Synthesis and characterization of polyurethane-urea-amide based on functionalized polystyrene

Figures & data

Table 1. Mole fraction in feed, repeating length and the inherent viscosities of the polymers.

Polymer’s code	Mole fraction			Repeating unit length (g mol^−1)	ηinh (dL g^−1)
	OH-PS-OH	HMDI	6-X-6^a
Starting materials OH-PS-OH2000	–	–	–	2000	0.1
Series 1: Based on6A6
A1	1	2	1	2678	1.3
A2	2	3	1	4846	2.1
A3	3	4	1	7014	2.6
A4	4	5	1	9182	3.1
Series 1: Based on6T6
T1	1	2	1	2698	1.8
T2	2	3	1	4866	2.6
T3	3	4	1	7034	3.2
T4	4	5	1	9202	3.9

^a X can be either Adipate and terephthalate.

Figure 1. Effect of soft segment length on the molecular weight of the polymer.

Figure 2. Possible hydrogen bonding interactions of urea, urethane and amide groups.

Figure 3. FT-IR spectrum of two copolymers at room temperature: ♦, A1; ▲, T1.

Table 2. FT-IR data of the multiblock copolymer at room temperature.

Name of the polymer	N–H Urea (w)	C=O Urethane (cry.)	C=O urea (Crys.)		Amide C=O		Crystallinity (%)
			Monodentate	Bidentate	Crys.	Amor.
Series 1: Based on 6A6
A1	3310	1735	1670	–	1638	1685	60
A2	3320	1734	1672	–	1637	1683	54
A3	3301	1733	1673	–	1636	1682	46
A4	3332	1732	1669	–	1634	1681	38
Series 2: Based on 6T6
T1	3315	1730	1684	–	1625	1679	70
T2	3310	1732	1689	–	1624	1678	65
T3	3320	1731	1690	–	1623	1676	58
T4	3329	1732	1686	–	1624	1675	49

Figure 4. Temperature dependent FTIR spectrum of T1 copolymer at different temperatures.

Figure 5. Schematic diagram of the hydrogen bonding interaction in 6A6 HS.

Figure 6. Schematic diagram of the hydrogen bonding interaction in 6T6 HS.

Figure 7. WAXS pattern of the sample at room temperature: (a), A1; (b), T1.

Figure 8. DSC heating curve and cooling curve of two polymer: ♦, A1; ▲, T1.

Table 3. DSC, TGA, swelling ratio and solubility data of the polymer at room temperature.

Polymer code	HS (wt.%)	SS (wt.%)	ηinh (dL g^−1)	DSC				TGA °C	Water abs. (wt.%)	Solub.^a (wt.%)
				Tg °C	Tm °C	Tc °C	Tm-Tc °C
Starting material OH-PSt-OH2000	0	100	0.1	58	–	–	–	412	0	0
Series 1: Based on 6A6
A1	26	74	1.3	82	258	216	42	414	5	48
A2	18	82	2.1	80	248	–		415	8	68
A3	14	86	2.6	78	245	–	–	415	11	87
A4	13	87	3.1	76	239	–	–	416	13	96
Series 2: Based on 6T6
T1	27	73	1.8	88	265	241	24	416	8	35
T2	17	83	2.6	86	262	–	–	416	11	58
T3	14	86	3.2	83	250	–	–	417	14	77
T4	13	87	3.9	81	243	–	–	418	17	85

^a Solubility test is done in chloroform at room temperature.

Figure 9. Effect of HS concentration on the Tg of the soft phase: ♦, 6A6 series; ▲, 6T6 series.

Figure 10. TGA thermograms of the two polymer: ♦, A1; ▲, T1.

Scheme 1. The reaction pathway for the synthesis of semi-crystalline copolymer.

Table 4. WAXS data for PUUA based A1 and T1.

Code	2θ	FWHM	β = π/180 × FWHM	θ	D = Kλ/β.Cos θ	Cos θ	nm	A
A1	1.3458	1.2905	0.022533	0.6729	63.91	0.9999	0.639	6.39
	23.5500	0.4728	0.008254	11.7750	178.20	0.9790	1.782	17.82
T1	1.8313	1.0477	0.0183	0.916	78.75	0.9998	0.8	7.9
	20.9965	0.7283	0.0127	10.498	115.17	0.9832	1.2	11.5
	22.6064	0.6516	0.0114	11.303	129.07	0.9806	1.3	12.9
	23.7308	0.47275	0.0083	11.865	178.27	0.9786	1.8	17.8

Table 5. Simple peak indexing for PUUA based A1 and T1.

Code	Peak position 2θ	Sin^2 θ	1000 × Sin^2 θ	1000 × Sin^2 θ/41.49	Reflection	Remarks
A1	1.3	0.00015	0.150	0.0036	000	0+0+0
	23.55	0.04164	41.645	1.0037	100	1^2+0+0
T1	1.8313	0.00025	0.250	0.0076	000	0+0+0
	20.9965	0.0332	33.200	1.0076	100	1^2+0+0
	22.6064	0.0384	38.400	1.1654	100	1^2+0+0
	23.7308	0.0423	42.300	1.2838	100	1^2+0+0