P. Pion, Macromolecules1984, 17, 2248.

Figure 8. Optical textures of polymers 6. Melt-crystallizationwas carried out in the hot-stage. The spherulitic textures of poly-mer 6a, 6b, and 6c developed at 185 8C, 200 8C, and 150 8C.

synthesis and characterization of constitutional isomeric poly(amide-ester)s from adipoyl chloride...

Documents