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Synthesis and Characterization of Poly Diacrylamide Derivatives as Cross-linked Polymers

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الخلاصة :
حضر عدد من البوليمرات المتشابكه من مفاعلة بعض ثنائي الامين مثل الالوبيورينول وثلاثي مثيل ميثوبريم كأدويه ثنائية الامين , والبروفلافين , البنزدين , 3,1-فنيلين ثنائي الامين , ميلامين , اثلين داي امين , اثلين تراي امين , فنيل هيدرازين , 5,5,2,2-رباعي مثيل بنزدين , مع مولين من حامض الاكريليك بأستعمال الثايونيل كلورايد كعامل مكثف.
بلمرت الاكريل امايدات المعوضه بطريقه الجذور الحرة بأستخدام داي بنزويل بيروكسايد كبادئ. شخصت البوليمرات المتشابكه بطريقه اطياف الاشعه تحت الحمراء وطيف الرنين النووي المغناطيسي , درست ثباتيه السلوك الحراري بطريقه التحليل الحراري الوزني وطريقه المسح المسعري التفاضلي المحضره.

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لقد اعطت التحاليل الحراريه للبوليمرات المحفزه ثباتيه حراريه جيده , مع الحصول على بوليمرات ذات اذابه عاليه بواسطة الداي مثيل فورمايد (DMF) وفي الداي مثيل سلفوكسايد (DMSO).
اللزوجه الجوهريه كانت بمدى ( ) dl/g والتي تؤكد الاوزان الجزيئيه المناسبه , درست سرع التحرر الدوائي بدوال حامضيه مختلفه بدرجه 37 °م . النتائج اعطت صفات حراريه عالية وسرع تحلل دوائي بطيئه نتيجه التحلل المائي البطئ للبوليمرات الدوائيه المتشابكه المحضرة .

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Abstract:
Many cross-linked polyamides were synthesized from reaction of some activated diamines such as, Allopurinol and Tri methyl methoprim as drug diamines , and proflavine, benzidine, 1,3-phenylen diamine, melamine, ethylene diamine, diethylenetriamine, phenyl hydrazine, 2,2,5,5-tetra methyl benzidine and two moles of acrylic acid, using thionylchloride as a condensed agent, the disubstituted acrylamide derivatives were polymerized freeradically using dibenzoylperoxide as an initiator, the cross-linked polymers were characterized by conventional methods including FTIR and H-NMR spectroscopes .thermal stability and thermal behavior of polymers were studied using thermal gravimetric and differential scanning calorimetric methods. The cross-linked polymers showed good thermal stability. The obtained polymers showed excellent solubility in DMF and DMSO.

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The inherent viscosities were in the range (dl/g) which indicated suitable molecular weight. The drug substituted with diacrylamide polymers were studies. The controlled drug release was measured in different pH values at 37oC. The results gave high thermally stable properties with high sustained release due to the slow hydrolysis of drug polymer for crosslinked polymer chains.

6. 6 Synthesis of diacrylamide monomers (A1-A11):-
3g. (0.04mole) of acrylic acid was dissolved in 10ml of dioxane was added in a round bottomed flack equipped with condenser the excess of thionylchloride was added, reflexed the mixture with stirring about 1h the mixture was reflexed for 30min . The excess of thionylchloride was distilled off. (0.02mole) of suitable diamine was added in the presence of pyridine with vigorously stirring at room temperature about 1h. The reaction mixture was heated at 40 °C Filtered and a solvent was evaporated under a vacuum. The prepared monomer was washed with ether and dried.
Table (1) Physical properties of prepared diacrylamide monomers(1-11)

7. Table (1) Physical properties of prepared diacrylamide monomers(1-11)7 7
Table (1) Physical properties of prepared diacrylamide monomers(1-11)

8. 8 Free radical polymerization of monomers (12-22)
To a screw-capped polymerization bottle containing 2.5g of one of prepared monomer was dissolved in 10ml of dry DMF, 0.05g. (0.025 %) by weight of the monomer concentration of dibenzoyl peroxide was added, the solution was flushed with nitrogen gas. then the bottled was closed and incubated in a water bath at 90 °C for 1h. the mixture was cooled and container was poured into a beaker of methanol . A viscous polymer was formed, separated, washed and dried in a vacuum oven at 50 °C.

9. Table(2)Physical properties of prepared cross-linked polyamide(12_22)9 9
Table(2)Physical properties of prepared cross-linked polyamide(12_22)

10. Result and discussion: 10
Result and discussion:
1-Preparation of N,N- di acrylamide derivatives (A1-A11):
Some diamine Monomers were prepared from reaction of 2 moles of acrylic acid with. the N,N- diacrylamides were prepared in the presence of thionyl chloride and pyridine as a condensed agents. As illustrated in the following equation:-

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The mechanism of the reaction is described as neocleophilic attack of NH2 group on C=O group, which illustrated as below(21):
Scheme (1)

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The structural of prepared monomers were characterized using FTIR spectra fig (1) of monomer (9) shows the absorptions at 1300 cm-1 due to C-N, the absorption of N-H group at 3224 and disappearing OH carboxylic group at cm-1, the carbonyl group shifted from 1750 to 1655 cm-1 indicated the amide of acrylamide due to the resonance effect.

13. Fig (1) FTIR Spectrum of N,N diacrylamide diethylenetriamine (A9)13 9
Fig (1) FTIR Spectrum of N,N diacrylamide diethylenetriamine (A9)

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The absorption of –NH amine was observed at 3358 cm-1 of monomer A5 indicated the abserved at 3340, and the C=O amide reveated at 1641 cm-1, as shown in fig(2).
Fig (3) , FTIR soectrum of monomer A3 also indicated the absorption at 3354 cm-1 of NH group and C=O acrylamide at 1670 cm-1. All prepared diacrylamides were indicated FTIR spectra Fig (1)- Fig (4) the presence of C=C double bond appeared in the range cm-1 due to shift of conjugation of

15. Fig (2) FTIR Spectrum of monomer (5)15 9
Fig (2) FTIR Spectrum of monomer (5)
Fig (3) FTIR Spectrum of monomer (A3)

16. Fig (4) FTIR Spectrum of monomer (A6)16 9
Fig (4) FTIR Spectrum of monomer (A6)

17. Table (3) lists the mainabsorption of prepared monomers (A1-A11)17 9
Table (3) lists the mainabsorption of prepared monomers (A1-A11)

18. Preparation of N-Substituted Polyacrylamides: 18
Preparation of N-Substituted Polyacrylamides:
11 new polymers have been prepared by free-radical polymerization for N,N-disubstituted acrylamide monomers in the presence of initiator such as dibenzoyl peroxide :
The polymerization process going by free-radical polymerization mechanism.

19. 6 Characterization of N,N-disubstituted Poly acrylamides (A12-A22):19 6
Characterization of N,N-disubstituted Poly acrylamides (A12-A22):
The prepared polymers (A12-A22) have been diagnosed with FTIR spectra and analysis of NMR. Which showed the infrared spectrum Fig(5) of the polymer (Proflavine) it was observed at 3466 cm-1 due to vibration (N-H), absorption at 3064 cm-1 due to (C-H) aromatic, pack absorption revealed at 2860 cm-1 due to (C-H) aliphatic, the spectrum showed the pack absorption at 1693 cm-1 due to the stretching carbonyl of polyamide (C=O) as well as the absorption package when 1552 due to the double bond (C=C) in the benzene ring. Table (4) shows the infrared absorptions of polymers (A12-A22). Fig (6) shows the infrared spectrum of polymer (13). Fig (5) Indicated the structural of polymer (20).

20. Fig (5) FTIR Spectrum of polymer (20)9
Fig (5) FTIR Spectrum of polymer (20)
Fig (6) FTIR Spectrum of polymer (12)

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TGA, Fig (7) of polymer (20) shows the weight loss in tow stages , the first appeared at °C with 40% weight loss % and the second, ranged °C with total weight loss 95% as thermosetting polymer due to the presence of aromatic rangs in proflavine, and due to the crosslined polymer.

22. Fig (7) TGA of polymer (A19)22 9
Fig (7) TGA of polymer (A19)

23. Table (4) FTIR absorptions of prepared polymers [A12-A22]23 7
Table (4) FTIR absorptions of prepared polymers [A12-A22]

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Fig (8) of DTA of polymer (A19) showed the three exothermic area under peak, which summarized in Table (5).

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Table (5).

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It was concluded that the aromatic N,N-diacrylamides have high thermal stabilities with respect to the aliphatic N,N- diacrylamides . inspite of the polar interaction and hydrogen bonding between amide groups through the main chains of polymer.
Fig (9) showed microscopic photo of polymer (A13)which indicated the orientation of benzidine rings through ester groups of polyacrylate.
Fig (10) showed microscopic photo of polymer (A15), indicated the bulky melamin units were substituted with di or tri of amino group in melamine with acrylamide polymer, so no phase transition could be noticed, and all prepared polymers were decomposed at high temperatures.

27. Fig (9) Microscopic photograph of (A13)27 9
Fig (9) Microscopic photograph of (A13)
Fig (10) microscopic photograph of (A15)

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Fig (11a) shows the UV. Spectra of polymer (A17) at 37 °C in pH 7.4 and Fig
Fig (11b) shows UV. Spectra of polymer (A17) in pH 1.2

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Fig (12) controlled drug release of polymer (A17) containing allopurinol through the backbone of polymer chains, the hydrolysis of the amide groups of polymer through cross-linked polymer was observed the release in pH 7.4 at 37 °C, taking more than 5 days to release >80% of allopurinol from the polymer matrix, 14% minimal level over 1 day but maintain a sustained release over more than days , releasing from at least 40-50% in pH 7.4 as in the same media of gastro intestinal system .
The hydrolysis in pH 1.2 was slower than pH 7.4 .In basic medium more release due to the presence of -OH in basic which was observed a stronger nucleophilic with respect to water , and H2O takes place faster hydrolysis than acidic medium.
A swelling percentage of the prepared polymer was studied which equal to 10% in acetone and 12% 1n ethanol , swelling %was calculated according to the following . The swelling % of the cross-linked polymer was less than linier polymer as it was expected.

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Fig (12) Controlled drug release of allopurinol di acrylamide polymer A17 in pH 7.4 and 1.2 at 37 °C

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Fig (13) 1H-NMR spectrum of monomer (A6) shows the signals at ppm (CH=CH2) as triplet and doublet , the other signal was appeared at 7.4 ppm S. was attributed to 2(=CH) of allopurinol ring.
Fig (14) of 1H-NMR spectrum of polymer (A22) indicated the polymerization of acryl amide through the presence of signal at ( ) ppm of 6H (-CH-CH2) as d. and t. , the signal appeared at 6.6 ppm as 2(=CH) , as d.d. , the other 2(CH) aromatic appeared at 7.3 ppm , and the 2NH amidic was revealed at 10 ppm

32. Fig (13) 1H-NMR spectrum of polymer (A6)32 9
Fig (13) 1H-NMR spectrum of polymer (A6)
Fig (14) 1H-NMR spectrum of polymer (A22)