Design and synthesis of polymeric dispersant for water-borne paint by atom transfer radical polymerization

Figures & data

Table 1. Data of molecular weight for PBA by ATRP at 80 °C in dioxane.

S. no.	Polymer	[M]/[Initiator]/[CuX]/[Ligand]	Time (h)	Conversion (%)	Mn(GPC)	Mn(Theo)	PDI
1	PBA-Br-A	25:1:1:1	4	94	2820	3000	1.28
2	PBA-Br-B	25:1:1:1	4.5	95	4254	4500	1.29
3	PBA-Br-C	25:1:1:1	5	95	5820	6000	1.29

Notes: PBA-Br-A,B and C describes the macroinitiators, [M] = moles of BA, [CuX] = moles of CuBr, [Ligand] = moles of PMDETA, Mn_(GPC) = molecular weight determined by GPC and Mn_(Theo) = theoretical molecular weight.

Table 2. Data of block copolymerization from PBA by ATRP at 80 °C in dioxane.

S. no.	Polymer	[PBA]/[CuX]/[Ligand]	Time (h)	Conversion (%)	Mn(GPC)	Mn(Theo)	PDI
1	PBA-b-PHEMA-A	1:1:1	4	94	7601	7910	1.26
2	PBA-b-PHEMA-B	1:1:1	4	95	10,169	11,856	1.27
3	PBA-b-PHEMA-C	1:1:1	4	95	12,878	15,820	1.28

Notes: [PBA] = moles of macroinitiator, [CuX] = moles of CuBr, [Ligand] = moles of PMDETA, Mn_(GPC) = molecular weight determined by GPC and Mn_(Theo) = theoretical molecular weight.

Table 3. Data of triblock polymerization from PBA-b-PHEMA by ATRP at 80 °C in dioxane.

S. no	Polymer	[PBA-b-PHEMA]/[CuX]/[L]	Time (h)	Conversion (%)	Mn(GPC)	Mn(Theo)	PDI
1	PBHM-10^a	1:1:1	5	91	9100	10,000	1.25
2	PBHM-15^b	1:1:1	5	90	13,599	15,000	1.26
3	PBHM-20^c	1:1:1	5	91	18,223	20,000	1.28

Notes: [PBA-b-PHEMA] = moles of macroinitiator, [CuX] = moles of CuBr, [Ligand] = moles of PMDETA, Mn_(GPC) = molecular weight determined by GPC and Mn_(Theo) = theoretical molecular weight.

^a (PBA)_23.4-b-(PHEMA)₃₈-b-(MMA)₁₉.

^b (PBA)₃₅-b-(PHEMA)₅₇-b-(MMA)_29.

^c (PBA)₄₆-b-(PHEMA)₇₆-b-(MMA)_39.

Table 4. Recipe of post modification of PBHM.

S. no.	Polymers	Wt of PBHM	Hydroxy EQ	TEA^a	CEC^b
1	PBHM-10	10	296.66	3.41	4.81
2	PBHM-15	10	291.72	3.46	4.88
3	PBHM-20	10	286.95	3.52	4.96

^a TEA-Triethyl amine.

^b CEC-Cyclic ethylene chlorophosphate.

Table 5. Hydroxy value of PBHM.

S. no.	Polymer ID	Hydroxy value (mg KOH/gm)
1	PBHM-10	189.1
2	PBHM-15	192.3
3	PBHM-20	195.5

Figure 1. Spectrum (A) PBHM, Spectrum (B) Modified poly(BA)-b-poly(HEMA-COP)-b-poly(MMA), Spectrum (C) Modified poly(BA)-b-poly modified with phosphate group)-b(MMA)(MPBHM).

Figure 2. ¹H NMR spectrum of PBHM.

Figure 3. ¹H NMR spectrum of MPBHM.

Figure 4. ³¹P NMR of MPBHM.

Figure 5. GPC traces of copolymers.

Figure 6. Plot of conversion Vs time of PBA-Br (macroinitiators).

Figure 7. Plot of ln ([M]₀/[M]) versus time for ATRP of PBA-Br.

Figure 8. EDXS graph of MPBHM.

Table 6. Elemental analysis of MPBHM.

S. no.	Elements	Weight (%)	Atomic (%)
1	C	46.3	54.67
2	N	14.09	14.27
3	O	30.19	26.76
4	P	9.42	4.31
5	Total	100	100

Table 7. Data of surface tension and Critical Micelle Concentration of MPBHM.

S. no.	Polymers	Surface tension γ (mN m^−1)	Critical Micelle Concentration	Calculated HLB values	Wetting time (S)
1	MPBHM-10	34.80 ± 1	0.0536 g/l	9.14	22
2	MPBHM-15	30.31 ± 1	0.0327 g/l	9.19	23
3	MPBHM-20	29.79 ± 1	0.0189 g/l	9.19	25

Figure 9. Surface tension Vs concentration of aqueous solutions of MPBHM-10.

Figure 10. Surface tension Vs concentration of aqueous solutions of MPBHM-15.

Figure 11. Surface tension Vs concentration of aqueous solutions of MPBHM-20.

Table 8. Paint formulation.

S. no.	Ingredients (g)	Pigment volume concentration
		35	45	55
1	TiO2	5.98	6.91	7.69
2	Talc	27.27	31.56	35.03
3	Binder	43.47	33.03	24.55
4	W&D^a	0.83	0.962	1.06
5	Biocide	0.05	0.05	0.05
6	Defoamer	0.05	0.05	0.05
7	Water	23.26	28.28	32.12
	Total	100	100	100

Note: W&D – modified MPBHM.

^a 2.5% concentration based on total Pigment.

Figure 12. Ease of dispersion of paint with various MPBHM of 35 PVC.

Figure 13. Ease of dispersion of paint with various MPBHM of 45 PVC.

Figure 14. Ease of dispersion of paint with various MPBHM of 55 PVC.

Figure 15. Viscosity of paints of 35 PVC with 2.5% of MPBHM-10.

Figure 16. Viscosity of paints of 45 PVC with 2.5% of MPBHM-15.

Figure 17. Viscosity of paints of 55 PVC with 2.5% of MPBHM-20.

Figure 18. Whiteness index of paint with 2.5% of MPBHM-10, MPBHM-15, and MPBHM-20.

Figure 19. Yellowness index of paint with 2.5% of MPBHM-10,MPBHM-15, and MPBHM-20.

Figure 20. Gloss of paint with 2.5% of MPBHM.

Scheme 1. Reaction of ATRP of poly(BA)-b-poly(HEMA)-poly(MMA) and post modification.