Synthesis of High cis-Polybutadiene in Styrene Solution with Neodymium-Based Catalysts: Towards the Preparation of HIPS and ABS via In Situ Bulk Polymerization

Table 1

Recipes for coordination polymerization of 1,3-butadiene in styrene using the catalyst system NdV₃/DIBAH/EASC.

Run	[Al]/[Nd]	[Cl]/[Nd]	(mL)	Addition order	(%)	(g/mol)		content (%)	cis-1, (%)	(°C)
R1	20	0.62	200	S+B+Al+Nd+Cl	66.8	19000	7.5	24.4	95.8	−104.8
R2	20	0.62	300	S+B+Al+Nd+Cl	71.2	61000	4.1	14.4	96.1	−104.8
R3	30	0.62	300	S+B+Al+Nd+Cl	57.5	38000	5.7	13.2	96.1	−103.3
	20	0.62	200	S+B+Cl+Nd+Al	—	—	—	—	—	—
R5	20	0.62	200	S+Al+Nd+Cl+B	85.3	150000	3.3	7.7	96.4	−107.4
R6	20	0.62	300	S+B+(Al+Nd+Cl	67.2	88000	4.0	10.0	96.4	−104.9
R7	20	0.62	300	S+B+(Cl+Nd+Al	70.0	86000	5.6	14.3	96.5	−106.4
R8	30	0.62	300	S+B+(Al+Nd+Cl	60.1	42000	4.5	10.7	94.4	−104.2
R9	30	0.62	300	S+B+(Cl+Nd+Al	64.7	27000	8.4	11.7	94.8	−104.3
R10	30	0.90	300	S+B+(Al+Nd+Cl	67.2	54000	4.5	9.2	96.0	−103.5
	20	0.62	600	S+Al+Nd+Cl+B	88.1	125000	2.8	6.3	96.5	N.D
	30	0.62	600	S+B+(Al+Nd+Cl	64.8	39000	3.4	11.0	96.1	N.D

Note: isothermal polymerizations were performed in styrene at 60°C for 3.5 h;  mol;  mmol.
  polymerization was not possible in this way.
  at 60°C for 5 h;  mol;  mmol.
  system aged at 30°C for 3 min before use.
.
  by size exclusion chromatography (SEC) with polystyrene standards.
  content determined by ¹H NMR and cis-percentage determined by ¹³C NMR.
  by differential scanning calorimetry (DSC).
  determined.